Scientific Output

Over 10.000 scientific papers have been published by members of the Materials Chain since the foundation of the University Alliance Ruhr in 2010. This tremendous output is proof of the excellent environment the Ruhr Area provides for research in the field of materials science and technology.

Below, you can either scroll through the complete list of our annually published material, search for a specific author or term via the free text search, or use the interactive keyword cloud to get to know our research strengths. You can also review the publication record of every Materials Chain member via his or her personal member’s page.

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• 2022 • 253	A single-Pt-atom-on-Ru-nanoparticle electrocatalyst for CO-resilient methanol oxidation Poerwoprajitno, A.R. and Gloag, L. and Watt, J. and Cheong, S. and Tan, X. and Lei, H. and Tahini, H.A. and Henson, A. and Subhash, B. and Bedford, N.M. and Miller, B.K. and O’Mara, P.B. and Benedetti, T.M. and Huber, D.L. and Z... Nature Catalysis 5 231-237 (2022) Single Pt atom catalysts are key targets because a high exposure of Pt substantially enhances electrocatalytic activity. In addition, PtRu alloy nanoparticles are the most active catalysts for the methanol oxidation reaction. To combine the exceptional activity of single Pt atom catalysts with an active Ru support we must overcome the synthetic challenge of forming single Pt atoms on noble metal nanoparticles. Here we demonstrate a process that grows and spreads Pt islands on Ru branched nanoparticles to create single-Pt-atom-on-Ru catalysts. By following the spreading process by in situ TEM, we found that the formation of a stable single atom structure is thermodynamically driven by the formation of strong Pt–Ru bonds and the lowering of the surface energy of the Pt islands. The stability of the single-Pt-atom-on-Ru structure and its resilience to CO poisoning result in a high current density and mass activity for the methanol oxidation reaction over time. [Figure not available: see fulltext.] © 2022, The Author(s), under exclusive licence to Springer Nature Limited.
  	view abstract	doi: 10.1038/s41929-022-00756-9

• 2022 • 252	A thermo-viscoplasticity model for metals over wide temperature ranges- application to case hardening steel Oppermann, P. and Denzer, R. and Menzel, A. Computational Mechanics 69 541-563 (2022) In this contribution, a model for the thermomechanically coupled behaviour of case hardening steel is introduced with application to 16MnCr5 (1.7131). The model is based on a decomposition of the free energy into a thermo-elastic and a plastic part. Associated viscoplasticity, in terms of a temperature-depenent Perzyna-type power law, in combination with an isotropic von Mises yield function takes respect for strain-rate dependency of the yield stress. The model covers additional temperature-related effects, like temperature-dependent elastic moduli, coefficient of thermal expansion, heat capacity, heat conductivity, yield stress and cold work hardening. The formulation fulfils the second law of thermodynamics in the form of the Clausius–Duhem inequality by exploiting the Coleman–Noll procedure. The introduced model parameters are fitted against experimental data. An implementation into a fully coupled finite element model is provided and representative numerical examples are presented showing aspects of the localisation and regularisation behaviour of the proposed model. © 2021, The Author(s).
  	view abstract	doi: 10.1007/s00466-021-02103-4

• 2022 • 251	Ab initio investigations of point and complex defect structures in B2-FeAl Sözen, H.I. and Mendive-Tapia, E. and Hickel, T. and Neugebauer, J. Physical Review Materials 6 (2022) We study single-site and two-site defect structures in B2-type Fe-Al alloys by means of density functional theory supercell calculations. The defect formation energies are calculated as functions of the chemical potential, which are used to obtain the dependence of the defect concentrations on Al content at different temperatures. We also examine the converging behavior of the formation energies with respect to the supercell size to study the corresponding limit of dilute defects. The effect of magnetism is investigated by considering nonmagnetic, ferromagnetic, and paramagnetic states, calculations for the latter showing that the magnitude of the local magnetic moments strongly impacts the defect formation energies. The methodological studies are used to provide explanations for the wide spread of defect formation energies reported by experiments and other theoretical investigations. Based on these insights, the stability of the B2-FeAl structure as a function of Al concentration is obtained and discussed. © 2022 authors. Published by the American Physical Society.published article's title, journal citation, and DOI. Open access publication funded by the Max Planck Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.6.023603

• 2022 • 250	Chemical Affinity of Ag-Exchanged Zeolites for Efficient Hydrogen Isotope Separation Zhang, L. and Wulf, T. and Baum, F. and Schmidt, W. and Heine, T. and Hirscher, M. Inorganic Chemistry 61 9413-9420 (2022) We report an ion-exchanged zeolite as an excellent candidate for large-scale application in hydrogen isotope separation. Ag(I)-exchanged zeolite Y has been synthesized through a standard ion-exchange procedure. The D2/H2 separation performance has been systematically investigated via thermal desorption spectroscopy (TDS). Undercoordinated Ag+ in zeolite AgY acts as a strong adsorption site and adorbs preferentially the heavier isotopologue even above liquid nitrogen temperature. The highest D2/H2 selectivity of 10 is found at an exposure temperature of 90 K. Furthermore, the high Al content of the zeolite structure leads to a high density of Ag sites, resulting in a high gas uptake. In the framework, approximately one-third of the total physisorbed hydrogen isotopes are adsorbed on the Ag sites, corresponding to 3 mmol/g. A density functional theory (DFT) calculation reveals that the isotopologue-selective adsorption of hydrogen at Ag sites contributes to the outstanding hydrogen isotope separation, which has been directly observed through cryogenic thermal desorption spectroscopy. The overall performance of zeolite AgY, showing good selectivity combined with high gas uptake, is very promising for future technical applications. © 2022 The Authors.
  	view abstract	doi: 10.1021/acs.inorgchem.2c00028

• 2022 • 249	Combinatorial sputter deposition of CrMnFeCoNi high entropy alloy thin films on agitated particles Lourens, F. and Ludwig, Al. Surface and Coatings Technology 449 (2022) A method for combinatorial sputter deposition of thin films on microparticles is presented. The method is developed for a laboratory-scale magnetron sputter system and uses a piezoelectric actuator to agitate the microparticles through oscillation. Custom-made components enable to agitate up to nine separate batches of particles simultaneously. Due to the agitation, the whole surface of the particles can be exposed to the sputter flux and thus completely covered with a thin film. By sputtering a CrMnFeCoNi high entropy alloy target, separate batches of polystyrene microspheres (500 μm monodisperse diameter), Fe alloy particles (300 μm mean size) and NaCl salt particles (350 μm mean size) were simultaneously coated with a homogeneous thin film. In contrast, a CrMnFeCoNi thin film that was deposited on agglomerating Al particles (5 μm mean size) only partially covers the surface of the particles. By co-sputtering a CrMn, an FeCo and a Ni target, nine separate batches of Al particles (25 μm mean size) were coated with a CrMnFeCoNi thin film with a composition gradient. These depositions demonstrate the ability to coat different types of particles with uniform films (from elemental to multinary compositions) and to deposit films with composition gradients on uniform particles. © 2022 Elsevier B.V.
  	view abstract	doi: 10.1016/j.surfcoat.2022.128984

• 2022 • 248	Creating a Ferromagnetic Ground State with Tc Above Room Temperature in a Paramagnetic Alloy through Non-Equilibrium Nanostructuring Ye, X. and Fortunato, N. and Sarkar, A. and Geßwein, H. and Wang, D. and Chen, X. and Eggert, B. and Wende, H. and Brand, R.A. and Zhang, H. and Hahn, H. and Kruk, R. Advanced Materials (2022) Materials with strong magnetostructural coupling have complex energy landscapes featuring multiple local ground states, thus making it possible to switch among distinct magnetic-electronic properties. However, these energy minima are rarely accessible by a mere application of an external stimuli to the system in equilibrium state. A ferromagnetic ground state, with Tc above room temperature, can be created in an initially paramagnetic alloy by nonequilibrium nanostructuring. By a dealloying process, bulk chemically disordered FeRh alloys are transformed into a nanoporous structure with the topology of a few nanometer-sized ligaments and nodes. Magnetometry and Mössbauer spectroscopy reveal the coexistence of two magnetic ground states, a conventional low-temperature spin-glass and a hitherto-unknown robust ferromagnetic phase. The emergence of the ferromagnetic phase is validated by density functional theory calculations showing that local tetragonal distortion induced by surface stress favors ferromagnetic ordering. The study provides a means for reaching conventionally inaccessible magnetic states, resulting in a complete on/off ferromagnetic–paramagnetic switching over a broad temperature range. © 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.
  	view abstract	doi: 10.1002/adma.202108793

• 2022 • 247	Effect of laser shock peening without protective coating on the surface mechanical properties of NiTi alloy Wang, H. and Keller, S. and Chang, Y. and Kashaev, N. and Yan, K. and Gurevich, E.L. and Ostendorf, A. Journal of Alloys and Compounds 896 (2022) We study the effect of laser shock peening (LSP) without protective coating on the surface mechanical property of NiTi alloy. The Vickers microhardness and wear resistance are measured to determine the mechanical property of NiTi samples treated with different LSP parameters (3 J with 10 ns and 5 J with 20 ns). From the electron backscatter diffraction (EBSD) analysis, it can be found that the laser shock peening does not induce obvious grain refinement in the surface region of NiTi alloy. Both compressive and tensile residual stress in the top layer are determined using the hole drilling method. The results show that the LSP treatment without a protective coating increases the roughness and enhances the surface mechanical properties of NiTi alloy. © 2021 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jallcom.2021.163011

• 2022 • 246	Effects of Microstructure Modification by Friction Surfacing on Wear Behavior of Al Alloys with Different Si Contents Schütte, M.R. and Ehrich, J. and Linsler, D. and Hanke, S. Materials 15 (2022) In this work, Al alloys with 6.6%, 10.4%, and 14.6% Si were deposited as thick coatings by Friction Surfacing (FS), resulting in grain refinement and spheroidization of needle-shaped eutectic Si phase. Lubricated sliding wear tests were performed on a pin-on-disc tribometer using Al-Si alloys in as-cast and FS processed states as pins and 42CrMo4 steel discs. The chemical composition of the worn surfaces was analyzed by X-ray photoelectron spectroscopy (XPS). The wear mechanisms were studied by scanning electron microscopy (SEM) and focused ion beam (FIB), and the wear was evaluated by measuring the weight loss of the samples. For the hypoeutectic alloys, spheroidization of the Si phase particles in particular leads to a significant improvement in wear resistance. The needle-shaped Si phase in as-cast state fractures during the wear test and small fragments easily detach from the surface. The spherical Si phase particles in the FS state also break away from the surface, but to a smaller extent. No reduction in wear due to FS was observed for the hypereutectic alloy. Here, large bulky primary Si phase particles are already present in the as-cast state and do not change significantly during FS, providing high wear resistance in both material states. This study highlights the mechanisms and limitations of improved wear resistance of Si-rich Al alloys deposited as thick coatings by Friction Surfacing. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/ma15051641

• 2022 • 245	Elastic energy of multi-component solid solutions and strain origins of phase stability in high-entropy alloys Darvishi Kamachali, R. and Wang, L. Scripta Materialia 206 (2022) The elastic energy of mixing for multi-component solid solutions is derived by generalizing Eshelby's sphere-in-hole model. By surveying the dependence of the elastic energy on the chemical composition and lattice misfit, we derive a lattice strain coefficient λ*. Studying several high-entropy alloys and superalloys, we propose that most solid solution multi-component alloys are stable when λ*<0.16, generalizing the Hume-Rothery atomic-size rule for binary alloys. We also reveal that the polydispersity index δ, frequently used for describing strain in multi-component alloys, directly represents the elastic energy (e) with e=qδ2, q being an elastic constant. Furthermore, the effects of (i) the number and (ii) the atomic-size distribution of constituting elements on the phase stability of high-entropy alloys were quantified. The present derivations and discussions open for richer considerations of elastic effects in high-entropy alloys, offering immediate support for quantitative assessments of their thermodynamic properties and studying related strengthening mechanisms. © 2021
  	view abstract	doi: 10.1016/j.scriptamat.2021.114226

• 2022 • 244	Electrochemical dealloying in a magnetic field – Tapping the potential for catalyst and material design Rurainsky, C. and Nettler, D.-R. and Pahl, T. and Just, A. and Cignoni, P. and Kanokkanchana, K. and Tschulik, K. Electrochimica Acta 426 (2022) Nanocatalyst optimisation through electrochemical dealloying has been employed as a successful strategy to increase catalytic activity, while reducing the need for precious metals. We present here a new pathway to influence the electrochemical dealloying, through external homogeneous magnetic fields. A homogeneous magnetic field with a flux density of 450 mT in two orientations, parallel or perpendicular to the current direction, was used during electrochemical dealloying using cyclic voltammetry of AgAu nanoparticles. We found increased porosity for low dealloying cycle numbers and improved catalytic properties after longer cycling, compared to nanoparticles dealloyed in the absence of magnetic fields. These findings demonstrate that magnetic fields applied during electrochemical dealloying have currently untapped potential that can be used to influence material properties in a new way and give researchers another powerful tool for material design. © 2022
  	view abstract	doi: 10.1016/j.electacta.2022.140807

• 2022 • 243	Fatigue Assessment of Twin Wire Arc Sprayed and Machine Hammer-Peened ZnAl4 Coatings on S355 JRC+C Substrate Milz, M.P. and Wirtz, A. and Abdulgader, M. and Biermann, D. and Tillmann, W. and Walther, F. Materials 15 (2022) Structural elements for applications in maritime environments, especially offshore instal-lations, are subjected to various stresses, such as mechanical loads caused by wind or waves and corrosive attacks, e.g., by seawater, mist and weather. Thermally sprayed ZnAl coatings are often used for maritime applications, mainly due to good corrosion protection properties. Machine hammer peening (MHP) has the potential to increase fatigue and corrosion fatigue resistance of ZnAl coatings by adjusting various material properties such as hardness, porosity and roughness. This study investigates the fatigue behavior of twin wire arc sprayed and MHP post-treated ZnAl4 coat-ings. Unalloyed steel (S355 JRC+C) was selected as substrate material and tested as a reference. MHP achieved the desired improvements in material properties with increased hardness, decreased roughness and uniform coating thickness. Multiple and constant amplitude tests have been carried out to evaluate the fatigue capability of coating systems. In the high cycle fatigue regime, the addi-tional MHP post-treatment led to an improvement of the lifetime in comparison to pure sandblasted specimens. The surface was identified as a crack initiation point. ZnAl coating and MHP post-treat-ment are suitable to improve the fatigue behavior in the high cycle fatigue regime compared to uncoated specimens. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/ma15031182

• 2022 • 242	High-pressure CO, H2, CO2 and Ethylene Pulses Applied in the Hydrogenation of CO to Higher Alcohols over a Bulk Co-Cu Catalyst Telaar, P. and Schwiderowski, P. and Schmidt, S. and Stürmer, S. and Muhler, M. ChemCatChem 14 (2022) The reaction pathways of higher alcohol synthesis over a bulk Co−Cu catalyst (Co : Cu=2 : 1) were investigated by applying high-pressure pulse experiments as a surface-sensitive operando method at 280 °C and 60 bar. Using high-pressure CO and H2 pulses in a syngas flow with a H2:CO ratio of 1, it was shown that the surface of the working 2CoCu catalyst is saturated with adsorbed CO, but not with adsorbed atomic hydrogen, because only the H2 pulses increased the yields of all alcohols and alkanes. The reverse water gas shift reaction (WGSR) was investigated by pulsing CO2. The CO2 pulses poisoned the formation of methanol, ethanol, and 1-propanol, and the absence of significant CO and H2O responses indicates that the WGSR is not efficiently catalyzed by the applied 2CoCu catalyst excluding the presence of exposed Cu0 sites. A series of ethylene pulses showed that when a threshold mole fraction of ethylene of about 1 vol % is surpassed, 2CoCu is an active catalyst for the hydroformylation of ethylene to 1-propanol pointing to the presence of highly coordinatively unsaturated Co sites. © 2022 The Authors. ChemCatChem published by Wiley-VCH GmbH.
  	view abstract	doi: 10.1002/cctc.202200385

• 2022 • 241	Impact of local arrangement of Fe and Ni on the phase stability and magnetocrystalline anisotropy in Fe-Ni-Al Heusler alloys Sokolovskiy, V.V. and Miroshkina, O.N. and Buchelnikov, V.D. and Gruner, M.E. Physical Review Materials 6 (2022) On the basis of density functional calculations, we report on a comprehensive study of the influences of atomic arrangement and Ni substitution for Al on the ground-state structural and magnetic properties for Fe2Ni1+xAl1-x Heusler alloys. We discuss systematically the competition between five Heusler-type structures formed by shuffles of Fe and Ni atoms and their thermodynamic stability. All Ni-rich Fe2Ni1+xAl1-x tend to decompose into a dual-phase mixture consisting of Fe2NiAl and FeNi. The successive replacement of Ni by Al leads to a change of ground-state structure and eventually an increase in magnetocrystalline anisotropy energy (MAE). We predict for stoichiometric Fe2NiAl a ground-state structure with nearly cubic lattice parameters but alternating layers of Fe and Ni possessing a uniaxial MAE that is even larger than tetragonal L10-FeNi. This opens an alternative route for improving the phase stability and magnetic properties in FeNi-based permanent magnets. © 2022 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.6.025402

• 2022 • 240	Incorporation of Cu/Ni in Ordered Mesoporous Co-Based Spinels to Facilitate Oxygen Evolution and Reduction Reactions in Alkaline Media and Aprotic Li−O2 Batteries Priamushko, T. and Budiyanto, E. and Eshraghi, N. and Weidenthaler, C. and Kahr, J. and Jahn, M. and Tüysüz, H. and Kleitz, F. ChemSusChem 15 (2022) Ordered mesoporous CuNiCo oxides were prepared via nanocasting with varied Cu/Ni ratio to establish its impact on the electrochemical performance of the catalysts. Physicochemical properties were determined along with the electrocatalytic activities toward oxygen evolution/reduction reactions (OER/ORR). Combining Cu, Ni, and Co allowed creating active and stable bifunctional electrocatalysts. CuNiCo oxide (Cu/Ni≈1 : 4) exhibited the highest current density of 411 mA cm−2 at 1.7 V vs. reversible hydrogen electrode (RHE) and required the lowest overpotential of 312 mV to reach 10 mA cm−2 in 1 m KOH after 200 cyclic voltammograms. OER measurements were also conducted in the purified 1 m KOH, where CuNiCo oxide (Cu/Ni≈1 : 4) also outperformed NiCo oxide and showed excellent chemical and catalytic stability. For ORR, Cu/Ni incorporation provided higher current density, better kinetics, and facilitated the 4e− pathway of the oxygen reduction reaction. The tests in Li−O2 cells highlighted that CuNiCo oxide can effectively promote ORR and OER at a lower overpotential. © 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH
  	view abstract	doi: 10.1002/cssc.202102404

• 2022 • 239	Influence of a Partial Substitution of Co by Fe on the Phase Stability and Fatigue Behavior of a CoCrWC Hard Alloy at Room Temperature Brackmann, L. and Schuppener, J. and Röttger, A. and Weber, S. Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 53 2708-2723 (2022) The deformation-induced phase transition from fcc to hcp causes local embrittlement of the metal matrix in Cobalt-base alloys, facilitating subcritical crack growth under cyclic loading and reducing fatigue resistance. Our approach to increasing the fatigue life of Co-based hard alloys is to suppress the phase transition from fcc to hcp by an alloy modification that increases the stacking fault energy (SFE) of the metal matrix. Therefore, we substitute various contents (15, 25, and 35 mass pct) of Co by Fe and analyze the effect on the fatigue life and resistance against subcritical crack growth. Subcritical crack growth in the specimens takes place in a cyclic load test. The proceeding crack growth and the occurrence of phase transformations are monitored by scanning electron microscope (SEM) investigations and electron backscatter diffraction (EBSD). We determined an SFE of 35 mJ/m2 at an iron content of 35 mass pct, which leads to a change of the main deformation mechanism from deformation-induced martensitic transformation to deformation twinning. Analysis of cyclically loaded specimens revealed that the resistance against subcritical crack growth in the metal matrix is facilitated with increasing Fe content, leading to a significant increase in fatigue life. © 2022, The Author(s).
  	view abstract	doi: 10.1007/s11661-022-06700-7

• 2022 • 238	Integration of Hot Isostatic Pressing and Heat Treatment for Advanced Modified γ-TiAl TNM Alloys Bernal, D. and Chamorro, X. and Hurtado, I. and Lopez-Galilea, I. and Bürger, D. and Weber, S. and Madariaga, I. Materials 15 (2022) The conventional processing route of TNM (Ti-Nb-Mo) alloys combines casting and Hot Isostatic Pressing (HIP) followed by forging and multiple heat treatments to establish optimum properties. This is a time-consuming and costly process. In this study we present an advanced alternative TNM alloy processing route combining HIP and heat treatments into a single process, which we refer to as IHT (integrated HIP heat treatment), applied to a modified TNM alloy with 1.5B. A Quintus HIP lab unit with a quenching module was used, achieving fast and controlled cooling, which differs from the slow cooling rates of conventional HIP units. A Ti-42.5Al-3.5Nb-1Mo-1.5B (at.%) was subjected to an integrated two HIP steps at 200 MPa, one at 1250◦ C for 3 h and another at 1260◦ C for 1 h, both under a protective Ar atmosphere and followed by cooling at 30 K/min down to room temperature. The results were compared against the Ti-43.5Al-3.5Nb-1Mo-0.8B (at.%) thermomechanically processed in a conventional way. Applying IHT processing to the 1.5B alloy does indeed achieve good creep strength, and the secondary creep rate of the IHT processed materials is similar to that of conventionally forged TNM alloys. Thus, the proposed advanced IHT processing route could manufacture more cost-effective TiAl components. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/ma15124211

• 2022 • 237	Linear growth of reaction layer during in-situ TEM annealing of thin film Al/Ni diffusion couples Kostka, A. and Naujoks, D. and Oellers, T. and Salomon, S. and Somsen, C. and Öztürk, E. and Savan, A. and Ludwig, A. and Eggeler, G. Journal of Alloys and Compounds 922 (2022) During reactive layer growth in binary diffusion couples new phases can nucleate and grow. In the present work we perform in- and ex-situ interdiffusion studies in the system Ni-Al using X-ray diffraction (XRD) and analytical transmission electron microscopy (TEM). We investigate the reaction between 270 °C and 500 °C. We show that in the early stages of the solid-state reaction a small polycrystalline aluminide layer forms, while preferential grain growth follows in the later stage. In the reaction layer we detect the presence of Al3Ni by XRD and electron diffraction. Local chemical analysis by EDX in the TEM suggests that a second aluminide phase forms simultaneously. An in-situ TEM study at 380 °C shows layer growth of about 0.042 nm/s with a linear time dependence. We interpret this rate law on the basis of an interface-controlled reaction and discuss our results in the light of what is known about layer growth in thin film diffusion couples (presence/absence of predicted phases, linear/parabolic rate laws) and in view of results from the Ni-Al system published in the literature. Areas in need of further work are identified. © 2022 The Authors
  	view abstract	doi: 10.1016/j.jallcom.2022.165926

• 2022 • 236	MEAM interatomic potentials of Ni, Re, and Ni-Re alloys for atomistic fracture simulations Alam, M. and Lymperakis, L. and Groh, S. and Neugebauer, J. Modelling and Simulation in Materials Science and Engineering 30 (2022) Second nearest neighbor modified embedded atom method (2NN-MEAM) interatomic potentials are developed for the Ni, Re, and Ni-Re binaries. To construct the potentials, density functional theory (DFT) calculations have been employed to calculate fundamental physical properties that play a dominant role in fracture. The potentials are validated to accurately reproduce material properties that correlate with material's fracture behavior. The thus constructed potentials were applied to perform large scale simulations of mode I fracture in Ni and Ni-Re binaries with low Re content. Substitutional Re did not alter the ductile nature of crack propagation, though it resulted in a monotonous increase of the critical stress intensity factor with Re content. © 2021 The Author(s). Published by IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-651X/ac3a15

• 2022 • 235	Microstructural and Tribo-mechanical Properties of Arc-Sprayed CoCr-Based Coatings Hagen, L. and Paulus, M. and Tillmann, W. Journal of Thermal Spray Technology 31 2229-2242 (2022) Due to their superior wear and oxidation resistance, Stellite™ coatings are widely used in industrial applications, where the coatings are exposed to high temperature. Common processes for applying Stellite™ coatings include the high-velocity oxy-fuel spraying, laser cladding, and plasma transferred arc welding. Although Stellite™ welding consumables or similar welding consumables in the form of cored wires (CoCr base without industrial property rights) are commercially available, there are hardly any studies on arc-sprayed Stellite™ coatings available in the literature. In this study, the microstructural characteristics of arc-sprayed deposits were investigated, which were produced using a CoCr-based cored wire with addition of 4.5 wt.% tungsten. The produced deposits were examined in its as-sprayed state as well as after exposed to elevated temperatures. The microstructure was scrutinized by means of electron microscopy, energy-dispersive x-ray spectroscopy, as well as x-ray diffraction analyses using synchrotron radiation. Tribo-mechanical tests were conducted in order to assess the performance of the arc-sprayed coating. The findings were discussed and compared to those obtained from conventional CoCr-based coatings. It was found that the arc-sprayed CoCr-based coating is predominantly composed of Co-rich, Cr-rich lamellae or lamellae comprising a Co(Cr)-rich solid solution interspersed with various oxides between the individual lamellae. Solid solution hardening serves as dominant strengthening mechanism, while precipitation hardening effects are hardly evident. With regard to the oxidation behaviour, the as-sprayed coating mainly contains CoCr2O4 as well as traces of Co3O4. For heating above 550 °C, coating surface additionally consists of Fe2O3 and Co3O4. In dry sliding experiments, the arc-sprayed CoCr-based coating shows a decreased wear resistance compared to CoCr-based coatings processed by HVOF and PTA, whereas the coefficient of friction (COF) sliding against alumina was similar to the COF observed for the HVOF-sprayed CoCr-based coating, but lower than the COF obtained for the CoCr-based hardfacing alloy deposited by PTA. © 2022, The Author(s).
  	view abstract	doi: 10.1007/s11666-022-01440-x

• 2022 • 234	Microstructure analysis and mechanical properties of electron beam powder bed fusion (PBF-EB)-manufactured γ-titanium aluminide (TiAl) at elevated temperatures Kotzem, D. and Teschke, M. and Juechter, V. and Körner, C. and Walther, F. Materialpruefung/Materials Testing 64 636-646 (2022) Additively manufactured γ-titanium aluminide has a high specific strength and temperature resistance. This opens new possibilities for future lightweight constructions for aerospace applications. The objective of this work was to characterize additively manufactured Ti-48Al-2Cr-2Nb alloy specimens, which were successfully manufactured by electron beam powder bed fusion. For microstructural characterization, the as-built state was investigated with light and scanning electron microscopy. In the electron backscatter diffraction analysis, the size and the orientation of the grains were observed. The pore size and distribution were examined in computer tomographic scans, which showed a near fully dense material with a relative density of >99.9%. Furthermore, the hardness curve over the building height was examined in hardness mappings. Thereby, a strong decrease in hardness could be observed with an increase in part height. To evaluate the reliability of the manufactured alloy, quasi-static compression tests were carried out at temperatures up to 650 °C. Within these tests, a high compression strength (σc,p,0.2,650 °C = 684 MPa) was determined, which implicated a potential substitution of nickel-based superalloy components in aerospace applications under compressive loads. © 2022 Walter de Gruyter GmbH, Berlin/Boston.
  	view abstract	doi: 10.1515/mt-2021-2137

• 2022 • 233	Microstructure and residual stress evolution in nanocrystalline Cu-Zr thin films Chakraborty, J. and Oellers, T. and Raghavan, R. and Ludwig, A. and Dehm, G. Journal of Alloys and Compounds 896 (2022) Grazing incidence X-ray diffraction (GIXRD) and scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) were employed to study the microstructure evolution and stress development in the nanocrystalline Cu100−X-ZrX (2.5 at% ≤ x ≤ 5.5 at%) alloy thin films. Small Zr additions to Cu led to significant lattice parameter anisotropy in the as-deposited Cu-Zr thin films both due to macroscopic lattice strain and stacking faults in the Cu matrix. Strain free lattice parameters obtained after the XRD stress analysis of Cu-Zr thin films confirmed formation of a supersaturated substitutional Cu-Zr solid solution. For the first time, the study of film microstructure by XRD line profile analysis (XLPA) confirmed progressive generation of dislocations and planar faults with increasing Zr composition in Cu-Zr alloy films. These microstructural changes led to the generation of tensile stresses in the thin films along with considerable stress gradients across the films thicknesses which are quantified by the traditional dψhkl−Sin2ψ and GIXRD stress measurement methods. The origin of tensile stresses and stress gradients in the Cu-Zr film are discussed on the basis of film growth and heterogeneous microstructure with changing Zr composition. © 2021
  	view abstract	doi: 10.1016/j.jallcom.2021.162799

• 2022 • 232	Pseudoelastic cycling of ultra-fine-grained NiTi shape-memory wires Yawny, A. and Sade, M. and Eggeler, G. International Journal of Materials Research 96 608-618 (2022) In the present study, we investigate pseudoelastic pull-pull cycling of ultra-fine-grained (40 nm) Ni-rich (50.9 at.% Ni) NiTi shape-memory wires at temperatures ranging from 301 to 323 K. Strain-controlled experiments were performed using incremental strain steps and different constant maximum strains. Pull-pull cycling results in decreasing/increasing plateau stresses characterizing the forward/reverse transformations and an accumulation of non-recoverable strain. Saturation is reached after 30 cycles. We interpret our results in terms of a microstructural scenario where dislocations, which are introduced during the martensitic transformation (lattice invariant shear) and during pull-pull cycling (dislocation plasticity), interact with the stress-induced formation of martensite. We show that the slopes of stress-strain curves naturally depend on the total strain imposed in strain-controlled testing. We also provide a dislocation-based explanation for the evolving stress levels of the loading and unloading plateaus during pseudoelastic cycling. And most importantly, we show how dislocations act as microstructural markers which allow the material to remember its previous stress-strain history. © 2005 Carl Hanser Verlag, München.
  	view abstract	doi: 10.3139/ijmr-2005-0108

• 2022 • 231	Revealing in-plane grain boundary composition features through machine learning from atom probe tomography data Zhou, X. and Wei, Y. and Kühbach, M. and Zhao, H. and Vogel, F. and Darvishi Kamachali, R. and Thompson, G.B. and Raabe, D. and Gault, B. Acta Materialia 226 (2022) Grain boundaries (GBs) are planar lattice defects that govern the properties of many types of polycrystalline materials. Hence, their structures have been investigated in great detail. However, much less is known about their chemical features, owing to the experimental difficulties to probe these features at the atomic length scale inside bulk material specimens. Atom probe tomography (APT) is a tool capable of accomplishing this task, with an ability to quantify chemical characteristics at near-atomic scale. Using APT data sets, we present here a machine-learning-based approach for the automated quantification of chemical features of GBs. We trained a convolutional neural network (CNN) using twenty thousand synthesized images of grain interiors, GBs, or triple junctions. Such a trained CNN automatically detects the locations of GBs from APT data. Those GBs are then subjected to compositional mapping and analysis, including revealing their in-plane chemical decoration patterns. We applied this approach to experimentally obtained APT data sets pertaining to three case studies, namely, Ni-P, Pt-Au, and Al-Zn-Mg-Cu alloys. In the first case, we extracted GB specific segregation features as a function of misorientation and coincidence site lattice character. Secondly, we revealed interfacial excesses and in-plane chemical features that could not have been found by standard compositional analyses. Lastly, we tracked the temporal evolution of chemical decoration from early-stage solute GB segregation in the dilute limit to interfacial phase separation, characterized by the evolution of complex composition patterns. This machine-learning-based approach provides quantitative, unbiased, and automated access to GB chemical analyses, serving as an enabling tool for new discoveries related to interface thermodynamics, kinetics, and the associated chemistry-structure-property relations. © 2022 The Authors
  	view abstract	doi: 10.1016/j.actamat.2022.117633

• 2022 • 230	Simultaneous Multi-Property Probing During Magneto-Structural Phase Transitions: An Element-Specific and Macroscopic Hysteresis Characterization at ID12 of the ESRF Aubert, A. and Skokov, K. and Gomez, G. and Chirkova, A. and Radulov, I. and Wilhelm, F. and Rogalev, A. and Wende, H. and Gutfleisch, O. and Ollefs, K. IEEE Transactions on Instrumentation and Measurement 71 (2022) We present a new instrument for advanced magnetic studies based on the high field X-ray magnetic circular dichroism (XMCD) end-station developed at the beamline ID12 of the European Synchrotron Radiation Facility (ESRF, Grenoble, France). It offers a unique possibility to measure simultaneously element-specific and macroscopic properties related to magnetic, electronic, and structural degrees of freedom of magnetic materials. Under strictly the same experimental conditions, one can measure the XMCD response, macroscopic magnetization, volume changes, and caloric properties of a magnetic material as a function of magnetic field (up to 17 T) and temperature (5-325 K). To illustrate the performance of this new instrument, we present a case study of an equiatomic FeRh alloy across the first-order magneto-structural transition. This development is the first step toward a new fully dedicated end-station based on a 7 T split-coil superconducting magnet with an additional capability to perform X-ray diffraction experiments. © 1963-2012 IEEE.
  	view abstract	doi: 10.1109/TIM.2022.3157001

• 2022 • 229	Strain rate dependent deformation behavior of BCC-structured Ti29Zr24Nb23Hf24 high entropy alloy at elevated temperatures Cao, T. and Guo, W. and Lu, W. and Xue, Y. and Lu, W. and Su, J. and Liebscher, C.H. and Li, C. and Dehm, G. Journal of Alloys and Compounds 891 (2022) The mechanical behavior and deformation mechanisms of a body-centered cubic (BCC) Ti29Zr24Nb23Hf24 (at%) high entropy alloy (HEA) was investigated in temperatures and strain rates from 700° to 1100 °C and 10−3 to 10 s−1, respectively. The HEA exhibits a substantial increase in yield stress with increasing strain rate. The strain rate sensitivity (SRS) coefficient is ~3 times that of BCC alloy Nb-1Zr and even ~3.5 times that of pure Nb. This high SRS is attributed to the high Peierls stress of the HEA, which is about twice the Peierls stress of pure Nb. On the other hand, the flow stress exhibits a tendency from strain softening to strain hardening with the increase of strain rate especially at the relatively low temperatures. This behavior is explained by a change in dislocation motion from climbing to multiple slip with the increase of strain rate. Taking the specimen subjected to 800 ºC for example, dislocation walls formed at the early stage of deformation and at low strain rate of 10−3 s−1. In this case there is sufficient time to activate dislocations climb, which results in discontinuous dynamic recrystallization, and strain softening. However, when the strain rate amounts to 1 s−1, thermally activated processes such as dislocation climb are too sluggish. As a consequence, multiple slip systems are activated, and the dislocation interactions lead to the evolution of deformation bands, leading to strain hardening. © 2021 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jallcom.2021.161859

• 2022 • 228	Systematic in-depth study on material constitutive parameter identification for numerical cutting simulation on 16MnCr5 comparing temperature-coupled and uncoupled Split Hopkinson pressure bars Saelzer, J. and Thimm, B. and Zabel, A. Journal of Materials Processing Technology 302 (2022) A comprehensive systematic comparative study on high-strain-rate tests (Split Hopkinson Pressure Bar), with and without in-situ heating of the specimens and their respective influence on the quality of empirical material models is presented. The determination of material constitutive model parameters is one of the most challenging aspects of the modelling and simulation of machining processes. Chip formation and process forces show a significant dependence on the actual constitutive model and its parameters as well as on the testing method. Typically, the influences of strain, strain rate, and temperature are investigated in separate experiments of quasi-static compression tests and tests, because the most widespread phenomenological constitutive material models (e.g. Johnson–Cook model) neglect interactions between temperature and strain rate. In contrast, the presented work demonstrates, that a coupled experimental approach of strain rate and temperature in the same test increases the quality of such uncoupled material models as well. The authors compared both approaches (separated and in situ temperature-dependent experiments) by determining the constitutive model parameters for AISI 5115 steel samples taken from a single material batch. The parameters are calculated based on a covariance matrix adaptation evolution strategy and applied in identical two-dimensional orthogonal FEM cutting simulations. Process forces and chip thickness values were used for comparison with the machining experiments. The work therefore gives new aspects to decide for a suitable experimental approach when calibrating a constitutive equation. © 2022 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jmatprotec.2021.117478

• 2022 • 227	Unravelling the lamellar size-dependent fracture behavior of fully lamellar intermetallic γ-TiAl Neogi, A. and Janisch, R. Acta Materialia 227 (2022) Strengthening of metals by incorporating nano-scale coherent twin boundaries is one of the important breakthroughs of recent years in overcoming the strength-ductility trade-off. To this effect, also twin boundaries in nano-lamellar lightweight Ti-Al alloys promise a great potential, but their contribution to the deformation and fracture behavior needs to be better understood for designing optimal microstructures. To this end, we carry out linear elastic fracture mechanics informed large-scale atomistic simulations of fully lamellar microstructures consisting of the so-called ”true twin” boundaries in γ-TiAl. We find that nano-scale lamellae are not only effective in improving the fracture toughness and crack growth resistance, but also that the lamellar size controls the crack tip mechanisms. We identify a critical lamella thickness in the region between 1.64 and 3.04 nm, above which the crack tip events are primarily dislocation-based plasticity and the critical fracture initiation toughness exhibits an increasing trend with decreasing lamella size. Below the critical thickness, a decline in fracture toughness is observed and the crack tip propagation mechanisms are quasi-brittle in nature, i.e. the cleavage of atomic bonds at the crack tip is accompanied by plasticity events, such as twin-boundary migration and dislocation nucleation. A layer-wise analysis of the unstable stacking fault energy, the energy barrier for dislocation nucleation, that the critical thickness is of a similar value as the distance from the twin boundary at which bulk properties are restored. © 2022
  	view abstract	doi: 10.1016/j.actamat.2022.117698

• 2022 • 226	Weak itinerant magnetic phases of La2Ni7 Wilde, J.M. and Sapkota, A. and Tian, W. and Bud'Ko, S.L. and Ribeiro, R.A. and Kreyssig, A. and Canfield, P.C. Physical Review B 106 (2022) La2Ni7 is an intermetallic compound that is thought to have itinerant magnetism with small moment (∼0.15μB/Ni) ordering below 65 K. A recent study of single crystal samples by Ribeiro et al. [Phys. Rev. B 105, 014412 (2022)2469-995010.1103/PhysRevB.105.014412] determined detailed anisotropic H-T phase diagrams and revealed three zero-field magnetic phase transitions at T1∼61.0 K, T2∼56.5 K, and T3∼42 K. In that study only the highest temperature phase is shown to have a clear ferromagnetic component. Here we present a single crystal neutron diffraction study determining the propagation vector and magnetic moment direction of the three magnetically ordered phases, two incommensurate and one commensurate, as a function of temperature. The higher temperature phases have similar, incommensurate propagation vectors, but with different ordered moment directions. At lower temperatures, the magnetic order becomes commensurate with magnetic moments along the c direction as part of a first-order magnetic phase transition. We find that the low-temperature commensurate magnetic order is consistent with a proposal from earlier DFT calculations. © 2022 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.106.075118

• 2021 • 225	3d transition-metal high-entropy Invar alloy developed by adjusting the valence-electron concentration Rao, Z. and Cąklr, A. and Özgün, Ö. and Ponge, D. and Raabe, D. and Li, Z. and Acet, M. Physical Review Materials 5 (2021) By considering the valence-electron concentration of 3d transition-metal alloys and compounds, we develop 3d high-entropy alloy Mn12.1Fe34.2Co33.5Ni12.3Cu7.9 with 8.7 electrons per atom, which is identical to that of Fe65Ni35 Invar. We carry out X-ray diffraction, scanning electron microscopy, magnetization, thermal expansion, and elastic modulus measurements, by which we show that the HEA alloy indeed carries Invar properties. This is evidenced particularly by the observed spontaneous volume magnetostriction and the lattice softening covering a broad temperature-range around the ferromagnetic Curie temperature. © 2021 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.5.044406

• 2021 • 224	A combined experimental and first-principles based assessment of finite-temperature thermodynamic properties of intermetallic al3sc Gupta, A. and Tas, B. and Korbmacher, D. and Dutta, B. and Neitzel, Y. and Grabowski, B. and Hickel, T. and Esin, V. and Divinski, S.V. and Wilde, G. and Neugebauer, J. Materials 14 (2021) We present a first-principles assessment of the finite-temperature thermodynamic properties of the intermetallic Al3Sc phase including the complete spectrum of excitations and compare the theoretical findings with our dilatometric and calorimetric measurements. While significant electronic contributions to the heat capacity and thermal expansion are observed near the melting temperature, anharmonic contributions, and electron–phonon coupling effects are found to be relatively small. On the one hand, these accurate methods are used to demonstrate shortcomings of empirical predictions of phase stabilities such as the Neumann–Kopp rule. On the other hand, their combination with elasticity theory was found to provide an upper limit for the size of Al3Sc nanoprecipitates needed to maintain coherency with the host matrix. The chemo-mechanical coupling being responsible for the coherency loss of strengthening precipitates is revealed by a combination of state-of-the-art simulations and dedicated experiments. These findings can be exploited to fine-tune the microstructure of Al-Sc-based alloys to approach optimum mechanical properties. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/ma14081837

• 2021 • 223	A thermodynamically consistent modelling framework for strongly time-dependent bainitic phase transitions Bartel, T. and Geuken, G.-L. and Menzel, A. International Journal of Solids and Structures 232 (2021) In this work, a thermodynamically consistent constitutive framework is introduced that is capable of reproducing the significant time-dependent behaviour of austenite-to-bainite phase transformations. In particular, the aim is to incorporate the effect of these diffusion-controlled processes by plasticity-like evolution equations instead of incorporating related global diffusion equations. To this end, a variational principle for inelastic solids is adopted and enhanced by an additional term. This term essentially contributes to the evolution equations for the phase volume fractions of several crystallography-based bainite variants. Due to the specific modifications, special attention has to be paid with respect to the fulfilment of thermodynamical consistency, which can be shown to be unconditionally satisfied for the newly proposed modelling framework. The phase transformation model itself is based on the convexification of a multi-well energy density landscape in order to provide the effective material response for possible phase mixtures. Several material parameters are determined via parameter identification based on available experimental results for 51CrV4, which also allow the quantitative evaluation of the predicted results. © 2021 The Authors
  	view abstract	doi: 10.1016/j.ijsolstr.2021.111172

• 2021 • 222	Ab initio based models for temperature-dependent magnetochemical interplay in bcc Fe-Mn alloys Schneider, A. and Fu, C.-C. and Waseda, O. and Barreteau, C. and Hickel, T. Physical Review B 103 (2021) Body-centered cubic (bcc) Fe-Mn systems are known to exhibit a complex and atypical magnetic behavior from both experiments and 0 K electronic-structure calculations, which is due to the half-filled 3d band of Mn. We propose effective interaction models for these alloys, which contain both atomic-spin and chemical variables. They were parameterized on a set of key density functional theory (DFT) data, with the inclusion of noncollinear magnetic configurations being indispensable. Two distinct approaches, namely a knowledge-driven and a machine-learning approach have been employed for the fitting. Employing these models in atomic Monte Carlo simulations enables the prediction of magnetic and thermodynamic properties of the Fe-Mn alloys, and their coupling, as functions of temperature. This includes the decrease of Curie temperature with increasing Mn concentration, the temperature evolution of the mixing enthalpy, and its correlation with the alloy magnetization. Also, going beyond the defect-free systems, we determined the binding free energy between a vacancy and a Mn atom, which is a key parameter controlling the atomic transport in Fe-Mn alloys. © 2021 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.103.024421

• 2021 • 221	Application of nanoindentation technique to test surface hardness and residual stress of NiTi alloy after femtosecond laser shock peening Wang, H. and Gurevich, E.L. and Ostendorf, A. Proceedings of SPIE - The International Society for Optical Engineering 11679 (2021) Laser shock peening is a new and important surface treatment technique that can enhance the mechanical properties of metal materials. Normally, the nanosecond laser with pulse-width between 5 ns and 20 ns is used to induce a high-pressure shock wave that can generate plastic deformation in the top layer of metals. The femtosecond laser shock peening in the air has been studied recently, which can induce higher pressure shock wave than that of traditional nanosecond laser shock peening in a very short time. The NiTi alloy is processed by femtosecond laser shock peening, then a nanoindentation device is used to measure its surface hardness and residual stress. The hardness results of NiTi alloy before and after treatment show that the femtosecond laser shock peening can increase the hardness of NiTi alloy, which also shows that the femtosecond laser can be used to perform laser shock peening on NiTi alloy without coating. © 2021 SPIE.
  	view abstract	doi: 10.1117/12.2593092

• 2021 • 220	Bayesian Optimization of High-Entropy Alloy Compositions for Electrocatalytic Oxygen Reduction** Pedersen, J.K. and Clausen, C.M. and Krysiak, O.A. and Xiao, B. and Batchelor, T.A.A. and Löffler, T. and Mints, V.A. and Banko, L. and Arenz, M. and Savan, A. and Schuhmann, W. and Ludwig, Al. and Rossmeisl, J. Angewandte Chemie - International Edition 60 24144-24152 (2021) Active, selective and stable catalysts are imperative for sustainable energy conversion, and engineering materials with such properties are highly desired. High-entropy alloys (HEAs) offer a vast compositional space for tuning such properties. Too vast, however, to traverse without the proper tools. Here, we report the use of Bayesian optimization on a model based on density functional theory (DFT) to predict the most active compositions for the electrochemical oxygen reduction reaction (ORR) with the least possible number of sampled compositions for the two HEAs Ag-Ir-Pd-Pt-Ru and Ir-Pd-Pt-Rh-Ru. The discovered optima are then scrutinized with DFT and subjected to experimental validation where optimal catalytic activities are verified for Ag–Pd, Ir–Pt, and Pd–Ru binary alloys. This study offers insight into the number of experiments needed for optimizing the vast compositional space of multimetallic alloys which has been determined to be on the order of 50 for ORR on these HEAs. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
  	view abstract	doi: 10.1002/anie.202108116

• 2021 • 219	Calibrating SECCM measurements by means of a nanoelectrode ruler. The intrinsic oxygen reduction activity of PtNi catalyst nanoparticles Tetteh, E.B. and Löffler, T. and Tarnev, T. and Quast, T. and Wilde, P. and Aiyappa, H.B. and Schumacher, S. and Andronescu, C. and Tilley, R.D. and Chen, X. and Schuhmann, W. Nano Research (2021) Scanning electrochemical cell microscopy (SECCM) is increasingly applied to determine the intrinsic catalytic activity of single electrocatalyst particle. This is especially feasible if the catalyst nanoparticles are large enough that they can be found and counted in post-SECCM scanning electron microscopy images. Evidently, this becomes impossible for very small nanoparticles and hence, a catalytic current measured in one landing zone of the SECCM droplet cannot be correlated to the exact number of catalyst particles. We show, that by introducing a ruler method employing a carbon nanoelectrode decorated with a countable number of the same catalyst particles from which the catalytic activity can be determined, the activity determined using SECCM from many spots can be converted in the intrinsic catalytic activity of a certain number of catalyst nanoparticles.[Figure not available: see fulltext.] © 2021, The Author(s).
  	view abstract	doi: 10.1007/s12274-021-3702-7

• 2021 • 218	Comparing Direct and Pulsed-Direct Current Electrophoretic Deposition on Neural Electrodes: Deposition Mechanism and Functional Influence Ramesh, V. and Rehbock, C. and Giera, B. and Karnes, J.J. and Forien, J.-B. and Angelov, S.D. and Schwabe, K. and Krauss, J.K. and Barcikowski, S. Langmuir 37 9724-9734 (2021) Electrophoretic deposition (EPD) of platinum nanoparticles (PtNPs) on platinum-iridium (Pt-Ir) neural electrode surfaces is a promising strategy to tune the impedance of electrodes implanted for deep brain stimulation in various neurological disorders such as advanced Parkinson's disease and dystonia. However, previous results are contradicting as impedance reduction was observed on flat samples while in three-dimensional (3D) structures, an increase in impedance was observed. Hence, defined correlations between coating properties and impedance are to date not fully understood. In this work, the influence of direct current (DC) and pulsed-DC electric fields on NP deposition is systematically compared and clear correlations between surface coating homogeneity and in vitro impedance are established. The ligand-free NPs were synthesized via pulsed laser processing in liquid, yielding monomodal particle size distributions, verified by analytical disk centrifugation (ADC). Deposits formed were quantified by UV-vis supernatant analysis and further characterized by scanning electron microscopy (SEM) with semiautomated interparticle distance analyses. Our findings reveal that pulsed-DC electric fields yield more ordered surface coatings with a lower abundance of particle assemblates, while DC fields produce coatings with more pronounced aggregation. Impedance measurements further highlight that impedance of the corresponding electrodes is significantly reduced in the case of more ordered coatings realized by pulsed-DC depositions. We attribute this phenomenon to the higher active surface area of the adsorbed NPs in homogeneous coatings and the reduced particle-electrode electrical contact in NP assemblates. These results provide insight for the efficient EPD of bare metal NPs on micron-sized surfaces for biomedical applications in neuroscience and correlate coating homogeneity with in vitro functionality. © 2021 American Chemical Society.
  	view abstract	doi: 10.1021/acs.langmuir.1c01081

• 2021 • 217	Correlating the Synthesis, Structure, and Catalytic Performance of Pt-Re/TiO2for the Aqueous-Phase Hydrogenation of Carboxylic Acid Derivatives Haus, M.O. and Meledin, A. and Leiting, S. and Louven, Y. and Roubicek, N.C. and Moos, S. and Weidenthaler, C. and Weirich, T.E. and Palkovits, R. ACS Catalysis 11 5119-5134 (2021) Pt-Re bimetallic catalysts have many applications, ranging from catalytic reforming to the reduction of carboxylic acid derivatives. However, the exact role of Re in these systems has remained a matter of discussion, partly due to the plethora of suggested synthesis protocols and analysis conditions. This study presents an extensive comparison of such literature protocols and the resulting materials. In detail, characterization by N2 physisorption, X-ray diffraction, temperature-programmed reduction, CO pulse chemisorption, Fourier-transform infrared spectroscopy of adsorbed CO, scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy, and in situ X-ray photoelectron spectroscopy is combined with catalytic testing to yield synthesis-structure-activity correlations. Accordingly, the investigated catalysts share common features, such as Pt0 nanoparticles (1-4 nm) decorated with partially reduced Re species (ReOx-y). The remaining rhenium oxide is spread over the TiO2 support and enhances Pt dispersion in sequential impregnation protocols. While differences in the number of active sites (Pt0/ReOx-y) mostly explain catalytic results, small variations in the extent of Re reduction and site composition cause additional modulations. The optimal bimetallic catalyst outperforms Ru/C (previous benchmark) in the reduction of N-(2-hydroxyethyl)succinimide, an important step in the production of a bio-based polyvinylpyrrolidone polymer. © 2021 American Chemical Society. All rights reserved.
  	view abstract	doi: 10.1021/acscatal.0c05612

• 2021 • 216	CrMnFeCoNi high entropy alloys with carbon and nitrogen: mechanical properties, wear and corrosion resistance Chmielak, L. and Mujica Roncery, L. and Niederhofer, P. and Weber, S. and Theisen, W. SN Applied Sciences 3 (2021) The use of interstitial elements has been a key factor for the development of different kinds of steels. However, this aspect has been little explored in the field of high entropy alloys (HEAs). In this investigation, the effect of carbon and nitrogen in a near-equiatomic CrMnFeCoNi HEA is studied, analyzing their impact on the microstructure, and mechanical properties from 77K to 673K, as well as wear, and corrosion resistance. Carbon and nitrogen are part of the FCC solid solution and contribute to the formation of precipitates. An increase in the yield and ultimate tensile strength accompanied with a decrease in the ductility are the main effects of C and N. The impact toughness of the interstitial-free material is higher than that of C and C+N alloyed systems. Compared to CrNi and CrMn austenitic steels, the wear resistance of the alloys at room temperature is rather low. The surface corrosion resistance of HEAs is comparable to austenitic steels; nevertheless HEAs are more susceptible to pitting in chloride containing solutions. © 2021, The Author(s).
  	view abstract	doi: 10.1007/s42452-021-04814-y

• 2021 • 215	Deformation behavior of 42CrMo4 over a wide range of temperatures and strain rates in Split-Hopkinson pressure bar tests Kimm, J.S. and Bergmann, J.A. and Wöste, F. and Pöhl, F. and Wiederkehr, P. and Theisen, W. Materials Science and Engineering A 826 (2021) In this research, Split-Hopkinson pressure bar tests were performed on samples made from the quenched and tempered steel 42CrMo4 in four different heat-treatment conditions. These samples were subjected to four different pressures and five different temperatures while deforming the samples at strain rates in the range of 103 s−1. Stress-strain curves and the strain rate were computed from the measured signals. The polished cross-sections of the samples were analyzed before and after testing by means of SEM, EBSD, nanoindentation, and microhardness testing. A variety of deformation characteristics were identified and correlated with the pre-test and post-test microstructure. This work focusses on the influence of the microstructure on deformation and provides a detailed understanding on the deformation of the 42CrMo4 steel over a wide range of parameter values. © 2021 Elsevier B.V.
  	view abstract	doi: 10.1016/j.msea.2021.141953

• 2021 • 214	Designing of low Pt electrocatalyst through immobilization on metal@C support for efficient hydrogen evolution reaction in acidic media Davodi, F. and Cilpa-Karhu, G. and Sainio, J. and Tavakkoli, M. and Jiang, H. and Mühlhausen, E. and Marzun, G. and Gökce, B. and Laasonen, K. and Kallio, T. Journal of Electroanalytical Chemistry 896 (2021) Nanoparticles comprising of transition metals encapsulated in an ultrathin graphene layer (NiFe@UTG) are utilized to anchor very low amount of finely dispersed pseudo-atomic Pt to function as a durable and active electrocatalyst (Pt/NiFe@UTG) for the hydrogen evolution reaction (HER) in acidic media. Our experiments show the vital role of the carbon shell thickness for efficient utilization of Pt. Furthermore, density functional theory calculations suggest that the metal-core has a crucial role in achieving promising electrocatalytic properties. The thin carbon shell allows the desired access of Pt atoms to the vicinity of the NiFe core while protecting the metallic core from oxidation in the harsh acidic media. In acidic media, the performance of this Pt/NiFe@UTG catalyst with 0.02 at% Pt is the same as that of commercial Pt/C (10 and 200 mV overpotential to reach 10 and 200 mA cm−2, respectively) with promising durability (5000 HER cycles). Our electrochemical characterization (cyclic voltammetry) shows no Pt specific peaks, indicating the existence of a very low Pt loading on the surface of the catalyst. Hence, this conductive core-shell catalyst support enables efficient utilization of Pt for electrocatalysis. © 2021 The Authors
  	view abstract	doi: 10.1016/j.jelechem.2021.115076

• 2021 • 213	Devitrification of thin film Cu–Zr metallic glass via ultrashort pulsed laser annealing Antonowicz, J. and Zalden, P. and Sokolowski-Tinten, K. and Georgarakis, K. and Minikayev, R. and Pietnoczka, A. and Bertram, F. and Chaika, M. and Chojnacki, M. and Dłużewski, P. and Fronc, K. and Greer, A.L. and Jastrzębski, ... Journal of Alloys and Compounds 887 (2021) In this work we report on an ultrashort pulsed laser annealing-driven devitrification of thin film Cu67Zr33 metallic glass characterized by micro-beam X-ray diffraction and electron microscopy techniques. The essential feature of ultrashort pulsed laser annealing is ultrafast heating (1014 K/s) by femtosecond optical excitation followed by extremely rapid cooling (1010–12 K/s) due to heat dissipation into the film substrate. During repetitive optical excitation, we take X-ray diffraction snapshots of the intermediate, frozen-in stages of the glass-crystal transformation to study its kinetics. A quantitative analysis of the diffraction patterns supported by electron microscopy result shows that the glass-crystal transformation proceeds by a rapid formation of an energetically favourable layer of crystalline ZrO2 on the free surface of the glassy film accompanied by nucleation and growth of fcc-Cu in the residual amorphous matrix. We demonstrate that at low effective annealing temperatures the devitrification kinetics of both products is correlated, while at high temperatures they decouple and ZrO2 forms an order of magnitude faster than Cu. © 2021 The Authors
  	view abstract	doi: 10.1016/j.jallcom.2021.161437

• 2021 • 212	Discovery and Implications of Hidden Atomic-Scale Structure in a Metallic Meteorite Kovács, A. and Lewis, L.H. and Palanisamy, D. and Denneulin, T. and Schwedt, A. and Scott, E.R.D. and Gault, B. and Raabe, D. and Dunin-Borkowski, R.E. and Charilaou, M. Nano Letters 21 8135-8142 (2021) Iron and its alloys have made modern civilization possible, with metallic meteorites providing one of the human's earliest sources of usable iron as well as providing a window into our solar system's billion-year history. Here highest-resolution tools reveal the existence of a previously hidden FeNi nanophase within the extremely slowly cooled metallic meteorite NWA 6259. This new nanophase exists alongside Ni-poor and Ni-rich nanoprecipitates within a matrix of tetrataenite, the uniaxial, chemically ordered form of FeNi. The ferromagnetic nature of the nanoprecipitates combined with the antiferromagnetic character of the FeNi nanophases gives rise to a complex magnetic state that evolves dramatically with temperature. These observations extend and possibly alter our understanding of celestial metallurgy, provide new knowledge concerning the archetypal Fe-Ni phase diagram and supply new information for the development of new types of sustainable, technologically critical high-energy magnets. ©
  	view abstract	doi: 10.1021/acs.nanolett.1c02573

• 2021 • 211	Electrocatalytic oxidation of 2-propanol on PtxIr100-x bifunctional electrocatalysts – A thin-film materials library study Kormányos, A. and Savan, A. and Ludwig, Al. and Speck, F.D. and Mayrhofer, K.J.J. and Cherevko, S. Journal of Catalysis 396 387-394 (2021) Due to the high demand for renewable and infrastructure compatible energy conversion and storage technologies, research on organic fuel cells receives increasing interest again recently. Organic fuels such as alcohols provide an attractive avenue to overcome the drawbacks of hydrogen as an energy carrier. Particularly interesting are secondary alcohols that almost exclusively form ketones as the final oxidation product, as they can be utilized in “zero emission” concepts without CO2 as a by-product. The state-of-the-art electrocatalyst in secondary alcohol oxidation is Pt-Ru, which demonstrates low onset potentials for the oxidation of the most facile secondary alcohol isopropanol. Yet, the achievable current densities are still relatively low and decrease rapidly due to the formed product acetone, which can poison the catalyst surface over time. Therefore, there is an inevitable need for the development of novel electrocatalyst materials circumventing these challenges. In this study, we employ a high-throughput electrochemical approach coupled to on-line inductively-coupled plasma mass spectrometry to map the composition-dependent activity and stability of PtxIr100-x alloy electrocatalysts toward the electro-oxidation of isopropanol. The activity and stability of magnetron sputtered PtxIr100-x material libraries are studied in 0.1 M HClO4 both in the absence and presence of isopropanol. The highest current densities are achieved for the sample containing the least amount of Ir (3.4 at.%), with a continuous decrease with the increasing amount of Ir. The alloys are inactive towards the oxidation of isopropanol when the amount of Ir exceeded 80 at%. The presence of isopropanol also has a notable effect on stability: while dissolution rates do not change in the case of pure Pt and Ir, a significant increase in stability is observed for the PtxIr100-x thin-film samples at all applied upper potential limits. This is explained by the strong adsorption of acetone on the surface of the catalyst that inhibits the formation of surface oxides. © 2021 Elsevier Inc.
  	view abstract	doi: 10.1016/j.jcat.2021.02.021

• 2021 • 210	Elemental segregation to lattice defects in the CrMnFeCoNi high-entropy alloy during high temperature exposures Heczko, M. and Mazánová, V. and Gröger, R. and Záležák, T. and Hooshmand, M.S. and George, E.P. and Mills, M.J. and Dlouhý, A. Acta Materialia 208 (2021) The influence of small plastic pre-strains on the elevated-temperature stability and microstructure of the equiatomic CrMnFeCoNi FCC solid solution is investigated. Particular attention is given to whether any of the alloy elements segregate to individual dislocations. To that end, CrMnFeCoNi samples were first deformed in tension at room temperature to plastic strains of 0.2 and 2.3%, and subsequently annealed at 973 K for 800 hours. The pre-strains activated planar slip of 1/2<110>-type dislocations on {111}-type glide planes. Interactions of this planar slip with special Σ3 grain boundaries formed a large number of dislocation segments with a <110>-type crystallographic orientation suitable for a credible end-on analysis of dislocation cores in HR-STEM. The cores of the 1/2<110> dislocations pushed up against the investigated grain boundaries were found to be close to the compact configuration. Within the sensitivity of the Super-X EDS mapping, no concentration gradient was detected near dislocations that would indicate enrichment at dislocation cores of any of the elemental constituents of the alloy after the pre-deformation and annealing. However, a Cr-rich tetragonal sigma phase nucleated and grew at grain boundary triple junctions during this anneal, processes that were not accelerated by the enhanced dislocation density present after pre-strain. A clear chromium gradient was observed in the Cr-depleted zones near grain boundaries suggesting that Cr transport occurred by relatively slow diffusion from the bulk to the grain boundaries and then by relatively fast diffusion along the grain boundaries to the precipitates. Accompanying the Cr depletion near grain boundaries is a simultaneous Ni and Mn enrichment, which promotes formation of the L10 NiMn phase that is observed on the grain boundaries after prolonged annealing. © 2021
  	view abstract	doi: 10.1016/j.actamat.2021.116719

• 2021 • 209	Evidence for a large Rashba splitting in PtPb4 from angle-resolved photoemission spectroscopy Lee, K. and Mou, D. and Jo, N.H. and Wu, Y. and Schrunk, B. and Wilde, J.M. and Kreyssig, A. and Estry, A. and Bud'Ko, S.L. and Nguyen, M.C. and Wang, L.-L. and Wang, C.-Z. and Ho, K.-M. and Canfield, P.C. and Kaminski, A. Physical Review B 103 (2021) We studied the electronic structure of PtPb4 using laser angle-resolved photoemission spectroscopy (ARPES) and density functional theory (DFT) calculations. This material is closely related to PtSn4, which exhibits exotic topological properties such as Dirac node arcs. The Fermi surface (FS) of PtPb4 consists of two electron pockets at the center of the Brillouin zone (BZ) and several hole pockets around the zone boundaries. Our ARPES data reveal significant Rashba splitting at the Γ point, in agreement with DFT calculations. The presence of Rashba splitting may render this material of potential interest for spintronic applications. © 2021 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.103.085125

• 2021 • 208	Faceting diagram for Ag segregation induced nanofaceting at an asymmetric Cu tilt grain boundary Peter, N.J. and Duarte, M.J. and Kirchlechner, C. and Liebscher, C.H. and Dehm, G. Acta Materialia 214 (2021) In this work, we experimentally establish the isothermal nanofacet evolution at an asymmetric ∑5 tilt grain boundary in the Cu-Ag system using a diffusion couple approach. We investigate the nanofacet formation along the grain boundary in dependence of the Ag solute excess concentration. The initial grain boundary dissociates into asymmetric Ag-lean segments and Ag-rich symmetric (210) segments. Increasing Ag excess leads to an increase in Ag-rich facet segment length, while the length of the asymmetric facets remains constant. From this, we construct a grain boundary nanofaceting diagram deduced from our experiments relating local atomic structure, overall inclination and Ag solute excess. © 2021 The Author(s)
  	view abstract	doi: 10.1016/j.actamat.2021.116960

• 2021 • 207	Formation of Co-Au Core-shell nanoparticles with thin gold shells and soft magnetic ϵ?cobalt cores ruled by thermodynamics and kinetics Johny, J. and Kamp, M. and Prymak, O. and Tymoczko, A. and Wiedwald, U. and Rehbock, C. and Schürmann, U. and Popescu, R. and Gerthsen, D. and Kienle, L. and Shaji, S. and Barcikowski, S. Journal of Physical Chemistry C 125 9534-9549 (2021) Bimetallic core-shell nanoparticles (CSNPs), where a ferromagnetic core (e.g., Co) is surrounded by a noblemetal thin plasmonic shell (e.g., Au), are highly interesting for applications in biomedicine and catalysis. Chemical synthesis of such structures, however, requires multistep procedures and often suffers from impaired oxidation resistance of the core. Here, we utilized a one-step environmentally friendly laser ablation in liquid technique to fabricate colloidal Co?Au CSNPs with core?shell yields up to 78% in mass. An in-depth analysis of the CSNPs down to single-particle levels revealed the presence of a unique nested core?shell structure with a very thin gold-rich shell, a nanocrystalline ϵ-cobalt sublayer, and a nested gold-rich core. The generated Co?Au CSNPs feature soft magnetic properties, while all gold-rich phases (thin shells and nested cores) exhibit a face-centered cubic solid solution with substantial cobalt substitution. The experimental findings are backed by refined thermodynamic surface energy calculations, which more accurately predict the predominance of solid solution and core?shell phase structures in correlation with particle size and nominal composition. Based on the Co?Au bulk phase diagram and in conjunction with previously reported results on the Fe?Au core?shell system as well as Co? Pt controls, we deduce four general rules for core?shell formation in non-or partially miscible laser-generated bimetallic nanosystems. ©2021 American Chemical Society.
  	view abstract	doi: 10.1021/acs.jpcc.1c02138

• 2021 • 206	Gd-Ru Nanoparticles Supported on Zr0.5Ce0.5O2Nanorods for Dry Methane Reforming Das, S. and Sengupta, M. and Bag, A. and Saini, A. and Muhler, M. and Bordoloi, A. ACS Applied Nano Materials 4 2547-2557 (2021) Dry reforming of methane is considered a potential reaction for the utilization of waste greenhouse gases to generate valuable chemicals. However, catalyst deactivation under a harsh reaction condition appears as the main obstacle toward its commercialization. In the present work, a facile hydrothermal synthesis procedure was adopted to prepare a robust Ru-based catalyst. Among the various combinations, a 1% Ru supported over Zr0.5Ce0.5O2 nanorod catalyst showed enhanced coke resistance and almost stable activity during 200 h activity analysis. Promotion of Ru/Zr0.5Ce0.5O2 with an optimum amount of Gd2O3 improved catalyst stability, which was attributed to the strong interaction of Ru with Gd2O3 leading to smaller Ru particle size (∼5 nm) and an improved OSC was inhibiting coke deposition. Promotion with 0.5% Gd2O3 further lowered the apparent activation energy of methane conversion to ∼20.6 kcal/mol without changing the reaction orders significantly. DFT calculation confirmed, due to the orbital similarity, methane cracking is preferred over Ru atoms and CO2 activation occurred on Gd atoms. ©
  	view abstract	doi: 10.1021/acsanm.0c03140

• 2021 • 205	Generation of terahertz transients from Co2Fe0.4 M0.6 Si-Heusler-alloy/normal-metal nanobilayers excited by femtosecond optical pulses Heidtfeld, S. and Adam, R. and Kubota, T. and Takanashi, K. and Cao, D. and Schmitz-Antoniak, C. and Bürgler, D.E. and Wang, F. and Greb, C. and Chen, G. and Komissarov, I. and Hardtdegen, H. and Mikulics, M. and Sobolewski, R. a... Physical Review Research 3 (2021) We generated pulses of electromagnetic radiation in the terahertz (THz) frequency range by optical excitation of (CFMS)/normal-metal (NM) bilayer structures. The CFMS is a Heusler alloy showing a band gap in one spin channel and is therefore a half metal. We compared the THz emission efficiency in a systematic manner for four different CFMS/NM bilayers, where NM was either Pt, Ta, Cr, or Al. Our measurements show that the THz intensity is highest for a Pt capping. We also demonstrate the tunability of the THz amplitude by varying the magnetic field for all four bilayers. We attribute the THz generation to the inverse spin Hall effect. In order to investigate the role of the interface in THz generation, we measured the spin mixing conductance for each CFMS/NM bilayer using a ferromagnetic resonance method. We found that the spin-orbit coupling cannot completely describe the THz generation in the bilayers and that the spin transmission efficiency of the CFMS/NM interface and the spin diffusion length, as well as the oxidation of the NM layer, play crucial roles in the THz emission process. © 2021 Published by the American Physical Society
  	view abstract	doi: 10.1103/PhysRevResearch.3.043025

• 2021 • 204	In situ nanoindentation during electrochemical hydrogen charging: a comparison between front-side and a novel back-side charging approach Duarte, M.J. and Fang, X. and Rao, J. and Krieger, W. and Brinckmann, S. and Dehm, G. Journal of Materials Science 56 8732-8744 (2021) The effects of hydrogen in metals are a pressing issue causing severe economic losses due to material deterioration by hydrogen embrittlement. A crucial understanding of the interactions of hydrogen with different microstructure features can be reached by nanoindentation due to the small volumes probed. Even more, in situ testing while charging the sample with hydrogen prevents the formation of concentration gradients due to hydrogen desorption. Two custom electrochemical cells for in situ testing were built in-house to charge the sample with hydrogen during nanoindentation: “front-side” charging with the sample and the indenter tip immersed into the electrolyte, and “back-side” charging where the analyzed region is never in contact with the solution. During front-side charging, surface degradation often occurs which also negatively influences analyses after hydrogen charging. The back-side charging approach proposed in this work is a promising technique for studying in situ the effects of hydrogen in alloys under mechanical loads, while completely excluding the influence of the electrolyte on the nanoindented surface. Hydrogen diffusion from the charged back-side toward the testing surface is here demonstrated by Kelvin probe measurements in ferritic FeCr alloys, used as a case study due to the high mobility of hydrogen in the bcc lattice. During nanoindentation, a reduction on the shear stress necessary for dislocations nucleation due to hydrogen was observed using both setups; however, the quantitative data differs and a contradictory behavior was found in hardness measurements. Finally, some guidelines for the use of both approaches and a summary of their advantages and disadvantages are presented. Graphical abstract: [Figure not available: see fulltext.] © 2021, The Author(s).
  	view abstract	doi: 10.1007/s10853-020-05749-2

• 2021 • 203	Incorporating elasticity into CALPHAD-informed density-based grain boundary phase diagrams reveals segregation transition in Al-Cu and Al-Cu-Mg alloys Wang, L. and Darvishi Kamachali, R. Computational Materials Science 199 (2021) The phase-like behavior of grain boundaries (GBs), recently evidenced in several materials, is opening up new possibilities in the design of alloy microstructures. In this context, GB phase diagrams are contributing to a predictive description of GB segregation and (interfacial) phase changes. The influence of chemo-mechanical solute-GB interactions on the GB phase diagram remains elusive so far. This is particularly important for multi-component alloys where the elastic interactions among solute atoms, of various sizes and bonding energies, can prevail, governing a complex co-segregation phenomenon. Recently, we developed a density-based model for GB thermodynamics that intrinsically accounts for GB elasticity in pure elements. In this work, we incorporate the homogeneous and heterogeneous elastic energies associated with the solutes into the density-based framework. We derive the multi-component homogeneous elastic energy by generalizing the continuum misfitting sphere model and extend it for GBs. The density-based free energy functional directly uses bulk CALPHAD thermodynamic data. The model is applied to binary and ternary Al alloys. We reveal that the elastic energy can profoundly affect the GB solubility and segregation behavior, leading to Cu segregation in otherwise Cu-depleted Al GBs. Consequently, GB segregation transition, i.e., a jump in the GB segregation as a function of alloy composition, is revealed in Al-Cu and Al-Cu-Mg alloy systems with implications for subsequent GB precipitation in these alloys. CALPHAD-informed elasticity-incorporated GB phase diagrams enable addressing a broader range of GB phenomena in engineering multi-component alloys. © 2021 Elsevier B.V.
  	view abstract	doi: 10.1016/j.commatsci.2021.110717

• 2021 • 202	Influence of crystalline defects on magnetic nanodomains in a rare-earth-free magnetocrystalline anisotropic alloy Palanisamy, D. and Kovács, A. and Hegde, O. and Dunin-Borkowski, R.E. and Raabe, D. and Hickel, T. and Gault, B. Physical Review Materials 5 (2021) A complex interplay between magnetic domain structure and crystalline imperfections, here twins, is revealed in a rare-earth-free MnAl bulk magnet. The magnetic domains are observed to be in the nanometer range for a large part of the magnetic structure and to scale with the number density of twins formed during thermal processing. We explain this phenomenon by a reduction in domain-wall energy at the twinned regions as proven by ab initio calculations. In addition, our atomic-scale analysis reveals that the twin boundaries contain excess Mn atoms that reduce the local magnetization, serving as an obstacle for domain wall motion. These insights can help guide the strategic design of magnetic materials by controlling the initial phase distribution to tailor the twin density and hence, the distribution of domains. © 2021 authors.
  	view abstract	doi: 10.1103/PhysRevMaterials.5.064403

• 2021 • 201	Investigation of joints from laser powder fusion processed and conventional material grades of 18MAR300 nickel maraging steel Tillmann, W. and Wojarski, L. and Henning, T. Welding in the World 65 1323-1331 (2021) Even though the buildup rate of laser powder bed fusion processes (LPBF) has steadily increased in recent years by using more and more powerful laser systems, the production of large-volume parts is still extremely cost-intensive. Joining of an additively manufactured complex part to a high-volume part made of conventional material is a promising technology to enhance economics. Today, constructors have to select the most economical joining process with respect to the individual field of application. The aim of this research was to investigate the hybrid joint properties of LBPF and conventionally casted 18MAR300 nickel maraging steel depending on the manufacturing process and the heat treatment condition. Therefore, the microstructure and the strength of the hybrid joints manufactured by LPBF or vacuum brazing were examined and compared to solid material and joints of similar material. It was found that the vacuum-brazed hybrid joints using a 50.8-μm-thick AuNi18 foil provide a high tensile strength of 904 MPa which is sufficient for a broad field of application. Furthermore, the additively manufactured hybrid samples offered with 1998 MPa a tensile strength more than twice as high but showed a considerable impact of buildup failures to the strength in general. © 2021, The Author(s).
  	view abstract	doi: 10.1007/s40194-021-01096-1

• 2021 • 200	Laboratory-Scale Processing and Performance Assessment of Ti–Ta High-Temperature Shape Memory Spring Actuators Paulsen, A. and Dumlu, H. and Piorunek, D. and Langenkämper, D. and Frenzel, J. and Eggeler, G. Shape Memory and Superelasticity 7 222-234 (2021) Ti75Ta25 high-temperature shape memory alloys exhibit a number of features which make it difficult to use them as spring actuators. These include the high melting point of Ta (close to 3000 °C), the affinity of Ti to oxygen which leads to the formation of brittle α-case layers and the tendency to precipitate the ω-phase, which suppresses the martensitic transformation. The present work represents a case study which shows how one can overcome these issues and manufacture high quality Ti75Ta25 tensile spring actuators. The work focusses on processing (arc melting, arc welding, wire drawing, surface treatments and actuator spring geometry setting) and on cyclic actuator testing. It is shown how one can minimize the detrimental effect of ω-phase formation and ensure stable high-temperature actuation by fast heating and cooling and by intermediate rejuvenation anneals. The results are discussed on the basis of fundamental Ti–Ta metallurgy and in the light of Ni–Ti spring actuator performance. © 2021, The Author(s).
  	view abstract	doi: 10.1007/s40830-021-00334-1

• 2021 • 199	Limited Elemental Mixing in Nanoparticles Generated by Ultrashort Pulse Laser Ablation of AgCu Bilayer Thin Films in a Liquid Environment: Atomistic Modeling and Experiments Shih, C.-Y. and Chen, C. and Rehbock, C. and Tymoczko, A. and Wiedwald, U. and Kamp, M. and Schuermann, U. and Kienle, L. and Barcikowski, S. and Zhigilei, L.V. Journal of Physical Chemistry C (2021) Pulsed laser ablation in liquids (PLAL) is a promising technique for the generation of colloidal alloy nanoparticles that are of high demand in a broad range of fields, including catalysis, additive manufacturing, and biomedicine. Many of the applications have stringent requirements on the nanoparticle composition and size distributions, which can only be met through innovations in the PLAL technique guided by a clear understanding of the nanoparticle formation mechanisms. In this work, we undertake a combined computational and experimental study of the nanoparticle formation mechanisms in ultrashort PLAL of Ag/Cu and Cu/Ag bilayer thin films. Experimental probing of the composition of individual nanoparticles and predictions from large-scale atomistic simulations provide consistent evidence of limited mixing between the two components from bilayer films by PLAL. The simulated and experimental distributions of nanoparticle compositions exhibit an enhanced abundance of Ag-rich and Cu-rich nanoparticles, as well as a strongly depressed population of well-mixed alloy nanoparticles. The surprising observation that the nanoscale phase separation of the two components in the bilayer films manifests itself in the sharp departure from the complete quantitative mixing in the colloidal nanoparticles is explained by the complex dynamic interaction between the ablation plume and liquid environment revealed in the simulations of the initial stage of the ablation process. The simulations predict that rapid deceleration of the ablation plume by the liquid environment results in the formation of a transient hot and dense metal region at the front of the plume, which hampers the mixing of the two components and, at the same time, contributes to the stratification of the plume in the emerging cavitation bubble. As a result, nanoparticles of different sizes and compositions are produced in different parts of the emerging cavitation bubble during the first nanoseconds of the ablation process. Notably, the diameters of the largest nanoparticles generated in the simulations of the initial stage of the ablation process are more than twice larger than the thickness of the original bilayer films. This observation provides a plausible scenario for the formation of large nanoparticles observed in the experiments. The conclusion on limited elemental mixing in the nanoparticles is validated in simulations of bilayers with different spatial order of Cu and Ag layers, even though the two systems exhibit some notable quantitative differences mainly related to the different strength of electron-phonon coupling in Cu and Ag. Overall, the results of this study provide new insights into the formation mechanism of bimetallic nanoparticles in ultrashort PLAL from thin bilayer targets and suggest that the formation of alloy nanoparticles from immiscible elements may be hampered for targets featuring distinctive elemental segregation. © 2021 American Chemical Society.
  	view abstract	doi: 10.1021/acs.jpcc.0c09970

• 2021 • 198	Mechanochemical Synthesis of Supported Bimetallic Catalysts De Bellis, J. and Felderhoff, M. and Schüth, F. Chemistry of Materials 33 2037-2045 (2021) In a previous publication, ball milling was introduced as an effective method for the preparation of supported metal catalysts, simply from the coarse powders of the metal and metal oxide support. In this follow-up study, we demonstrate that mixing multiple metal sources can result in supported alloyed nanoparticles, extending the field of application of the method to the synthesis of supported bimetallic catalysts. Ball milling Au and Pd or Au and Cu in a high-energy regime (shaker mill) indeed led to the formation of Au-Pd and Au-Cu nanoparticles, supported on MgO or yttria-stabilized zirconia (YSZ), which were explored as model systems. Powder X-ray diffraction and electron microscopy were the primary means to investigate as-synthesized materials. The catalytic performance in CO oxidation was also investigated to understand better how the synthetic method could affect the features of the final materials as catalysts. © 2021 The Authors. Published by American Chemical Society.
  	view abstract	doi: 10.1021/acs.chemmater.0c04134

• 2021 • 197	Molecular Level Synthesis of InFeO3and InFeO3/Fe2O3Nanocomposites Nahrstedt, V. and Stadler, D. and Fischer, T. and Duchoň, T. and Mueller, D.N. and Schneider, C.M. and Mathur, S. Inorganic Chemistry 60 3719-3728 (2021) New heterometallic In-Fe alkoxides [InFe(OtBu)4(PyTFP)2] (1), [InFe2(OneoPen)9(Py)] (2), and [InFe3(OneoPen)12] (3) were synthesized and structurally characterized. The arrangement of metal centers in mixed-metal framework was governed by the In:Fe ratio and the coordination preferences of Fe(III) and In(III) centers to be in tetrahedral and octahedral environments, respectively. 3 displayed a star-shaped so-called "Mitsubishi"motif with the central In atom coordinated with three tetrahedral {Fe(OneoPen)4}- anionic units. The deterministic structural influence of the larger In atom was evident in 1 and 2 which displayed the coordination of neutral coligands to achieve the desired coordination number. Thermal decomposition studies of compounds 1-3 under inert conditions with subsequent powder diffraction studies revealed the formation of Fe2O3 and In2O3 in the case of 3 and 2, whereas 1 intriguingly produced elemental In and Fe. In contrary, the thermal decomposition of 1-3 under ambient conditions produced a ternary oxide, InFeO3, with additional Fe2O3 present as a secondary phase in a different stoichiometric ratio predetermined through the In:Fe ratio in 2 and 3. The intimate mixing of different phases in InFeO3/Fe2O3 nanocomposites was confirmed by transmission electron microscopy of solid residues obtained after the decomposition of 1 and 2. The pure InFeO3 particles demonstrated ferromagnetic anomalies around 170 K as determined by temperature-dependent field-cooled and zero-field-cooled magnetization experiments. A first-order magnetic transition with an increase in the ZFC measurements was explained by temperature-induced reduction of the Fe-Fe distance and the corresponding increase in superexchange. © 2021 American Chemical Society.
  	view abstract	doi: 10.1021/acs.inorgchem.0c03425

• 2021 • 196	Multidimensional thermally-induced transformation of nest-structured complex Au-Fe nanoalloys towards equilibrium Johny, J. and Prymak, O. and Kamp, M. and Calvo, F. and Kim, S.-H. and Tymoczko, A. and El-Zoka, A. and Rehbock, C. and Schürmann, U. and Gault, B. and Kienle, L. and Barcikowski, S. Nano Research (2021) Bimetallic nanoparticles are often superior candidates for a wide range of technological and biomedical applications owing to their enhanced catalytic, optical, and magnetic properties, which are often better than their monometallic counterparts. Most of their properties strongly depend on their chemical composition, crystallographic structure, and phase distribution. However, little is known of how their crystal structure, on the nanoscale, transforms over time at elevated temperatures, even though this knowledge is highly relevant in case nanoparticles are used in, e.g., high-temperature catalysis. Au-Fe is a promising bimetallic system where the low-cost and magnetic Fe is combined with catalytically active and plasmonic Au. Here, we report on the in situ temporal evolution of the crystalline ordering in Au-Fe nanoparticles, obtained from a modern laser ablation in liquids synthesis. Our in-depth analysis, complemented by dedicated atomistic simulations, includes a detailed structural characterization by X-ray diffraction and transmission electron microscopy as well as atom probe tomography to reveal elemental distributions down to a single atom resolution. We show that the Au-Fe nanoparticles initially exhibit highly complex internal nested nanostructures with a wide range of compositions, phase distributions, and size-depended microstrains. The elevated temperature induces a diffusion-controlled recrystallization and phase merging, resulting in the formation of a single face-centered-cubic ultrastructure in contact with a body-centered cubic phase, which demonstrates the metastability of these structures. Uncovering these unique nanostructures with nested features could be highly attractive from a fundamental viewpoint as they could give further insights into the nanoparticle formation mechanism under non-equilibrium conditions. Furthermore, the in situ evaluation of the crystal structure changes upon heating is potentially relevant for high-temperature process utilization of bimetallic nanoparticles, e.g., during catalysis. © 2021, The Author(s).
  	view abstract	doi: 10.1007/s12274-021-3524-7

• 2021 • 195	Nitrogen and Oxygen Functionalization of Multi-walled Carbon Nanotubes for Tuning the Bifunctional Oxygen Reduction/Oxygen Evolution Performance of Supported FeCo Oxide Nanoparticles Kazakova, M.A. and Koul, A. and Golubtsov, G.V. and Selyutin, A.G. and Ishchenko, A.V. and Kvon, R.I. and Kolesov, B.A. and Schuhmann, W. and Morales, D.M. ChemElectroChem (2021) The combination of nanostructured transition metal oxides and carbon materials is a promising approach to obtain inexpensive, highly efficient, and stable bifunctional electrocatalysts for the oxygen reduction (ORR) and the oxygen evolution (OER) reactions. We present a strategy for improving the bifunctional ORR/OER activity of supported FeCoOx nanoparticles by tuning the properties of multi-walled carbon nanotubes (MWCNT) via nitrogen doping during their synthesis in the presence of ammonia and subsequent oxidative functionalization. In-depth structural characterization indicates that oxidative treatment provides fine control of the dispersion and localization of FeCoOx nanoparticles in MWCNT, while the optimal degree of nitrogen doping leads to increased bifunctional activity due to enhanced electrical conductivity as well as improved catalyst stability, in both OER and ORR conditions, for nanoparticles formed by two different synthesis routes. The findings reported can be strategically considered for the design of high-performance reversible ORR/OER electrocatalysts. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH
  	view abstract	doi: 10.1002/celc.202100556

• 2021 • 194	On the synthesis and structural evolution of artificial CrN/TiN nanocomposites Tillmann, W. and Kokalj, D. and Stangier, D. and Fu, Q. and Kruis, F.E. and Kesper, L. and Berges, U. and Westphal, C. Applied Surface Science 535 (2021) The synthesis of nanocomposites is limited to thermodynamically immiscible phases or to phase separation by exceeding the limits of solution. Hence, the formation of nanocomposites based on transition metals, revealing a nanocrystalline Metal-Nitride/nanocrystalline Metal-Nitride structure, is restricted. These restrictions can be overruled by a spatially separated synthesis of the two phases and a recombination during the deposition. With this approach, the limits of current systems can be expanded, enabling the synthesis of artificial nanocomposites based on a variety of materials. We demonstrate the synthesis of a composite of two nanocrystalline phases of the miscible transition metal-nitrides CrN and TiN. TiN nanoparticles were synthesized using an atmospheric-pressure arc reactor and in-situ injected into a growing CrN thin film. The thin films are analyzed regarding their physical- and microstructure using two-dimensional GIXRD, XPS based on synchrotron radiation and TEM. The CrTiN thin film reveals a two-phase structure consisting of nanocrystalline CrN and TiN phases with crystallite sizes of 9 nm and 4 nm according to GIXRD. XPS indicates bonding of Cr-N, Cr-Cr, and Ti-N. No hint for Cr-Ti bonding was found, excluding (Cr,Ti)N solid solution formation. Based on the TEM-investigations, TiN nanoparticles are embedded as agglomerates in the CrN matrix. © 2020 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2020.147736

• 2021 • 193	Orientation-dependent plastic deformation mechanisms and competition with stress-induced phase transformation in microscale NiTi Choi, W.S. and Pang, E.L. and Ko, W.-S. and Jun, H. and Bong, H.J. and Kirchlechner, C. and Raabe, D. and Choi, P.-P. Acta Materialia 208 (2021) Understanding the orientation-dependent deformation behavior of NiTi shape-memory alloys at small length scales is of importance for designing nano- and micro-electromechanical systems. However, a complete understanding of the orientation- and size-dependent competition between the various modes of slip, deformation twinning, and martensitic transformation in NiTi shape-memory alloys is still lacking, especially in micron-scale specimens. In the present study, we perform micro-compression tests on [001]- and [112]-oriented micro-pillars of a solutionized Ti-49.9at.% Ni alloy. Post-mortem TEM analysis of the deformed pillars reveal that the operating plastic deformation modes are {011}<100> slip and {114}<221¯> deformation twinning, which compete with the martensitic transformation, depending on the crystal orientation. Furthermore, in both experiments and molecular dynamics simulations, we consistently find residual B19′ martensite in a herringbone microstructure composed of finely spaced (001)B19′ compound twins instead of the generally assumed [011]B19′ type II twins common in bulk samples, suggesting that the operative martensitic transformation mode may be size-dependent. Schmid factors in compression are calculated for all commonly reported slip, deformation twinning, and martensitic transformation modes as a function of crystallographic orientation, which rationalize the orientation-dependent competition between these deformation modes. © 2021 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2021.116731

• 2021 • 192	Phase decomposition in nanocrystalline Cr0.8Cu0.2 thin films Chakraborty, J. and Harzer, T.P. and Duarte, M.J. and Dehm, G. Journal of Alloys and Compounds 888 (2021) Metastable Cr0.8Cu0.2 alloy thin films with nominal thickness of 360 nm have been deposited on Si(100) substrate by co-evaporation of Cu and Cr using molecular beam epitaxy (MBE). Phase evolution, microstructure, stress development, and crystallographic texture in Cr0.8Cu0.2 thin films have been investigated by X-ray diffraction (XRD), atom probe tomography (APT) and transmission electron microscopy (TEM) combined with energy dispersive X-ray spectroscopy (EDS) during annealing of the films in the temperature range 200–450 °C. X-ray diffraction of the as-deposited thin film shows single phase bcc crystal structure of the film whereas APT observation of fine precipitates in the film matrix due to inherent compositional fluctuation indicates onset of phase separation via spinodal decomposition regime. XRD (in-situ) and APT investigation of 300 °C annealed film reveals that the early stage of phase separation involves localized formation of metastable intermediate bcc precipitate phase having 60 at% Cr and 40 at% Cu approximately (~Cr0.6Cu0.4). For longer duration of annealing at temperature ≥350 °C, such metastable bcc precipitates act as heterogeneous nucleation sites for the onset of precipitation of Cu rich fcc Cu(Cr) phase which indicates a change of phase separation mechanism from ‘spinodal decomposition’ to ‘nucleation and growth’. Annealing of the film at temperature ≥400 °C for longer duration leads to the formation of a two phase structure with Cu rich fcc precipitate phase in a Cr rich bcc matrix. Observed phase decomposition is accompanied by significant changes in the microstructure, residual stress and crystallographic texture in the Cr rich bcc film matrix which leads to the minimization of both surface and strain energies and thereby a reduction of total Gibbs free energy of the thin film. Thermodynamic model calculation has been presented in order to understand the nucleation pathway of Cu rich stable fcc Cu(Cr) precipitates via non-classical nucleation of metastable intermediate bcc Cr0.6Cu0.4 phase. © 2021 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jallcom.2021.161391

• 2021 • 191	Phase-field modeling of chemoelastic binodal/spinodal relations and solute segregation to defects in binary alloys Mianroodi, J.R. and Shanthraj, P. and Svendsen, B. and Raabe, D. Materials 14 (2021) Microscopic phase-field chemomechanics (MPFCM) is employed in the current work to model solute segregation, dislocation-solute interaction, spinodal decomposition, and precipitate formation, at straight dislocations and configurations of these in a model binary solid alloy. In particular, (i) a single static edge dipole, (ii) arrays of static dipoles forming low-angle tilt (edge) and twist (screw) grain boundaries, as well as at (iii) a moving (gliding) edge dipole, are considered. In the first part of the work, MPFCM is formulated for such an alloy. Central here is the MPFCM model for the alloy free energy, which includes chemical, dislocation, and lattice (elastic), contributions. The solute concentration-dependence of the latter due to solute lattice misfit results in a strong elastic influence on the binodal (i.e., coexistence) and spinodal behavior of the alloy. In addition, MPFCM-based modeling of energy storage couples the thermodynamic forces driving (Cottrell and Suzuki) solute segregation, precipitate formation and dislocation glide. As implied by the simulation results for edge dislocation dipoles and their configurations, there is a competition between (i) Cottrell segregation to dislocations resulting in a uniform solute distribution along the line, and (ii) destabilization of this distribution due to low-dimensional spinodal decomposition when the segregated solute content at the line exceeds the spinodal value locally, i.e., at and along the dislocation line. Due to the completely different stress field of the screw dislocation configuration in the twist boundary, the segregated solute distribution is immediately unstable and decomposes into precipitates from the start. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/ma14071787

• 2021 • 190	Room temperature synthesized solid solution AuFe nanoparticles and their transformation into Au/Fe Janus nanocrystals Efremova, M.V. and Spasova, M. and Heidelmann, M. and Grebennikov, I.S. and Li, Z.-A. and Garanina, A.S. and Tcareva, I.O. and Savchenko, A.G. and Farle, M. and Klyachko, N.L. and Majouga, A.G. and Wiedwald, U. Nanoscale 13 10402-10413 (2021) Solid solution AuFe nanoparticles were synthesized for the first time under ambient conditions by an adapted method previously established for the Fe3O4-Au core-shell morphology. These AuFe particles preserved the fcc structure of Au incorporated with paramagnetic Fe atoms. The metastable AuFe can be segregated by transformation into Janus Au/Fe particles with bcc Fe and fcc Au upon annealing. The ferromagnetic Fe was epitaxially grown on low index fcc Au planes. This preparation route delivers new perspective materials for magnetoplasmonics and biomedical applications and suggests the reconsideration of existing protocols for magnetite-gold core-shell synthesis. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/d1nr00383f

• 2021 • 189	Simulation of the θ’ precipitation process with interfacial anisotropy effects in Al-Cu alloys Ta, N. and Bilal, M.U. and Häusler, I. and Saxena, A. and Lin, Y.-Y. and Schleifer, F. and Fleck, M. and Glatzel, U. and Skrotzki, B. and Kamachali, R.D. Materials 14 1-19 (2021) The effects of anisotropic interfacial properties and heterogeneous elasticity on the growth and ripening of plate-like θ’-phase (Al2Cu) in Al-1.69 at.% Cu alloy are studied. Multi-phase-field simulations are conducted and discussed in comparison with aging experiments. The precipi-tate/matrix interface is considered to be anisotropic in terms of its energy and mobility. We find that the additional incorporation of an anisotropic interfacial mobility in conjunction with the elastic anisotropy result in substantially larger aspect ratios of the precipitates closer to the experimental observations. The anisotropy of the interfacial energy shows comparably small effect on the precip-itate’s aspect ratio but changes the interface’s shape at the rim. The effect of the chemo-mechanical coupling, i.e., the composition dependence of the elastic constants, is studied as well. We show that the inverse ripening phenomenon, recently evidenced for δ’ precipitates in Al-Li alloys (Park et al. Sci. Rep. 2019, 9, 3981), does not establish for the θ’ precipitates. This is because of the anisotropic stress fields built around the θ’ precipitates, stemming from the precipitate’s shape and the interaction among different variants of the θ’ precipitate, that disturb the chemo-mechanical effects. These results show that the chemo-mechanical effects on the precipitation ripening strongly depend on the degree of sphericity and elastic isotropy of the precipitate and matrix phases. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/ma14051280

• 2021 • 188	Spin polarization and magnetotransport properties of systematically disordered Fe60Al40 thin films Borisov, K. and Ehrler, J. and Fowley, C. and Eggert, B. and Wende, H. and Cornelius, S. and Potzger, K. and Lindner, J. and Fassbender, J. and Bali, R. and Stamenov, P. Physical Review B 104 (2021) We investigate the evolution of spin polarization, spontaneous Hall angle (SHA), saturation magnetization, and Curie temperature of B2-ordered Fe60Al40 thin films under varying antisite disorder, induced by Ne+-ion irradiation. The spin polarization increases monotonically as a function of ion fluence. A relatively high polarization of 46% and a SHA of 3.1% are achieved on 40 nm films irradiated with 2×1016 ions/cm2 at 30 keV. An interesting divergence in the trends of the magnetization and SHA is observed for low disorder concentrations. The high spin polarization and its broad tunability range make ion-irradiated Fe60Al40 a promising material for application in spin electronic devices. © 2021 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.104.134417

• 2021 • 187	Spinodal Decomposition in Nanocrystalline Alloys Zhou, X. and Darvishi Kamachali, R. and Boyce, B.L. and Clark, B.G. and Raabe, D. and Thompson, G.B. Acta Materialia 215 (2021) For more than half a century, spinodal decomposition has been a key phenomenon in considering the formation of secondary phases in alloys. The most prominent aspect of the spinodal phenomenon is the lack of an energy barrier on its transformation pathway, offering an alternative to the nucleation and growth mechanism. The classical description of spinodal decomposition often neglects the influence of defects, such as grain boundaries, on the transformation because the innate ability for like-atoms to cluster is assumed to lead the process. Nevertheless, in nanocrystalline alloys, with a high population of grain boundaries with diverse characters, the structurally heterogeneous landscape can greatly influence the chemical decomposition behavior. Combining atom-probe tomography, precession electron diffraction and density-based phase-field simulations, we address how grain boundaries contribute to the temporal evolution of chemical decomposition within the miscibility gap of a Pt-Au nanocrystalline system. We found that grain boundaries can actually have their own miscibility gaps profoundly altering the spinodal decomposition in nanocrystalline alloys. A complex realm of multiple interfacial states, ranging from competitive grain boundary segregation to barrier-free low-dimensional interfacial decomposition, occurs with a dependency upon the grain boundary character. © 2021
  	view abstract	doi: 10.1016/j.actamat.2021.117054

• 2021 • 186	The hidden structure dependence of the chemical life of dislocations Zhou, X. and Mianroodi, J.R. and Da Silva, A.K. and Koenig, T. and Thompson, G.B. and Shanthraj, P. and Ponge, D. and Gault, B. and Svendsen, B. and Raabe, D. Science Advances 7 (2021) Dislocations are one-dimensional defects in crystals, enabling their deformation, mechanical response, and transport properties. Less well known is their influence on material chemistry. The severe lattice distortion at these defects drives solute segregation to them, resulting in strong, localized spatial variations in chemistry that determine microstructure and material behavior. Recent advances in atomic-scale characterization methods have made it possible to quantitatively resolve defect types and segregation chemistry. As shown here for a Pt-Au model alloy, we observe a wide range of defect-specific solute (Au) decoration patterns of much greater variety and complexity than expected from the Cottrell cloud picture. The solute decoration of the dislocations can be up to half an order of magnitude higher than expected from classical theory, and the differences are determined by their structure, mutual alignment, and distortion field. This opens up pathways to use dislocations for the compositional and structural nanoscale design of advanced materials. © 2021 American Association for the Advancement of Science. All rights reserved.
  	view abstract	doi: 10.1126/sciadv.abf0563

• 2021 • 185	Twin-boundary assisted crack tip plasticity and toughening in lamellar γ-TiAl Neogi, A. and Janisch, R. Acta Materialia 213 (2021) The internal twin-boundaries in lamellar γ-TiAl alloys, namely true-twin (TT), rotational boundary (RB), and pseudo-twin (PT), are known to be effective in strengthening the TiAl microstructures. Nevertheless, for designing microstructures with optimised mechanical properties, a better understanding of the role of these boundaries on fracture behavior is still required. To this end, we study how and to what degree crack advancement is affected by the local lattice orientation and atomic structure at the various twin boundaries. Molecular statics simulations were performed in conjunction with a linear elastic fracture mechanics based analysis, to understand the inter-lamellar and as well as trans-lamellar crack advancement at a TT, RB, and PT interface. The fracture toughness as well as the crack advancement mechanisms of the inter-lamellar cracks depend critically on the propagation direction. For instance, cracks along 〈112¯] in the TT, RB, and PT plane always emit dislocations at the crack tip, while the cracks along the opposite direction are brittle in nature. When it comes to trans-lamellar crack advancement, the crack tip shows significant plastic deformation and toughening for all interfaces. However, at a TT, a brittle crack is able to penetrate through the interface at a higher applied load, and propagates in the adjacent γ′ phase, while in the case of RB and PT, the crack tip is blunted and arrested at or near the boundary, resulting in dislocation emission and crack tip toughening. This suggests that a variation of the sequence of the different rotational boundaries could be a possibility to tune the crack tip plasticity and toughening in lamellar TiAl. © 2021 The Author(s)
  	view abstract	doi: 10.1016/j.actamat.2021.116924

• 2021 • 184	Unravelling the Zn-Cu Interaction during Activation of a Zn-promoted Cu/MgO Model Methanol Catalyst Pandit, L. and Boubnov, A. and Behrendt, G. and Mockenhaupt, B. and Chowdhury, C. and Jelic, J. and Hansen, A.-L. and Saraçi, E. and Ras, E.-J. and Behrens, M. and Studt, F. and Grunwaldt, J.-D. ChemCatChem 13 4120-4132 (2021) We report on an inverse model Cu/MgO methanol catalyst modified with 5 % zinc oxide at the Cu surface to element-specifically probe the interplay of metallic copper and zinc oxide during reductive activation. The structure of copper and zinc was unraveled by in situ X-ray diffraction (XRD) and in situ X-ray absorption spectroscopy (XAS) supported by theoretical modelling of the extended X-ray absorption fine structure and X-ray absorption near-edge structure spectra. Temperature-programmed reduction in H2 during in situ XAS showed that copper was reduced starting at 145 °C. With increasing reduction temperature, zinc underwent first a geometrical change in its structure, followed by reduction. The reduced zinc species were identified as surface alloy sites, which coexisted from 200 °C to 340 °C with ZnO species at the copper surface. At 400 °C Zn−Cu bulk-alloyed particles were formed. According to in situ XRD and in situ XAS, about half of the ZnO was not fully reduced, which can be explained by a lack of contact with copper. Our experimental results were further substantiated by density functional theory calculations, which verified that ZnO with neighboring Cu atoms reduced more easily. By combining these results, the distribution, phase and oxidation state of Zn species on Cu were estimated for the activated state of this model catalyst. This insight into the interplay of Cu and Zn forms the basis for deeper understanding the active sites during methanol synthesis. © 2021 The Authors. ChemCatChem published by Wiley-VCH GmbH
  	view abstract	doi: 10.1002/cctc.202100692

• 2020 • 183	A model for grain boundary thermodynamics Darvishi Kamachali, R. RSC Advances 10 26728-26741 (2020) Systematic microstructure design requires reliable thermodynamic descriptions of each and all microstructure elements. While such descriptions are well established for most bulk phases, thermodynamic assessment of microstructure defects is challenging because of their individualistic nature. In this paper, a model is devised for assessing grain boundary thermodynamics based on available bulk thermodynamic data. We propose a continuous relative atomic density field and its spatial gradients to describe the grain boundary region with reference to the homogeneous bulk and derive the grain boundary Gibbs free energy functional. The grain boundary segregation isotherm and phase diagram are computed for a regular binary solid solution, and qualitatively benchmarked for the Pt-Au system. The relationships between the grain boundary's atomic density, excess free volume, and misorientation angle are discussed. Combining the current density-based model with available bulk thermodynamic databases enables constructing databases, phase diagrams, and segregation isotherms for grain boundaries, opening possibilities for studying and designing heterogeneous microstructures. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/d0ra04682e

• 2020 • 182	An approach to use sub-surface characteristics for the prediction of process forces during cutting operations Bergmann, J.A. and Kimm, J. and Theisen, W. and Wiederkehr, P. Procedia CIRP 88 276-281 (2020) During machining operations, complex engagement situations between the tool and workpiece lead to varying amplitudes and directions of cutting forces. Correlations between material properties, process parameters and resulting forces have to be analyzed to ensure the predictability of machining processes. To model the material removal, a detailed analysis of the material behavior during the engagement is needed. In this work, a geometric physically-based simulation system is extended to take the material behavior into account for improving the prediction accuracy of process forces. A detailed analysis of the low-alloyed steel 42CrMo4 and validation experiments are presented. © 2020 The Authors.
  	view abstract	doi: 10.1016/j.procir.2020.05.048

• 2020 • 181	Anisotropic failure behavior of ordered intermetallic TiAl alloys under pure mode-I loading Neogi, A. and Alam, M. and Hartmaier, A. and Janisch, R. Modelling and Simulation in Materials Science and Engineering 28 (2020) Whether a metallic material fractures by brittle cleavage or by ductile rupture is primarily governed by the competition between cleavage and dislocation emission at the crack tip. The linear elastic fracture mechanics (LEFM) based criterion of Griffith, respectively the one for dislocation emission of Rice, are sufficiently reliable for determining the possible crack tip propagation mechanisms in isotropic crystalline metals. However, the applicability of these criteria is questionable when non-cubic, anisotropic solids are considered, as e.g. ordered intermetallic TiAl phases, where slip systems are limited and elastic anisotropy is pronounced. We study brittle versus ductile failure mechanisms in face-centered tetragonal TiAl and hexagonal Ti3Al using large-scale atomistic simulations and compare our findings to the predictions of LEFM-based criteria augmented by elastic anisotropy. We observe that the augmented Griffith and Rice criteria are reliable for determining the direction dependent crack tip mechanisms, if all the available dislocation slip systems are taken into account. Yet, atomistic simulations are necessary to understand crack blunting due to mixed mechanisms, or shear instabilities other than dislocation emission. The results of our systematic study can be used as basis for modifications of the Griffith/Rice criteria in order to incorporate such effects. © 2020 The Author(s). Published by IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-651X/aba738

• 2020 • 180	Atomic scale configuration of planar defects in the Nb-rich C14 Laves phase NbFe2 Šlapáková, M. and Zendegani, A. and Liebscher, C.H. and Hickel, T. and Neugebauer, J. and Hammerschmidt, T. and Ormeci, A. and Grin, J. and Dehm, G. and Kumar, K.S. and Stein, F. Acta Materialia 183 362-376 (2020) Laves phases belong to the group of tetrahedrally close-packed intermetallic phases, and their crystal structure can be described by discrete layer arrangements. They often possess extended homogeneity ranges and the general notion is that deviations from stoichiometry are accommodated by anti-site atoms or vacancies. The present work shows that excess Nb atoms in a Nb-rich NbFe2 C14 Laves phase can also be incorporated in various types of planar defects. Aberration-corrected scanning transmission electron microscopy and density functional theory calculations are employed to characterize the atomic configuration of these defects and to establish stability criteria for them. The planar defects can be categorized as extended or confined ones. The extended defects lie parallel to the basal plane of the surrounding C14 Laves phase and are fully coherent. They contain the characteristic Zr4Al3-type (O) units found in the neighboring Nb6Fe7 µ phase. An analysis of the chemical bonding reveals that the local reduction of the charge transfer is a possible reason for the preference of this atomic arrangement. However, the overall layer stacking deviates from that of the perfect µ phase. The ab initio calculations establish why these exceptionally layered defects can be more stable configurations than coherent nano-precipitates of the perfect µ phase. The confined defects are observed with pyramidal and basal habit planes. The pyramidal defect is only ~1 nm thick and resembles the perfect µ phase. In contrast, the confined basal defect can be regarded as only one single O unit and it appears as if the stacking sequence is disrupted. This configuration is confirmed by ab initio calculations to be metastable. © 2019
  	view abstract	doi: 10.1016/j.actamat.2019.11.004

• 2020 • 179	Beyond Solid Solution High-Entropy Alloys: Tailoring Magnetic Properties via Spinodal Decomposition Rao, Z. and Dutta, B. and Körmann, F. and Lu, W. and Zhou, X. and Liu, C. and da Silva, A.K. and Wiedwald, U. and Spasova, M. and Farle, M. and Ponge, D. and Gault, B. and Neugebauer, J. and Raabe, D. and Li, Z. Advanced Functional Materials (2020) Since its first emergence in 2004, the high-entropy alloy (HEA) concept has aimed at stabilizing single- or dual-phase multi-element solid solutions through high mixing entropy. Here, this strategy is changed and renders such massive solid solutions metastable, to trigger spinodal decomposition for improving the alloys’ magnetic properties. The motivation for starting from a HEA for this approach is to provide the chemical degrees of freedom required to tailor spinodal behavior using multiple components. The key idea is to form Fe-Co enriched regions which have an expanded volume (relative to unconstrained Fe-Co), due to coherency constraints imposed by the surrounding HEA matrix. As demonstrated by theory and experiments, this leads to improved magnetic properties of the decomposed alloy relative to the original solid solution matrix. In a prototype magnetic FeCoNiMnCu HEA, it is shown that the modulated structures, achieved by spinodal decomposition, lead to an increase of the Curie temperature by 48% and a simultaneous increase of magnetization by 70% at ambient temperature as compared to the homogenized single-phase reference alloy. The findings thus open a pathway for the development of advanced functional HEAs. © 2020 The Authors. Advanced Functional Materials published by Wiley-VCH GmbH
  	view abstract	doi: 10.1002/adfm.202007668

• 2020 • 178	Bistability and oscillations in cooperative microtubule and kinetochore dynamics in the mitotic spindle Schwietert, F. and Kierfeld, J. New Journal of Physics 22 (2020) In the mitotic spindle microtubules attach to kinetochores via catch bonds during metaphase, and microtubule depolymerization forces give rise to stochastic chromosome oscillations. We investigate the cooperative stochastic microtubule dynamics in spindle models consisting of ensembles of parallel microtubules, which attach to a kinetochore via elastic linkers. We include the dynamic instability of microtubules and forces on microtubules and kinetochores from elastic linkers. A one-sided model, where an external force acts on the kinetochore is solved analytically employing a mean-field approach based on Fokker-Planck equations. The solution establishes a bistable force-velocity relation of the microtubule ensemble in agreement with stochastic simulations. We derive constraints on linker stiffness and microtubule number for bistability. The bistable force-velocity relation of the one-sided spindle model gives rise to oscillations in the two-sided model, which can explain stochastic chromosome oscillations in metaphase (directional instability). We derive constraints on linker stiffness and microtubule number for metaphase chromosome oscillations. Including poleward microtubule flux into the model we can provide an explanation for the experimentally observed suppression of chromosome oscillations in cells with high poleward flux velocities. Chromosome oscillations persist in the presence of polar ejection forces, however, with a reduced amplitude and a phase shift between sister kinetochores. Moreover, polar ejection forces are necessary to align the chromosomes at the spindle equator and stabilize an alternating oscillation pattern of the two kinetochores. Finally, we modify the model such that microtubules can only exert tensile forces on the kinetochore resulting in a tug-of-war between the two microtubule ensembles. Then, induced microtubule catastrophes after reaching the kinetochore are necessary to stimulate oscillations. The model can reproduce experimental results for kinetochore oscillations in PtK1 cells quantitatively. © 2020 The Author(s). Published by IOP Publishing Ltd on behalf of the Institute of Physics and Deutsche Physikalische Gesellschaft.
  	view abstract	doi: 10.1088/1367-2630/ab7ede

• 2020 • 177	Chip formation and phase transformation in orthogonal machining of NiTi shape memory alloy: microstructure-based modelling and experimental validation Kaynak, Y. and Manchiraju, S. and Jawahir, I.S. and Biermann, D. CIRP Annals 69 85-88 (2020) Phase transformation and shape memory response of NiTi alloys are sensitive to the variation of temperature and stress. Thus, the phase transformation of NiTi alloys becomes more complex during machining process. This study presents findings from a major study involving modelling of machining-induced phase transformation of NiTi alloys performed by modifying Helmholtz free energy-based microstructure model. Orthogonal cutting tests were performed to validate the predicted outputs from the simulation, such as cutting forces, temperatures and chip morphology. This work provides a strong evidence that the developed new model can accurately predict the experimentally recorded outputs in machining of NiTi alloys. © 2020
  	view abstract	doi: 10.1016/j.cirp.2020.04.025

• 2020 • 176	Cold Gas Spraying of Nickel-Titanium Coatings for Protection Against Cavitation Mauer, G. and Rauwald, K.-H. and Sohn, Y.J. and Weirich, T.E. Journal of Thermal Spray Technology (2020) Cavitation erosion is a sever wear mechanism that takes place in hydrodynamic systems. Examples are turbine vanes of hydropower plants or components of valves and pumps in hydraulic systems. Nickel-titanium shape memory alloys (NiTi) are attractive materials for cavitation-resistant coatings because of their pronounced intrinsic damping mitigating cavitation-induced erosion. In this work, NiTi coatings were produced by cold gas spraying. The phase transformation behaviors of the powder feedstock and the as-sprayed coatings were investigated. Regarding the obtained transformation temperatures, the measured substrate temperatures during spraying rule out that either the shape memory effect or the pseudoelasticity of NiTi could affect the deposition efficiency under the applied conditions of cold gas spraying. Another potential effect is stress-induced amorphization which could occur at the particle–substrate interfaces and impair particle bonding by stress relaxation. Moreover, also oxide formation can be significant. Thus, the presence of amorphous phases and oxides in the near-surface zone of particles bounced off after impact was investigated. Oxidation could be confirmed, but no indication of amorphous phase was found. Besides, also the evolution of local microstrains implies that the substrate temperatures affect the deposition efficiency. These temperatures were significantly influenced by the spray gun travel speed. © 2020, The Author(s).
  	view abstract	doi: 10.1007/s11666-020-01139-x

• 2020 • 175	Comparison of cryogenic deformation of the concentrated solid solutions CoCrFeMnNi, CoCrNi and CoNi Tirunilai, A.S. and Hanemann, T. and Reinhart, C. and Tschan, V. and Weiss, K.-P. and Laplanche, G. and Freudenberger, J. and Heilmaier, M. and Kauffmann, A. Materials Science and Engineering A 783 (2020) The current work compares the deformation behavior of CoCrFeMnNi and CoCrNi in the temperature interval between 295 K and 8 K through a series of quasi-static tensile tests. Temperature-dependent yield stress variation was found to be similarly high in these two alloys. Previous investigations only extended down to 77 K and showed that a small amount of ε-martensite was formed in CoCrNi while this phase was not observed in CoCrFeMnNi. The present study extends these investigations down to 8 K where similar low levels of ε-martensite were presently detected. Based on this result, a rough assessment has been made estimating the importance of deformation twinning to the strength. The relative work hardening rates of CoCrFeMnNi and CoCrNi were comparable in value despite the differences in ε-martensite formation during deformation. CoCrFeMnNi deforms by dislocation slip and deformation twinning while deformation in CoCrNi is also accommodated by the formation of ε-martensite at cryogenic temperatures. Additionally, CoNi, a solid solution from the Co–Cr–Fe–Mn–Ni system with low strength, was used for comparison, showing contrasting deformation behavior at cryogenic temperatures. © 2020 Elsevier B.V.
  	view abstract	doi: 10.1016/j.msea.2020.139290

• 2020 • 174	Competition of defect ordering and site disproportionation in strained LaCoO3 on SrTiO3 (001) Geisler, B. and Pentcheva, R. Physical Review B 101 (2020) The origin of the 3×1 reconstruction observed in epitaxial LaCoO3 films on SrTiO3(001) is assessed by first-principles calculations including a Coulomb repulsion term. We compile a phase diagram as a function of the oxygen pressure, which shows that (3×1)-ordered oxygen vacancies (LaCoO2.67) are favored under commonly used growth conditions, while stoichiometric films emerge under oxygen-rich conditions. Growth of further reduced LaCoO2.5 brownmillerite films is impeded by phase separation. We report two competing ground-state candidates for stoichiometric films: a semimetallic phase with 3×1 low-spin/intermediate-spin/intermediate-spin (LS/IS/IS) magnetic order and a semiconducting phase with IS/IS/IS magnetic order. This demonstrates that tensile strain induces ferromagnetism even in the absence of oxygen vacancies. Both phases exhibit an intriguing (3×1)-reconstructed octahedral rotation pattern and accordingly modulated La-La distances. In particular, charge and bond disproportionation and concomitant orbital order of the t2g hole emerge at the Co sites that are also observed for unstrained bulk LaCoO3 in the IS state and explain structural data obtained by x-ray diffraction at elevated temperature. Site disproportionation drives a metal-to-semiconductor transition that reconciles the IS state with the experimentally observed low conductivity during spin-state crossover without the presence of Jahn-Teller distortions. © 2020 American Physical Society. ©2020 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.101.165108

• 2020 • 173	Composition and structure of magnetic high-temperature-phase, stable Fe-Au core-shell nanoparticles with zero-valent bcc Fe core Kamp, M. and Tymoczko, A. and Popescu, R. and Schürmann, U. and Nadarajah, R. and Gökce, B. and Rehbock, C. and Gerthsen, D. and Barcikowski, S. and Kienle, L. Nanoscale Advances 2 3912-3920 (2020) Advanced quantitative TEM/EDXS methods were used to characterize different ultrastructures of magnetic Fe-Au core-shell nanoparticles formed by laser ablation in liquids. The findings demonstrate the presence of Au-rich alloy shells with varying composition in all structures and elemental bcc Fe cores. The identified structures are metastable phases interpreted by analogy to the bulk phase diagram. Based on this, we propose a formation mechanism of these complex ultrastructures. To show the magnetic response of these magnetic core nanoparticles protected by a noble metal shell, we demonstrate the formation of nanostrands in the presence of an external magnetic field. We find that it is possible to control the lengths of these strands by the iron content within the alloy nanoparticles. This journal is © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/d0na00514b

• 2020 • 172	Composition dependence of hardness and elastic modulus of the cubic and hexagonal NbCo2 Laves phase polytypes studied by nanoindentation Luo, W. and Kirchlechner, C. and Li, J. and Dehm, G. and Stein, F. Journal of Materials Research 35 185-195 (2020) Regarding the effect of composition on the mechanical properties of intermetallic phases such as Laves phases, there is conflicting information in the literature. Some authors observed defect hardening when deviating from stoichiometric Laves phase composition, whereas others find defect softening. Here, we present a systematic investigation of the defect state, hardness, and elastic modulus of cubic and hexagonal NbCo2 Laves phases as a function of crystal structure and composition. For this purpose, diffusion couples were prepared which exhibit diffusion layers of the cubic C15 and hexagonal C14 and C36 NbCo2 Laves phases, with concentration gradients covering their entire homogeneity ranges from 24 to 37 at.% Nb. Direct observations of dislocations and stacking faults in the diffusion layers as a function of composition were performed by electron channeling contrast imaging, and the hardness and elastic modulus were probed in the diffusion layers along the concentration gradients by nanoindentation. © 2020 Materials Research Society.
  	view abstract	doi: 10.1557/jmr.2019.384

• 2020 • 171	Control of thermally stable core-shell nano-precipitates in additively manufactured Al-Sc-Zr alloys Kürnsteiner, P. and Bajaj, P. and Gupta, A. and Wilms, M.B. and Weisheit, A. and Li, X. and Leinenbach, C. and Gault, B. and Jägle, E.A. and Raabe, D. Additive Manufacturing 32 (2020) Laser Additive Manufacturing (LAM) of light metals such as high-strength Al-based alloys offers tremendous potential for e.g. weight reduction and associated reduced fuel consumptions for the transportation industry. Typically, commercial Sc-containing alloys, such as Scalmalloy®, rely on precipitation hardening to increase their strength. Conventional processing involves controlled ageing during which ordered and coherent Al3Sc precipitates form from a Sc-supersaturated solid solution. Here we show how the intrinsic heat treatment (IHT) of directed energy deposition (DED) can be used to trigger the precipitation of Al3Sc already during the LAM process. High number densities of 1023 nano-precipitates per m3 can be realized through solid-state phase transformation from the supersaturated Al-Sc matrix that results from the fast cooling rate in LAM. Yet, the IHT causes precipitates to coarsen, hence reducing their strengthening effect. We implement alternative solidification conditions to exploit the IHT to form a Zr-rich shell around the Al3Sc precipitates that prevents coarsening. Our approach is applicable to a wide range of precipitation-hardened alloys to trigger in-situ precipitation during LAM. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.addma.2019.100910

• 2020 • 170	Corrosion behavior of NiTi alloy subjected to femtosecond laser shock peening without protective coating in air environment Wang, H. and Jürgensen, J. and Decker, P. and Hu, Z. and Yan, K. and Gurevich, E.L. and Ostendorf, A. Applied Surface Science 501 (2020) Laser shock peening with femtosecond laser was used to improve the corrosion resistance of biomedical NiTi alloy without protective coating in the air environment. The energy dispersive X-ray analysis (EDX) and X-ray diffraction (XRD) based analysis showed that the laser ablation could produce titanium oxide layer and femtosecond laser shock peening (FsLSP) can generate residual stress in the surface layer of NiTi alloy. The FsLSP improved the corrosion resistance of NiTi in 3.5% NaCl solution and Hank's solution and also prevented the formation of corrosion cracks and pits during corrosion testing. The reasons for the improvement of corrosion behavior may be the generation of residual stress and titanium oxide film during the laser surface treatment. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2019.144338

• 2020 • 169	Crystal structure and composition dependence of mechanical properties of single-crystalline NbCo2 Laves phase Luo, W. and Kirchlechner, C. and Zavašnik, J. and Lu, W. and Dehm, G. and Stein, F. Acta Materialia 184 151-163 (2020) Extended diffusion layers of the cubic C15 and hexagonal C14 and C36 NbCo2 Laves phases with concentration gradients covering their entire homogeneity ranges were produced by the diffusion couple technique. Single-phase and single-crystalline micropillars of the cubic and hexagonal NbCo2 Laves phases were prepared in the diffusion layers by focused ion beam (FIB) milling. The influence of chemical composition, structure type, orientation and pillar size on the deformation behavior and the critical resolved shear stress (CRSS) was studied by micropillar compression tests. The pillar orientation influences the activated slip systems, but the deformation behavior and the CRSS are independent of orientation. The deformation of the smallest NbCo2 micropillars (0.8 µm in top diameter) appears to be dislocation nucleation controlled and the CRSS approaches the theoretical shear stress for dislocation nucleation. The CRSS of the 0.8 µm-sized NbCo2 micropillars is nearly constant from 26 to 34 at.% Nb where the C15 structure is stable. It decreases as the composition approaches the Co-rich and Nb-rich boundaries of the homogeneity range where the C15 structure transforms to the C36 and the C14 structure, respectively. The decrease in the CRSS at these compositions is related to the reduction of shear modulus and stacking fault energy. As the pillar size increases, stochastic deformation behavior and large scatter in the CRSS values occur and obscure the composition effect on the CRSS. © 2019
  	view abstract	doi: 10.1016/j.actamat.2019.11.036

• 2020 • 168	Deactivating deformation twinning in medium-entropy CrCoNi with small additions of aluminum and titanium Slone, C.E. and LaRosa, C.R. and Zenk, C.H. and George, E.P. and Ghazisaeidi, M. and Mills, M.J. Scripta Materialia 178 295-300 (2020) High strain-hardening rates in equiatomic CrCoNi and other multi-principal element alloys have been attributed to deformation twinning. This work shows that small additions of Al and Ti to a CrCoNi alloy deactivate deformation twinning with only minor changes to uniform elongation and ultimate tensile strength. The initial microstructure is free of chemically ordered (Al,Ti)-rich precipitates after solutionizing and quenching. Tensile properties for the alloy are reported and compared to equiatomic CrCoNi, and the post-deformation microstructure is assessed. Density functional theory calculations indicate that energetically unfavorable Al-Al bonds may discourage shearing via partial dislocations, which are necessary for twinning to occur. © 2019
  	view abstract	doi: 10.1016/j.scriptamat.2019.11.053

• 2020 • 167	Deformation mechanisms in a superelastic NiTi alloy: An in-situ high resolution digital image correlation study Polatidis, E. and Šmíd, M. and Kuběna, I. and Hsu, W.-N. and Laplanche, G. and Van Swygenhoven, H. Materials and Design 191 (2020) An in-situ high resolution digital image correlation investigation during uniaxial tensile deformation reveals the recoverable and the non-recoverable strain mechanisms in a Ni51Ti49 alloy with a mean grain size of 35 μm. Recoverable strain is due to the martensitic transformation, for which more than one variant per grain can be activated. The majority of the activated variants exhibit high Schmid factor. The variant selection can be influenced by shear transmission across grain boundaries, when the geometrical compatibility between the neighboring habit plane variants is favourable; in these cases variants that do not have the highest Schmid factor, with respect to the macroscopically applied load, are activated. The experimentally determined transformation strains agree well with theoretical calculations for single crystals. The non-recoverable strain is due to deformation slip in austenite, twinning in martensite and residual martensite. The results are discussed in view of possible twinning modes that can occur in austenite resulting in significant non-recoverable strain. © 2020 The Authors
  	view abstract	doi: 10.1016/j.matdes.2020.108622

• 2020 • 166	Diffusion, defects and understanding the growth of a multicomponent interdiffusion zone between Pt-modified B2 NiAl bond coat and single crystal superalloy Esakkiraja, N. and Gupta, A. and Jayaram, V. and Hickel, T. and Divinski, S.V. and Paul, A. Acta Materialia 195 35-49 (2020) Composition-dependent diffusion coefficients are determined in B2-Ni(CoPt)Al system following the pseudo-binary and pseudo-ternary diffusion couple methods, which would not be possible otherwise in a quaternary inhomogeneous material fulfilling the conditions to solve the equations developed based on the Onsager formalism. The end-member compositions to produce ideal/near-ideal diffusion profiles are chosen based on thermodynamic details. The pseudo-binary interdiffusion coefficients of Ni and Al decrease in the presence of Co but increase in the presence of Pt. The pseudo-ternary interdiffusion coefficients indicate that the main interdiffusion coefficients increase significantly in the presence of Pt. Marginal changes of the cross interdiffusion coefficients substantiate a minor change of the diffusional interactions between the components. The thermodynamic driving forces show opposite trends with respect to composition as compared to the changes of the interdiffusion coefficients advocating a dominating role of the Pt(Co)-induced modifications of point defect concentrations. DFT-based calculations revealed that Pt alloying increases the Ni vacancy concentration and decreases the activation energy for the triple defect diffusion mechanism. These findings explain the increase in the thickness of the interdiffusion zone between the B2-Ni(Pt)Al bond coat and the single crystal superalloy René N5 because of Pt addition. Furthermore, the EPMA and TEM analyses reveal the growth of refractory elements-enriched precipitates. © 2020 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2020.04.016

• 2020 • 165	Effect of Oxygen on High-temperature Phase Equilibria in Ternary Ti-Al-Nb Alloys Distl, B. and Dehm, G. and Stein, F. Zeitschrift fur Anorganische und Allgemeine Chemie 646 1151-1156 (2020) Alloys based on titanium aluminides received a lot of attention because of their capability to substitute Ni-based superalloys in high-temperature applications. However, the phase equilibria between the main microstructure constituents (αTi), (βTi), γ (TiAl) and α2(Ti3Al) can be shifted significantly by impurities such as oxygen especially at high temperatures. This behavior is investigated on the tie-triangle (αTi) + (βTi) + γ (TiAl) in the ternary Ti-Al-Nb system at 1300 °C. An explanation for this behavior could be the occupation of octahedral voids by impurities in certain phases. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
  	view abstract	doi: 10.1002/zaac.202000098

• 2020 • 164	Effects of Mo on the mechanical behavior of γ/γʹ-strengthened Co-Ti-based alloys Im, H.J. and Lee, S. and Choi, W.S. and Makineni, S.K. and Raabe, D. and Ko, W.-S. and Choi, P.-P. Acta Materialia 197 69-80 (2020) We investigated the flow behavior of γ/γʹ-strengthened Co-12Ti and Co-12Ti-4Mo (at.%) alloys at room and elevated temperatures (up to 900°C) by electron microscopy and density functional theory. The Mo-added alloy exhibited an enhanced compressive yield strength and strain hardening behavior as compared to the reference binary alloy. This behavior could be attributed to a ~25% larger γʹ volume fraction and ~7% higher planar fault energies in Co-12Ti-4Mo. Using electron channeling contrast imaging, we observed interrupted slip bands in the Co-12Ti-4Mo alloy deformed to a strain of 6%, which led to enhanced strain hardening, in contrast to extended slip bands along {111} planes in the Co-12Ti alloy. Interrupted slip band formation in Co-12Ti-4Mo could be explained by rapid exhaustion of dislocation sources and a higher energy barrier required to cut the γʹ precipitates. These effects are due to a reduced γ channel width and substantial hardening effect of γʹ-Co3(Ti,Mo) in the ternary alloy as well as due to the large shear modulus difference between γʹ and γ. © 2020
  	view abstract	doi: 10.1016/j.actamat.2020.07.037

• 2020 • 163	Electrochemical dealloying as a tool to tune the porosity, composition and catalytic activity of nanomaterials Rurainsky, C. and Manjón, A.G. and Hiege, F. and Chen, Y.-T. and Scheu, C. and Tschulik, K. Journal of Materials Chemistry A 8 19405-19413 (2020) Electrochemical dealloying as a post-Treatment can greatly improve the catalytic activity of nanoparticles. To date, selecting suitable conditions to reach desired porosity, composition and catalytic activity is based on trial-And-error-Attempts, due to insufficient understanding of the electrochemically induced morphological and compositional changes of the nanoparticles. These changes are elucidated here by combining electrochemistry with identical location electron microscopy analyses and linking them to the electrocatalytic properties of the obtained nanocatalysts. Using AgAu alloy nanoparticles and the hydrogen evolution reaction as a model system, the influence of cyclic voltammetry parameters on the catalytic activity upon electrochemical dealloying is investigated. Increasing the number of cycles initially results in a decreased Ag content and a sharp improvement in activity. Additional dealloying increases the nanoparticle porosity, while marginally altering their composition, due to surface motion of atoms. Since this is accompanied by particle aggregation, a decrease in catalytic activity results upon extensive cycling. This transition between porosity formation and particle aggregation marks the optimum for nanocatalyst post-production. The gained insights may aid speeding up the development of new materials by electrochemical dealloying as an easy-To-control post-processing route to tune the properties of existing nanoparticles, instead of having to alter usually delicate synthesis routes as a whole. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/d0ta04880a

• 2020 • 162	Electroenzymatic Nitrogen Fixation Using a MoFe Protein System Immobilized in an Organic Redox Polymer Lee, Y.S. and Ruff, A. and Cai, R. and Lim, K. and Schuhmann, W. and Minteer, S.D. Angewandte Chemie - International Edition 59 16511-16516 (2020) We report an organic redox-polymer-based electroenzymatic nitrogen fixation system using a metal-free redox polymer, namely neutral-red-modified poly(glycidyl methacrylate-co-methylmethacrylate-co-poly(ethyleneglycol)methacrylate) with a low redox potential of −0.58 V vs. SCE. The stable and efficient electric wiring of nitrogenase within the redox polymer matrix enables mediated bioelectrocatalysis of N3−, NO2− and N2 to NH3 catalyzed by the MoFe protein via the polymer-bound redox moieties distributed in the polymer matrix in the absence of the Fe protein. Bulk bioelectrosynthetic experiments produced 209±30 nmol NH3 nmol MoFe−1 h−1 from N2 reduction. 15N2 labeling experiments and NMR analysis were performed to confirm biosynthetic N2 reduction to NH3. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA
  	view abstract	doi: 10.1002/anie.202007198

• 2020 • 161	Femtosecond laser shock peening on the surface of NiTi shape memory alloy Wang, H. and Gurevich, E.L. and Ostendorf, A. Procedia CIRP 94 910-913 (2020) Laser shock peening with a femtosecond laser system was presented in this research work. The NiTi shape memory alloy was processed by the femtosecond laser shock peening (FsLSP) treatment without a protective layer in the air. Femtosecond laser shock peening is a new surface technology, which can induce an intense shock wave with low single laser pulse energy under atmospheric conditions. The surface topography, roughness, microhardness, and wear resistance were measured on the surface of NiTi alloy before and after femtosecond laser peening treatment. The results showed that the surface roughness and microhardness could be increased after femtosecond laser shock peening, which may be due to the laser ablation and micro-plastic deformation induced by the shock wave. The wear property of NiTi alloy was improved, which may be attributed to the FsLSPed surface texturing and enhancement of surface microhardness. © 2020 The Authors. Published by Elsevier B.V.
  	view abstract	doi: 10.1016/j.procir.2020.09.071

• 2020 • 160	Formation of a 2D Meta-stable Oxide by Differential Oxidation of AgCu Alloys Schweinar, K. and Beeg, S. and Hartwig, C. and Rajamathi, C.R. and Kasian, O. and Piccinin, S. and Prieto, M.J. and Tanase, L.C. and Gottlob, D.M. and Schmidt, T. and Raabe, D. and Schlögl, R. and Gault, B. and Jones, T.E. and Gr... ACS Applied Materials and Interfaces 12 23595-23605 (2020) Metal alloy catalysts can develop complex surface structures when exposed to reactive atmospheres. The structures of the resulting surfaces have intricate relationships with a myriad of factors, such as the affinity of the individual alloying elements to the components of the gas atmosphere and the bond strengths of the multitude of low-energy surface compounds that can be formed. Identifying the atomic structure of such surfaces is a prerequisite for establishing structure-property relationships, as well as for modeling such catalysts in ab initio calculations. Here, we show that an alloy, consisting of an oxophilic metal (Cu) diluted into a noble metal (Ag), forms a meta-stable two-dimensional oxide monolayer, when the alloy is subjected to oxidative reaction conditions. The presence of this oxide is correlated with selectivity in the corresponding test reaction of ethylene epoxidation. In the present study, using a combination of in situ, ex situ, and theoretical methods (NAP-XPS, XPEEM, LEED, and DFT), we determine the structure to be a two-dimensional analogue of Cu2O, resembling a single lattice plane of Cu2O. The overlayer holds a pseudo-epitaxial relationship with the underlying noble metal. Spectroscopic evidence shows that the oxide's electronic structure is qualitatively distinct from its three-dimensional counterpart, and because of weak electronic coupling with the underlying noble metal, it exhibits metallic properties. These findings provide precise details of this peculiar structure and valuable insights into how alloying can enhance catalytic properties. Copyright © 2020 American Chemical Society.
  	view abstract	doi: 10.1021/acsami.0c03963

• 2020 • 159	In situ synthesis of a binary Ti–10at% Nb alloy by electron beam melting using a mixture of elemental niobium and titanium powders Surmeneva, M.A. and Koptyug, A. and Khrapov, D. and Ivanov, Y.F. and Mishurova, T. and Evsevleev, S. and Prymak, O. and Loza, K. and Epple, M. and Bruno, G. and Surmenev, R.A. Journal of Materials Processing Technology 282 (2020) This study reports the results of the preliminary assessment to fabricate Ti-10at% Nb alloy by electron beam melting (EBM®) from a blend of elemental Nb and Ti powders. The microstructure of the EBM-manufactured Ti-10at% Nb alloys is sensitive to the following factors: different sintering properties of Nb and Ti powders, powder particle properties, material viscosities at varying melt pool temperatures, β-stabilizer element content and the EBM® process parameters. Three phases were observed in as-manufactured Ti-10at% Nb alloy: μm-size Nb phase, a Nb-rich β-solid solution surrounding Nb phase, lamellar structured α-phase and β-solid solution with different distribution and volume fraction. Thus, the combination of powder particle characteristics, very short time material spends in molten condition and sluggish kinetics of mixing and diffusional process in Ti-Nb alloy results in heterogeneous microstructures depending on the local Nb content in the powder blend and the EBM® process conditions. © 2020 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jmatprotec.2020.116646

• 2020 • 158	In situ X-ray emission and high-resolution X-ray absorption spectroscopy applied to Ni-based bimetallic dry methane reforming catalysts Beheshti Askari, A. and Al Samarai, M. and Hiraoka, N. and Ishii, H. and Tillmann, L. and Muhler, M. and Debeer, S. Nanoscale 12 15185-15192 (2020) The promoting effect of cobalt on the catalytic activity of a NiCoO Dry Methane Reforming (DMR) catalyst was studied by a combination of in situ Kβ X-ray Emission Spectroscopy (XES) and Kβ-detected High Energy Resolution Fluorescence Detected X-ray absorption spectroscopy (HERFD XAS). Following the calcination process, Ni XES and Kβ-detected HERFD XAS data revealed that the NiO coordination in the NiCoO catalyst has a higher degree of symmetry and is different than that of pure NiO/γ-Al2O3. Following the reductive activation, it was found that the NiCoO/γ-Al2O3 catalyst required a relatively higher temperature compared to the monometallic NiO/γ-Al2O3 catalyst. This finding suggests that Co is hampering the reduction of Ni in the NiCoO catalyst by modulation of its electronic structure. It has also been previously shown that the addition of Co enhances the DMR activity. Further, the Kβ XES spectrum of the partly reduced catalysts at 450 °C reveals that the Ni sites in the NiCoO catalyst are electronically different from the NiO catalyst. The in situ X-ray spectroscopic study demonstrates that reduced metallic Co and Ni are the primary species present after reduction and are preserved under DMR conditions. However, the NiCo catalyst appears to always be somewhat more oxidized than the Ni-only species, suggesting that the presence of cobalt modulates the Ni electronic structure. The electronic structural modulations resulting from the presence of Co may be the key to the increased activity of the NiCo catalyst relative to the Ni-only catalyst. This study emphasizes the potential of in situ X-ray spectroscopy experiments for probing the electronic structure of catalytic materials during activation and under operating conditions. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/d0nr01960g

• 2020 • 157	In Situ X-ray Microscopy Reveals Particle Dynamics in a NiCo Dry Methane Reforming Catalyst under Operating Conditions Beheshti Askari, A. and Al Samarai, M. and Morana, B. and Tillmann, L. and Pfänder, N. and Wandzilak, A. and Watts, B. and Belkhou, R. and Muhler, M. and Muhler, M. and Debeer, S. ACS Catalysis 10 6223-6230 (2020) Herein, we report the synthesis of a γ-Al2O3-supported NiCo catalyst for dry methane reforming (DMR) and study the catalyst using in situ scanning transmission X-ray microscopy (STXM) during the reduction (activation step) and under reaction conditions. During the reduction process, the NiCo alloy particles undergo elemental segregation with Co migrating toward the center of the catalyst particles and Ni migrating to the outer surfaces. Under DMR conditions, the segregated structure is maintained, thus hinting at the importance of this structure to optimal catalytic functions. Finally, the formation of Ni-rich branches on the surface of the particles is observed during DMR, suggesting that the loss of Ni from the outer shell may play a role in the reduced stability and hence catalyst deactivation. These findings provide insights into the morphological and electronic structural changes that occur in a NiCo-based catalyst during DMR. Further, this study emphasizes the need to study catalysts under operating conditions in order to elucidate material dynamics during the reaction. © 2020 American Chemical Society.
  	view abstract	doi: 10.1021/acscatal.9b05517

• 2020 • 156	Influence of lattice misfit on the deformation behaviour of α2/γ lamellae in TiAl alloys Chauniyal, A. and Janisch, R. Materials Science and Engineering A 796 (2020) Interfaces play a significant role in the deformation behaviour of lamellar two-phase TiAl alloys and contribute to their increased strength. We study the deformation behaviour of α2/γ bilayers with either coherent or semicoherent interfaces, using atomistic simulations. We identify the nucleation sites for dislocations and decouple the effects of the microstructural parameters volume fraction and layer thickness on the yield stress and strain. Uniaxial tensile tests are carried out on bi-layer specimens with α2 and γ phases along directions parallel and perpendicular to the interface. Coherent α2∕γ bi-layers show residual stresses due to lattice mismatch which are linearly related to the volume fractions of the phases. These residual stresses, superimposed with tensile stresses during loading, lead to early yielding of the γ phase. In contrast, a semi-coherent interface leads to negligible residual stresses, but contains misfit dislocations which create localized stresses within the γ layer and thus contributes to dislocation nucleation. We show that along loading directions parallel to the interface, the layer thickness does not affect the deformation behaviour, irrespective of the type of interface, instead volume fraction is the governing parameter. When loading perpendicular to the interface, the absolute layer thickness does not affect the deformation behaviour of a bi-layer with a coherent interface, but determines the yield stress and strain in case of a semi coherent interface. © 2020 Elsevier B.V.
  	view abstract	doi: 10.1016/j.msea.2020.140053

• 2020 • 155	Influence of precipitation hardening on the high-temperature sliding wear resistance of an aluminium alloyed iron-nickel base alloy Krell, J. and Röttger, A. and Ziesing, U. and Theisen, W. Tribology International 148 (2020) This work investigates the effects of precipitation hardening on hot hardness and high-temperature sliding wear resistance of an iron-nickel base alloy. Three variants of a carbide rich alloy containing 0, 2 and 3 wt.-% aluminium were manufactured and aged for 24 h at 650, 700 and 750 °C. Hot hardness (20–800 °C) and sliding wear tests (600 °C) were conducted for each condition. The addition of aluminium has little effect on the type or volume content of the carbides. Ageing caused the precipitation of NiAl in the aluminium-containing alloys. The precipitation-hardened samples show higher hot hardness and better hot wear resistance. The lower wear loss can mainly be attributed to the improved support of the carbides by the precipitation strengthened matrix. © 2020
  	view abstract	doi: 10.1016/j.triboint.2020.106342

• 2020 • 154	Influence of Ti3Ni4 precipitates on the indentation-induced two-way shape-memory effect in Nickel-Titanium Laursen, C.M. and Peter, N.J. and Gerstein, G. and Maier, H.J. and Dehm, G. and Frick, C.P. Materials Science and Engineering A 792 (2020) Nickel Titanium (NiTi) alloys have been used for many years based on their unique ability to exhibit the shape-memory and pseudoelastic effects. The indentation-induced two-way shape memory effect (TWSME) is a specific sub-capability of this alloy such that a repeatably switchable surface can be created by “training” the material through mechanical indentation and activated through temperature transitions between the austenitic and martensitic phases. This study sought to observe the effect Ti3Ni4 precipitate aging would have on the indentation-induced TWSME. Ti3Ni4 has previously been shown as an effective method to alter NiTi transformation temperatures, yet it was unclear what effect localized stress fields around precipitates would have on the TWSME. The results presented here indicate that growth of precipitates in the alloy before training suppresses the resultant indentation-induced TWSME, and small precipitates, which cause minimal lattice mismatch to the matrix (i.e. highest coherency), have the strongest role in suppressing the effect. It is suggest that lattice coherency acts to inhibit plastic deformation, suppressing the creation of the preferred microstructure under the indent required to guide the TWSME. Therefore, precipitate aging is not a recommended alternative to precise alloying in order to alter transformation temperatures with the goal of maximizing the indentation-induced TWSME effect within a targeted temperate transformation regime. © 2020 Elsevier B.V.
  	view abstract	doi: 10.1016/j.msea.2020.139373

• 2020 • 153	Local and Nonlocal Electron Dynamics of Au/Fe/MgO (001) Heterostructures Analyzed by Time-Resolved Two-Photon Photoemission Spectroscopy Beyazit, Y. and Beckord, J. and Zhou, P. and Meyburg, J.P. and Kühne, F. and Diesing, D. and Ligges, M. and Bovensiepen, U. Physical Review Letters 125 (2020) Employing femtosecond laser pulses in front and back side pumping of Au/Fe/MgO(001) combined with detection in two-photon photoelectron emission spectroscopy, we analyze local relaxation dynamics of excited electrons in buried Fe, injection into Au across the Fe-Au interface, and electron transport across the Au layer at 0.6 to 2.0 eV above the Fermi energy. By analysis as a function of Au film thickness we obtain the electron lifetimes of bulk Au and Fe and distinguish the relaxation in the heterostructure's constituents. We also show that the excited electrons propagate through Au in a superdiffusive regime and conclude further that electron injection across the epitaxial interface proceeds ballistically by electron wave packet propagation. © 2020 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevLett.125.076803

• 2020 • 152	Magnetic response of FeRh to static and dynamic disorder Eggert, B. and Schmeink, A. and Lill, J. and Liedke, M.O. and Kentsch, U. and Butterling, M. and Wagner, A. and Pascarelli, S. and Potzger, K. and Lindner, J. and Thomson, T. and Fassbender, J. and Ollefs, K. and Keune, W. and Bal... RSC Advances 10 14386-14395 (2020) Atomic scale defects generated using focused ion as well as laser beams can activate ferromagnetism in initially non-ferromagnetic B2 ordered alloy thin film templates. Such defects can be induced locally, confining the ferromagnetic objects within well-defined nanoscale regions. The characterization of these atomic scale defects is challenging, and the mechanism for the emergence of ferromagnetism due to sensitive lattice disordering is unclear. Here we directly probe a variety of microscopic defects in systematically disordered B2 FeRh thin films that are initially antiferromagnetic and undergo a thermally-driven isostructural phase transition to a volatile ferromagnetic state. We show that the presence of static disorder i.e., the slight deviations of atoms from their equilibrium sites is sufficient to induce a non-volatile ferromagnetic state at room temperature. A static mean square relative displacement of 9 × 10-4 Å-2 is associated with the occurrence of non-volatile ferromagnetism and replicates a snapshot of the dynamic disorder observed in the thermally-driven ferromagnetic state. The equivalence of static and dynamic disorder with respect to the ferromagnetic behavior can provide insights into the emergence of ferromagnetic coupling as well as achieving tunable magnetic properties through defect manipulations in alloys. This journal is © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/d0ra01410a

• 2020 • 151	Magneto-structural correlations in a systematically disordered B2 lattice Ehrler, J. and Sanyal, B. and Grenzer, J. and Zhou, S. and Böttger, R. and Eggert, B. and Wende, H. and Lindner, J. and Fassbender, J. and Leyens, C. and Potzger, K. and Bali, R. New Journal of Physics 22 (2020) Ferromagnetism in certain B2 ordered alloys such as Fe60Al40 can be switched on, and tuned, via antisite disordering of the atomic arrangement. The disordering is accompanied by a ∼1 % increase in the lattice parameter. Here we performed a systematic disordering of B2 Fe60Al40 thin films, and obtained correlations between the order parameter (S), lattice parameter (a 0), and the induced saturation magnetization (M s). As the lattice is gradually disordered, a critical point occurs at 1-S = 0.6 and a 0 = 2.91 Å, where a sharp increase of the M s is observed. DFT calculations suggest that below the critical point the system magnetically behaves as it would still be fully ordered, whereas above, it is largely the increase of a 0 in the disordered state that determines the M s. The insights obtained here can be useful for achieving tailored magnetic properties in alloys through disordering. © 2020 The Author(s). Published by IOP Publishing Ltd on behalf of the Institute of Physics and Deutsche Physikalische Gesellschaft.
  	view abstract	doi: 10.1088/1367-2630/ab944a

• 2020 • 150	Micro-, macromechanical and aeroelastic investigation of glass - fiber based, lightweight turbomachinery components Iseni, S. and Prasad, M.R.G. and Hartmaier, A. and Holeczek, K. and Modeler, N. and di Mare, F. Proceedings of the ASME Turbo Expo 10A-2020 (2020) A major technical challenge for modern aero engines is the development of designs which reduce noise and emission whilst increasing aerodynamic efficiency and ensuring aeroelastic stability of low-temperature engine components such as fans and low-pressure compressors. Composites are used in aviation due to their excellent stiffness and strength properties, which also enable additional flexibility in the design process. The weight reduction of the turbomachine components, due to composite materials and lighter engines, is especially relevant for the design and developments of hybrid-electric or distributed propulsion systems [1]. To accomplish this, a representative volume element (RVE) of a glass-fiber reinforced polymer is created, describing the geometrical arrangement of the textile reinforcement structure within the polymer matrix. For both phases, realistic linear elastic properties are assumed. This RVE will be investigated with the finite element method under various loading conditions to assess its anisotropic elastic properties and also its damping behaviour for elastic waves. To study the influence of delamination on the mechanical properties, small defects will be introduced into the model at the interface between reinforcement and matrix. Based on this micromechanical approach, a constitutive model for the composite will be formulated that describes the anisotropic properties as well as the damping behaviour. This constitutive model is then used to describe the material response in a macro-mechanical model, which serves as the basis for an aeroelastic analysis of a 1/3-scaled high-speed fan using a conventional (Ti-6Al -4V) and fiber composite material. Copyright © 2020 ASME
  	view abstract	doi: 10.1115/GT2020-14951

• 2020 • 149	Microhardness and microabrasion behaviour of NiTi shape memory alloy after femtosecond laser shock peening without coating in air Wang, H. and Gurevich, E.L. and Ostendorf, A. Proceedings of SPIE - The International Society for Optical Engineering 11273 (2020) The experiment study presents the influence of femtosecond laser shock peening (FsLSP) without a protective layer in the air on the surface hardness and surface mechanical property of NiTi shape memory alloy. Femtosecond laser shock peening is a new possibility of direct laser ablation without any protective layer under atmospheric conditions, which can produce intense shock waves with low pulse energy in the air. The average surface roughness values of the NiTi alloy samples were measured, because the surface roughness may affect its friction resistance. The results showed that the surface roughness of NiTi increased after femtosecond laser shock peening treatment. In comparison with the initial state, the coefficient of friction decreased and surface microhardness increased after femtosecond laser shock peening treatment with different FsLSP parameters. This improvement of wear properties may be attributed to the enhancement of surface microhardness and surface titanium oxide layer induced by the shock wave and laser ablation during FsLSP treatment. © 2020 SPIE.
  	view abstract	doi: 10.1117/12.2543550

• 2020 • 148	Nanoglass–Nanocrystal Composite—a Novel Material Class for Enhanced Strength–Plasticity Synergy Katnagallu, S. and Wu, G. and Singh, S.P. and Nandam, S.H. and Xia, W. and Stephenson, L.T. and Gleiter, H. and Schwaiger, R. and Hahn, H. and Herbig, M. and Raabe, D. and Gault, B. and Balachandran, S. Small 16 (2020) The properties of a material can be engineered by manipulating its atomic and chemical architecture. Nanoglasses which have been recently invented and comprise nanosized glassy particles separated by amorphous interfaces, have shown promising properties. A potential way to exploit the structural benefits of nanoglasses and of nanocrystalline materials is to optimize the composition to obtain crystals forming within the glassy particles. Here, a metastable Fe-10 at% Sc nanoglass is synthesized. A complex hierarchical microstructure is evidenced experimentally at the atomic scale. This bulk material comprises grains of a Fe90Sc10 amorphous matrix separated by an amorphous interfacial network enriched and likely stabilized by hydrogen, and property-enhancing pure-Fe nanocrystals self-assembled within the matrix. This composite structure leads a yield strength above 2.5 GPa with an exceptional quasi-homogeneous plastic flow of more than 60% in compression. This work opens new pathways to design materials with even superior properties. © 2020 The Authors. Published by Wiley-VCH GmbH
  	view abstract	doi: 10.1002/smll.202004400

• 2020 • 147	Nitrogen doping of MoSx thin films sputtered by reactive High Power Impulse Magnetron Sputtering Tillmann, W. and Wittig, A. and Moldenhauer, H. and Thomann, C.-A. and Debus, J. and Aurich, D. and Bruemmer, A. Thin Solid Films 713 (2020) Incorporating nitrogen into non-stoichiometric molybdenum disulfide (MoSx) thin films is a promising approach in order to improve the mechanical properties. Nevertheless, the adhesion between the film and the substrate is still challenging and the interaction between the mechanical and the tribological properties is not fully understood yet. Subsequently, reactive High Power Impulse Magnetron Sputtering (HiPIMS) is used to deposit nitrogen doped MoSx thin films with different nitrogen amounts on 16MnCr5 steel. The interaction between the structural changes, the mechanical properties and the tribological behavior depending on the nitrogen amount is investigated. The results prove that an increasing amount of nitrogen significantly affects the structure and the tribo-mechanical properties of the thin films. X-ray diffraction analysis reveals a transformation from crystalline to amorphous with an increasing amount of nitrogen from (7.1 ± 0.3) at.-% to (19.5 ± 0.5) at.-%. This transformation is related to a suppression of the columnar microstructure as well as an increasing hardness and Young‘s modulus from (0.14 ± 0.02) GPa, and (5.28 ± 0.32) GPa for the undoped film, to (5.12 ± 0.32) GPa and (92.5 ± 6.2) GPa, for the film with the highest nitrogen amount. The results of the Rockwell indentation tests show that the films with a small amount of nitrogen exhibit an improved adhesion behavior. The wear coefficient can be reduced to a quarter of the value of the undoped MoSx film, whereas coefficients of friction are at similar level of 0.2 in ambient air. Reactive HiPIMS has proven to be promising to deposit nitrogen doped MoSx thin films on steel substrates, which reveal improved mechanical properties and an excellent transfer film built-up during the tribo-tests without failures. © 2020 Elsevier B.V.
  	view abstract	doi: 10.1016/j.tsf.2020.138267

• 2020 • 146	Picosecond laser-induced surface structures on alloys in liquids and their influence on nanoparticle productivity during laser ablation Nadarajah, R. and Barcikowski, S. and Gökce, B. Optics Express 28 2909-2924 (2020) The productivity of nanoparticles formed by laser ablation of gold-silver and iron-gold alloy as well as copper and iron-nickel alloy targets in water is correlated with the formation of laser-induced surface structures. At a laser fluence optimized for maximum nanoparticle productivity, it is found that a binary alloy with an equimolar ratio forms laser-induced periodic surface structures (LIPSS) after ablation, if one of the constituent metals also form LIPSS. The ablation rate of nanoparticles linearly depends on the laser fluence if LIPSS is not formed, while a logarithmic trend and a decrease in productivity is evident when LIPSS is formed. To cancel LIPSS formation and recover from this decrease, a change to circularly polarized light is performed and an increase in nanoparticle productivity of more than 30% is observed. © 2020 Optical Society of America under the terms of the OSA Open Access Publishing Agreement
  	view abstract	doi: 10.1364/OE.28.002909

• 2020 • 145	Probing catalytic surfaces by correlative scanning photoemission electron microscopy and atom probe tomography Schweinar, K. and Nicholls, R.L. and Rajamathi, C.R. and Zeller, P. and Amati, M. and Gregoratti, L. and Raabe, D. and Greiner, M. and Gault, B. and Kasian, O. Journal of Materials Chemistry A 8 388-400 (2020) The chemical composition and the electronic state of the surface of alloys or mixed oxides with enhanced electrocatalytic properties are usually heterogeneous at the nanoscale. The non-uniform distribution of the potential across their surface affects both activity and stability. Studying such heterogeneities at the relevant length scale is crucial for understanding the relationships between structure and catalytic behaviour. Here, we demonstrate an experimental approach combining scanning photoemission electron microscopy and atom probe tomography performed at identical locations to characterise the surface's structure and oxidation states, and the chemical composition of the surface and sub-surface regions. Showcased on an Ir-Ru thermally grown oxide, an efficient catalyst for the anodic oxygen evolution reaction, the complementary techniques yield consistent results in terms of the determined surface oxidation states and local oxide stoichiometry. Significant chemical heterogeneities in the sputter-deposited Ir-Ru alloy thin films govern the oxide's chemistry, observed after thermal oxidation both laterally and vertically. While the oxide grains have a composition of Ir0.94Ru0.06O2, the composition in the grain boundary region varies from Ir0.70Ru0.30O2 to Ir0.40Ru0.60O2 and eventually to Ir0.75Ru0.25O2 from the top surface into the depth. The influence of such compositional non-uniformities on the catalytic performance of the material is discussed, along with possible engineering levers for the synthesis of more stable and reactive mixed oxides. The proposed method provides a framework for investigating materials of interest in the field of electrocatalysis and beyond. This journal is © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c9ta10818a

• 2020 • 144	Sintering and biocompatibility of blended elemental Ti-xNb alloys Chen, Y. and Han, P. and Dehghan-Manshadi, A. and Kent, D. and Ehtemam-Haghighi, S. and Jowers, C. and Bermingham, M. and Li, T. and Cooper-White, J. and Dargusch, M.S. Journal of the Mechanical Behavior of Biomedical Materials 104 (2020) Titanium-niobium (Ti–Nb) alloys have great potential for biomedical applications due to their superior biocompatibility and mechanical properties that match closely to human bone. Powder metallurgy is an ideal technology for efficient manufacture of titanium alloys to generate net-shape, intricately featured and porous components. This work reports on the effects of Nb concentrations on sintered Ti-xNb alloys with the aim to establish an optimal composition in respect to mechanical and biological performances. Ti-xNb alloys with 33, 40, 56 and 66 wt% Nb were fabricated from elemental powders and the sintering response, mechanical properties, microstructures and biocompatibility assessed and compared to conventional commercial purity titanium (CPTi). The sintered densities for all Ti-xNb compositions were around 95%, reducing slightly with increasing Nb due to increasing open porosity. Higher Nb levels retarded sintering leading to more inhomogeneous phase and pore distributions. The compressive strength decreased with increasing Nb, while all Ti-xNb alloys displayed higher strengths than CPTi except the Ti–66Nb alloy. The Young's moduli of the Ti-xNb alloys with ≥40 wt% Nb were substantially lower (30–50%) than CPTi. In-vitro cell culture testing revealed excellent biocompatibility for all Ti-xNb alloys comparable or better than tissue culture plate and CPTi controls, with the Ti–40Nb alloy exhibiting superior cell-material interactions. In view of its mechanical and biological performance, the Ti–40Nb composition is most promising for hard tissue engineering applications. © 2020
  	view abstract	doi: 10.1016/j.jmbbm.2020.103691

• 2020 • 143	Stepwise Bi-Bi Bond Formation: From a Bi-centered Radical to Bi4Butterfly and Bi8Cuneane-Type Clusters Krüger, J. and Wölper, C. and Schulz, S. Inorganic Chemistry 59 11142-11151 (2020) In contrast to their lighter homologues (P, As, Sb), the synthesis of polybismuthane clusters is still restricted to classical solid-state approaches. We herein report on systematic reduction reactions of different bismuth precursors with Ga(I) and Mg(I) complexes. This study not only yielded the first metal-coordinated tetrabismuthane ([{L1(Cl)Ga}2-μ,η1:1-Bi4] 3, L1 = HC[C(Me)N(2,6-i-Pr2C6H3)]2) and realgar-type bismuth cluster ([(L2Mg)4(μ4,η2:2:2:2-Bi8)] 4, L2 = HC[C(Me)N(2,4,6-Me3C6H2)]2) in addition to the bismuth-centered radical [L1Ga(Cl)]2Bi• 1 and dibismuthene [L1(Cl)GaBi]2 2, but clearly demonstrates the crucial role of the substituents and the oxidation state of the bismuth precursor as well as the specific reduction potential of the main group metal reductants on the product formation. Compounds 3 and 4 were spectroscopically characterized (1H, 13C NMR, IR), and the structures of 1-4 were determined by single-crystal X-ray diffraction. Computational calculations gave deeper insights into the electronic structures of 1′, 3′, and 4′. Copyright © 2020 American Chemical Society.
  	view abstract	doi: 10.1021/acs.inorgchem.0c01657

• 2020 • 142	Structural evolution and magnetic properties of high-entropy CuCrFeTiNi alloys prepared by high-energy ball milling and spark plasma sintering Shkodich, N.F. and Spasova, M. and Farle, M. and Kovalev, D.Y. and Nepapushev, A.A. and Kuskov, K.V. and Vergunova, Y.S. and Scheck, Y.B. and Rogachev, A.S. Journal of Alloys and Compounds 816 (2020) A powder of equiatomic CuCrFeTiNi high-entropy alloy (HEA) was prepared by short-term (30 min) high-energy ball milling (HEBM). Our structural and chemical analysis showed that micron sized particles of bcc CuCrFeTiNi consisting of nanosized crystalline grains (∼6 nm) could be obtained after 30 min of HEBM. The influence of milling time (30 ÷ 240 min) on structural and magnetic transformations of CuCrFeTiNi powder mixture was investigated. The HEA powders were thermally stable up to 500°С based on DSC results. The HEA powder was subsequently consolidated by spark plasma sintering at 700 °C resulting in a consolidated bulk HEA with co-existing bcc and fcc phases. The as-milled CuCrFeTiNi powder blend contained a solid solution with bcc (Im3m) structure. Annealing at 600°С (t = 180 min) increased the crystallinity of the α-phase (bcc) and gave rise to formation of the γ-phase (fcc, Fm3m) whose amount grew with increasing dwell time. Between 800 and 1000°С, a tetragonal intermetallic σ-phase – most likely FeCr - appeared and subsequently vanished. At 1000°С, the final product was found to contain two solid solutions based on the γ-phase (fcc). The Vickers hardness HvHEBM = 7.7 GPa of the SPS consolidated CuCrFeTiNi alloy (milled for t = 180 min) was markedly higher than the one of SPS-produced ones without HEBM (Hv = 2.1 GPa). Paramagnetic behavior at room temperature with a small ferromagnetic contribution at low fields was observed for as-milled powder after 180 min of HEBM. A small magnetic hysteresis was observed at 5 K and 300 K with a coercive field of around 16 kA/m. Above 100 K, the inverse susceptibility of a HEA powder ball-milled for t = 240 min showed a clear paramagnetic response. The Curie temperature TC ∼50 K was found. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jallcom.2019.152611

• 2020 • 141	Structural evolution of bimetallic Co-Cu catalysts in CO hydrogenation to higher alcohols at high pressure Göbel, C. and Schmidt, S. and Froese, C. and Fu, Q. and Chen, Y.-T. and Pan, Q. and Muhler, M. Journal of Catalysis 383 33-41 (2020) Bimetallic Co-Cu catalysts are widely applied in higher alcohol synthesis (HAS), but the formation of the final active structure has not yet been fully clarified, especially for Co-rich catalysts. We investigated the structural evolution of a Co-Cu catalyst (Co:Cu = 2) from the hydrotalcite precursor containing additional Al3+ and Zn2+ to the final active state after 80 h under reaction conditions at 280 °C and 60 bar. The reconstruction of the bimetallic Co-Cu nanoparticles obtained by H2 reduction was induced by the feed gas consisting of an equimolar H2 and CO syngas mixture resulting in fast phase separation and sintering of metallic Cu0 and Co0 in the first 2 h time on stream (TOS) and a continuous carbidization of Co0 forming Co2C and its sintering until steady state was reached after 40 h TOS. An intergrowth of metallic Cu0 nanoparticles with Co2C nanoparticles was observed to occur under reaction conditions. The high selectivity to oxygenates amounting to 41% compared with 29% to hydrocarbons is ascribed to the multi-functional Co2C/Cu0 interface enabling dissociative CO adsorption, hydrogenation and CO insertion. The formation of hydrogenated carbon species (CxHy) originating from dissociative CO chemisorption is assumed to be favored by hydrogen spillover from Cu0 to Co2C. The adsorption sites for molecular CO provided by both Cu0 and Co2C facilitate its insertion into the CxHy intermediates thus leading to a higher selectivity to alcohols following the Anderson-Schulz-Flory distribution. © 2020 Elsevier Inc.
  	view abstract	doi: 10.1016/j.jcat.2020.01.004

• 2020 • 140	Structural stability of Co–V intermetallic phases and thermodynamic description of the Co–V system Wang, P. and Hammerschmidt, T. and Kattner, U.R. and Olson, G.B. Calphad: Computer Coupling of Phase Diagrams and Thermochemistry 68 (2020) The Co–V system has been reviewed. Density functional theory (DFT) calculations using the generalized gradient approximation (GGA) were used to obtain the energies for the end-members for all three intermediate phases, Co3V, σ and CoV3. Results from DFT calculations considering spin polarization were used to evaluate the CALPHAD (Calculation of phase diagrams) model parameters. The method to evaluate the contribution of the magnetism to the energies of Co-rich compounds that was introduced in our previous work is presented in more detail in the present work. For the description of the σ phase, the magnetic part of the total energy is included in the description of the pure Co end-member compound resulting in a non-linear description of the magnetic contribution over composition. The calculated phase diagram obtained from the present CALPHAD description is in good agreement with the experimental data. The metastable FCC-L12 phase diagram was calculated and compared with experimental data. © 2019 Elsevier Ltd
  	view abstract	doi: 10.1016/j.calphad.2019.101729

• 2020 • 139	Surface modification of NiTi alloy by ultrashort pulsed laser shock peening Wang, H. and Kalchev, Y. and Wang, H. and Yan, K. and Gurevich, E.L. and Ostendorf, A. Surface and Coatings Technology 394 (2020) This research paper presents the attempt at ultrashort pulsed laser shock peening with absence of absorptive layer and confining medium which could enhance surface microhardness and the abrasion property of NiTi shape memory alloy. The average roughness values of NiTi specimen were measured on the surface, because the roughness would affect the friction resistance. The microhardness and Young's modulus were investigated at different position of single laser spot by nanoindentation technique. The pin-on-plate sliding abrasion testing were performed with different load-force (0.5 N and 2 N) for different testing time. Results showed that ultrashort pulsed laser shock peening treatment would cause a significant improvement on friction coefficient and abrasion property, which was attributed to the change of surface modification, such as roughness, microhardness, microstructure and titanium oxide layer, but the ultrashort pulsed laser shock peening treatment did not enhance its tensile strength during present research. © 2020 Elsevier B.V.
  	view abstract	doi: 10.1016/j.surfcoat.2020.125899

• 2020 • 138	The importance of nanoscale confinement to electrocatalytic performance Wordsworth, J. and Benedetti, T.M. and Alinezhad, A. and Tilley, R.D. and Edwards, M.A. and Schuhmann, W. and Gooding, J.J. Chemical Science 11 1233-1240 (2020) Electrocatalytic nanoparticles that mimic the three-dimensional geometric architecture of enzymes where the reaction occurs down a substrate channel isolated from bulk solution, referred to herein as nanozymes, were used to explore the impact of nano-confinement on electrocatalytic reactions. Surfactant covered Pt-Ni nanozyme nanoparticles, with Ni etched from the nanoparticles, possess a nanoscale channel in which the active sites for electrocatalysis of oxygen reduction are located. Different particle compositions and etching parameters allowed synthesis of nanoparticles with different average substrate channel diameters that have varying amounts of nano-confinement. The results showed that in the kinetically limited regime at low overpotentials, the smaller the substrate channels the higher the specific activity of the electrocatalyst. This is attributed to higher concentrations of protons, relative to bulk solution, required to balance the potential inside the nano-confined channel. However, at higher overpotentials where limitation by mass transport of oxygen becomes important, the nanozymes with larger substrate channels showed higher electrocatalytic activity. A reaction-diffusion model revealed that the higher electrocatalytic activity at low overpotentials with smaller substrate channels can be explained by the higher concentration of protons. The model suggests that the dominant mode of mass transport to achieve these high concentrations is by migration, exemplifying how nano-confinement can be used to enhance reaction rates. Experimental and theoretical data show that under mass transport limiting potentials, the nano-confinement has no effect and the reaction only occurs at the entrance of the substrate channel at the nanoparticle surface. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c9sc05611d

• 2020 • 137	The steady-state kinetics of CO hydrogenation to higher alcohols over a bulk Co-Cu catalyst Göbel, C. and Schmidt, S. and Froese, C. and Bujara, T. and Viktor Scherer and Muhler, M. Journal of Catalysis (2020) The kinetics of higher alcohol synthesis was investigated using a hydrotalcite-derived Co-Cu-based catalyst aiming at a deeper understanding of the complex reaction network. At steady state similar chain growth probabilities of about 0.4 according to the Anderson-Schulz-Flory distribution were observed for alcohols, hydrocarbons and olefins indicating common intermediates. Alkanes were found to be formed consecutively from primarily formed olefins. The observed decrease of the selectivities to alcohols with increasing CO conversion at higher temperatures and higher residence times is ascribed to an increased availability of adsorbed atomic hydrogen, which decreases the saturated coverage of CO-derived CxHyOz species favoring hydrocarbon formation. Correspondingly, reaction orders of 0 and 0.8 for CO and H2, respectively, were derived based on a power-law approach including an apparent activation energy of 140 kJ mol−1. A reaction network based on the CO insertion factor was established, in which the competing reactions β-hydrogen elimination, chain growth and CO insertion proceed from common adsorbed CxHy intermediates. Selective higher alcohol formation was favored at low temperatures and short residence times, high pressures and a moderate H2:CO ratio of 1 requiring a compromise between conversion and selectivity. © 2020 Elsevier Inc.
  	view abstract	doi: 10.1016/j.jcat.2020.10.017

• 2020 • 136	The sum is more than its parts: stability of MnFe oxide nanoparticles supported on oxygen-functionalized multi-walled carbon nanotubes at alternating oxygen reduction reaction and oxygen evolution reaction conditions Morales, D.M. and Kazakova, M.A. and Purcel, M. and Masa, J. and Schuhmann, W. Journal of Solid State Electrochemistry 24 2901-2906 (2020) Successful design of reversible oxygen electrocatalysts does not only require to consider their activity towards the oxygen reduction (ORR) and the oxygen evolution reactions (OER), but also their electrochemical stability at alternating ORR and OER operating conditions, which is important for potential applications in reversible electrolyzers/fuel cells or metal/air batteries. We show that the combination of catalyst materials containing stable ORR active sites with those containing stable OER active sites may result in a stable ORR/OER catalyst if each of the active components can satisfy the current demand of their respective reaction. We compare the ORR/OER performances of oxides of Mn (stable ORR active sites), Fe (stable OER active sites), and bimetallic Mn0.5Fe0.5 (reversible ORR/OER catalyst) supported on oxidized multi-walled carbon nanotubes. Despite the instability of Mn and Fe oxide for the OER and the ORR, respectively, Mn0.5Fe0.5 exhibits high stability for both reactions. © 2020, The Author(s).
  	view abstract	doi: 10.1007/s10008-020-04667-2

• 2020 • 135	Thermodynamic modelling of the Ni–Zr system Jana, A. and Sridar, S. and Fries, S.G. and Hammerschmidt, T. and Kumar, K.C.H. Intermetallics 116 (2020) In this work, we report the thermodynamic modelling of the Ni–Zr system using the Calphad method combined with ab initio calculations. Density functional theory (DFT) is employed to calculate the enthalpy of formation of the intermediate phases. The calculated enthalpies of formation are in close agreement with the experimental data. An approach based on special quasirandom structures (SQS) was used for calculating the enthalpy of mixing of the fcc solid solution. The vibrational contribution to the heat capacities of NiZr, NiZr2, Ni3Zr and Ni7Zr2 phases were calculated using the quasiharmonic approximation (QHA) and the corresponding electronic contribution was obtained using an approach based on Mermin statistics. The total heat capacities for these phases were fitted to appropriate expressions and integrated to obtain the Gibbs energy functions valid down to 0 K. The calculated thermochemical properties along with critically selected experimental constitutional and thermochemical data served as input for the thermodynamic optimisation of the system. The calculated phase equilibria and the thermodynamic properties using the optimised Gibbs energy functions are in good agreement with the input data. The calculated congruent melting points of NiZr and NiZr2 phases are close to the recent experimental data. The Ni10Z7 phase forms by a peritectic reaction, which is also in agreement with the experimental data. © 2019 Elsevier Ltd
  	view abstract	doi: 10.1016/j.intermet.2019.106640

• 2020 • 134	Trends in elastic properties of Ti-Ta alloys from first-principles calculations Chakraborty, T. and Rogal, J. Journal of Physics Condensed Matter 33 (2020) The martensitic start temperature (M s) is a technologically fundamental characteristic of high-temperature shape memory alloys. We have recently shown [Chakraborty et al 2016 Phys. Rev. B 94 224104] that the two key features in describing the composition dependence of M s are the T = 0 K phase stability and the difference in vibrational entropy which, within the Debye model, is directly linked to the elastic properties. Here, we use density functional theory together with special quasi-random structures to study the elastic properties of disordered martensite and austenite Ti-Ta alloys as a function of composition. We observe a softening in the tetragonal shear elastic constant of the austenite phase at low Ta content and a non-linear behavior in the shear elastic constant of the martensite. A minimum of 12.5% Ta is required to stabilize the austenite phase at T = 0 K. Further, the shear elastic constants and Young's modulus of martensite exhibit a maximum for Ta concentrations close to 30%. Phenomenological, elastic-constant-based criteria suggest that the addition of Ta enhances the strength, but reduces the ductile character of the alloys. In addition, the directional elastic stiffness, calculated for both martensite and austenite, becomes more isotropic with increasing Ta content. The reported trends in elastic properties as a function of composition may serve as a guide in the design of alloys with optimized properties in this interesting class of materials. © 2020 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-648X/abba67

• 2020 • 133	Trivalent iron rich CoFe layered oxyhydroxides for electrochemical water oxidation Weiß, S. and Ertl, M. and Varhade, S.D. and Radha, A.V. and Schuhmann, W. and Breu, J. and Andronescu, C. Electrochimica Acta 350 (2020) Layered double hydroxides (LDHs) are presently among the best-performing oxygen evolution reaction (OER) electrocatalysts in alkaline media. The high activity of LDHs is due to synergistic effects between two transition metals as well as the layered structure which facilitates electron transfer. Because of a perfect match with the size of interlayer carbonate a ratio of 2:1 for the di- and tri-valent octahedral cations is energetically preferred. Here we present a strategy, where first mixed valent (Co2+ 1-zFe2+ z)4 Fe3+ 2 - LDHs, with z values between 0 and 0.75 are synthesized, which are subsequently oxidized to Co2+Fe3+ LDH-type layered (oxy)hydroxides with an unusual high trivalent Fe content. Characterization of the chemically oxidized materials using bulk and surface techniques demonstrated the successful synthesis of LDH-like trivalent iron rich (Co2+)4-4z (Fe3+)2+4z (oxy)hydroxides with a final Fe content ranging from 33.3 to 83.3%. Current densities of up to 200 mA cm−2 were obtained at potentials lower than 1.7 V vs. RHE for (Co2+)4-4z (Fe3+)2+4z (oxy)hydroxides containing a maximum of 80% Fe. © 2020 Elsevier Ltd
  	view abstract	doi: 10.1016/j.electacta.2020.136256

• 2020 • 132	Unfolding the complexity of phonon quasi-particle physics in disordered materials Mu, S. and Olsen, R.J. and Dutta, B. and Lindsay, L. and Samolyuk, G.D. and Berlijn, T. and Specht, E.D. and Jin, K. and Bei, H. and Hickel, T. and Larson, B.C. and Stocks, G.M. npj Computational Materials 6 (2020) The concept of quasi-particles forms the theoretical basis of our microscopic understanding of emergent phenomena associated with quantum-mechanical many-body interactions. However, the quasi-particle theory in disordered materials has proven difficult, resulting in the predominance of mean-field solutions. Here, we report first-principles phonon calculations and inelastic X-ray and neutron-scattering measurements on equiatomic alloys (NiCo, NiFe, AgPd, and NiFeCo) with force-constant dominant disorder—confronting a key 50-year-old assumption in the Hamiltonian of all mean-field quasi-particle solutions for off-diagonal disorder. Our results have revealed the presence of a large, and heretofore unrecognized, impact of local chemical environments on the distribution of the species-pair-resolved force-constant disorder that can dominate phonon scattering. This discovery not only identifies a critical analysis issue that has broad implications for other elementary excitations, such as magnons and skyrmions in magnetic alloys, but also provides an important tool for the design of materials with ultralow thermal conductivities. © 2020, The Author(s).
  	view abstract	doi: 10.1038/s41524-020-0271-3

• 2020 • 131	Unveiling the mechanism of abnormal magnetic behavior of FeNiCoMnCu high-entropy alloys through a joint experimental-theoretical study Rao, Z. and Dutta, B. and Körmann, F. and Ponge, D. and Li, L. and He, J. and Stephenson, L. and Schäfer, L. and Skokov, K. and Gutfleisch, O. and Raabe, D. and Li, Z. Physical Review Materials 4 (2020) We combined experimental investigations and theoretical calculations to unveil an abnormal magnetic behavior caused by addition of the nonmagnetic element Cu in face-centered-cubic FeNiCoMn-based high-entropy alloys (HEAs). Upon Cu addition, the probed HEAs show an increase of both Curie temperature and saturation magnetization in as-cast and homogenized states. Specifically, the saturation magnetization of the as-cast HEAs at room temperature increases by 77% and 177% at a Cu content of 11 and 20 at. %, respectively, compared to the as-cast equiatomic FeNiCoMn HEA without Cu. The increase in saturation magnetization of the as-cast HEAs is associated with the formation of an Fe-Co rich phase in the dendritic regions. For the homogenized HEAs, the magnetic state at room temperature transforms from paramagnetism to ferromagnetism after 20 at. % Cu addition. The increase of the saturation magnetization and Curie temperature cannot be adequately explained by the formation of Cu enriched zones according to atom probe tomography analysis. Ab initio calculations suggest Cu plays a pivotal role in the stabilization of a ferromagnetic ordering of Fe, and reveal an increase of the Curie temperature caused by Cu addition which agrees well with the experimental results. The underlying mechanism behind this phenomenon lies in a combined change in unit-cell volume and chemical composition and the related energetic stabilization of the magnetic ordering upon Cu alloying as revealed by theoretical calculations. Thus, the work unveils the mechanisms responsible for the Cu effect on the magnetic properties of FeNiCoMn HEAs, and suggests that nonmagnetic elements are also crucial to tune and improve magnetic properties of HEAs. © 2020 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.4.014402

• 2020 • 130	Vertical bonding distances and interfacial band structure of PTCDA on a Sn-Ag surface alloy Knippertz, J. and Kelly, L.L. and Franke, M. and Kumpf, C. and Cinchetti, M. and Aeschlimann, M. and Stadtmüller, B. Physical Review B 102 (2020) Molecular materials enable a vast variety of functionalities for novel electronic and spintronic devices. The unique possibility to alter organic molecules or metallic substrates offers the opportunity to optimize interfacial properties for almost any desired field of application. For this reason, we extend the successful approach to control metal-organic interfaces by surface alloying. We present a comprehensive characterization of the structural and electronic properties of the interface formed between the prototypical molecule PTCDA and a Sn-Ag surface alloy grown on an Ag(111) single crystal surface. We monitor the changes of adsorption height of the surface alloy atoms and electronic valence band structure upon adsorption of one layer of PTCDA using the normal incidence X-ray standing wave technique in combination with momentum-resolved photoelectron spectroscopy. We find that the vertical buckling and the surface band structure of the SnAg2 surface alloy is not altered by the adsorption of one layer of PTCDA, in contrast to our recent study of PTCDA on a PbAg2 surface alloy [B. Stadtmüller, Phys. Rev. Lett. 117, 096805 (2016)PRLTAO0031-900710.1103/PhysRevLett.117.096805]. In addition, the vertical adsorption geometry of PTCDA and the interfacial energy level alignment indicate the absence of any chemical interaction between the molecule and the surface alloy. We attribute the different interactions at these PTCDA/surface alloy interfaces to the presence or absence of local σ-bonds between the PTCDA oxygen atoms and the surface atoms. Combining our findings with results from literature, we are able to propose an empiric rule for engineering the surface band structure of alloys by adsorption of organic molecules. © 2020 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.102.075447

• 2020 • 129	Zn- or Cu-containing CaP-based coatings formed by micro-arc oxidation on titanium and Ti-40Nb Alloy: Part I-Microstructure, composition and properties Komarova, E.G. and Sharkeev, Y.P. and Sedelnikova, M.B. and Prosolov, K.A. and Khlusov, I.A. and Prymak, O. and Epple, M. Materials 13 (2020) Zn- and Cu-containing CaP-based coatings, obtained by micro-arc oxidation process, were deposited on substrates made of pure titanium (Ti) and novel Ti-40Nb alloy. The microstructure, phase, and elemental composition, as well as physicochemical and mechanical properties, were examined for unmodified CaP and Zn- or Cu-containing CaP coatings, in relation to the applied voltage that was varied in the range from 200 to 350 V. The unmodified CaP coatings on both types of substrates had mainly an amorphous microstructure with a minimal content of the CaHPO4 phase for all applied voltages. The CaP coatings modified with Zn or Cu had a range from amorphous to nano- and microcrystalline structure that contained micro-sized CaHPO4 and Ca(H2PO4)2·H2O phases, as well as nano-sized β-Ca2P2O7, CaHPO4, TiO2, and Nb2O5 phases. The crystallinity of the formed coatings increased in the following order: CaP/TiNb < Zn-CaP/TiNb < Cu-CaP/TiNb < CaP/Ti < Zn-CaP/Ti < Cu-CaP/Ti. The increase in the applied voltage led to a linear increase in thickness, roughness, and porosity of all types of coatings, unlike adhesive strength that was inversely proportional to an increase in the applied voltage. The increase in the applied voltage did not affect the Zn or Cu concentration (~0.4 at%), but led to an increase in the Ca/P atomic ratio from 0.3 to 0.7. © 2020 by the authors.
  	view abstract	doi: 10.3390/ma13184116

• 2020 • 128	Zn- or Cu-containing CaP-Based Coatings Formed by Micro-Arc Oxidation on Titanium and Ti-40Nb Alloy: Part II—Wettability and Biological Performance Komarova, E.G. and Sharkeev, Y.P. and Sedelnikova, M.B. and Prymak, O. and Epple, M. and Litvinova, L.S. and Shupletsova, V.V. and Malashchenko, V.V. and Yurova, K.A. and Dzyuman, A.N. and Kulagina, I.V. and Mushtovatova, L.S. and... Materials 13 1-23 (2020) This work describes the wettability and biological performance of Zn-and Cu-containing CaP-based coatings prepared by micro-arc oxidation on pure titanium (Ti) and novel Ti-40Nb alloy. Good hydrophilic properties of all the coatings were demonstrated by the low contact angles with liquids, not exceeding 45◦ . An increase in the applied voltage led to an increase of the coating roughness and porosity, thereby reducing the contact angles to 6◦ with water and to 17◦ with glycerol. The free surface energy of 75 ± 3 mJ/m2 for all the coatings were determined. Polar component was calculated as the main component of surface energy, caused by the presence of strong polar PO43− and OH− bonds. In vitro studies showed that low Cu and Zn amounts (~0.4 at.%) in the coatings promoted high motility of human adipose-derived multipotent mesenchymal stromal cells (hAMMSC) on the implant/cell interface and subsequent cell ability to differentiate into osteoblasts. In vivo study demonstrated 100% ectopic bone formation only on the surface of the CaP coating on Ti. The Zn-and Cu-containing CaP coatings on both substrates and the CaP coating on the Ti-40Nb alloy slightly decreased the incidence of ectopic osteogenesis down to 67%. The MAO coatings showed antibacterial efficacy against Staphylococcus aureus and can be arranged as follows: Zn-CaP/Ti > Cu-CaP/TiNb, Zn-CaP/TiNb > Cu-CaP/Ti. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/ma13194366

• 2019 • 127	A neutron diffraction demonstration of long-range magnetic order in the quasicrystal approximant DyCd6 Ryan, D.H. and Cadogan, J.M. and Kong, T. and Canfield, P.C. and Goldman, A.I. and Kreyssig, A. AIP Advances 9 (2019) We have used neutron powder diffraction to demonstrate the existence of long-range antiferromagnetic order of Ising-like Dy moments in the DyCd6 quasicrystal approximant phase. This cubic compound undergoes a slight distortion to a monoclinic cell at low temperatures. The Néel temperature is 18.0(2) K and the magnetic order of the Dy sublattice may be described in the parent cubic Im3 structure using a combination of two propagation vectors, k1 = [0 0 0] and k2 = [12 0 12], yielding 'anti-I' order. Alternatively, when referred to the monoclinic C2/c cell, the magnetic structure may be described by a single propagation vector: k = [1 0 0]. © 2019 Author(s).
  	view abstract	doi: 10.1063/1.5079991

• 2019 • 126	Ab initio phase stabilities of Ce-based hard magnetic materials and comparison with experimental phase diagrams Sözen, H.Ä. and Ener, S. and MacCari, F. and Skokov, K.P. and Gutfleisch, O. and Körmann, F. and Neugebauer, J. and Hickel, T. Physical Review Materials 3 (2019) Recent developments in electrical transportation and renewable energies have significantly increased the demand of hard magnetic materials with a reduced critical rare-earth content, but with properties comparable to (Nd,Dy)-Fe-B permanent magnets. Though promising alternative compositions have been identified in high-throughput screenings, the thermodynamic stability of these phases against decomposition into structures with much less favorable magnetic properties is often unclear. In the case of Ce-Fe-Ti alloys, we have used finite temperature ab initio methods to provide this missing information. Employing state-of-the-art approaches for vibrational, electronic, and magnetic entropy contributions, the Helmholtz free energy, F(T,V), is calculated for the desired hard magnetic CeFe11Ti phase and all relevant competing phases. The latter have been confirmed experimentally by employing reactive crucible melting (RCM) and energy-dispersive x-ray spectroscopy (EDS). Our ab initio based free energy calculations reveal that the presence of the CeFe2 Laves phase suppresses the formation of CeFe11Ti up to 700 K. The result is in agreement with RCM, in which CeFe11Ti is only observed above 1000 K, while the CeFe2 and Ce2Fe17 phases are stable at lower temperatures. © 2019 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.3.084407

• 2019 • 125	Altering the stability of nanoislands through core-shell supports Sprodowski, C. and Morgenstern, K. Nanoscale 11 10314-10319 (2019) We follow the decay of two-dimensional Ag nanoclusters, called islands, on Cu-Ag core-shell supports by variable low temperature scanning tunneling microscopy in the temperature range between 160 and 260 K. We reveal two qualitatively different types of decay mechanisms, either linear in time, indicative of an interface-limited decay, or non-linear in time, indicative of diffusion-limited decay. In contrast to conventional decay on monometallic supports, the decay exponent of the diffusion-limited decay depends on temperature; it varies by one order of magnitude. Moreover, the decay rate decreases with increasing temperature. This unusual behaviour is traced back to the temperature-dependent shell of the core-shell support. © 2019 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c9nr00529c

• 2019 • 124	Bimetallic silver-platinum nanoparticles with combined osteo-promotive and antimicrobial activity Breisch, M. and Grasmik, V. and Loza, K. and Pappert, K. and Rostek, A. and Ziegler, N. and Ludwig, Al. and Heggen, M. and Epple, M. and Tiller, J.C. and Schildhauer, T.A. and Köller, M. and Sengstock, C. Nanotechnology 30 (2019) Bimetallic alloyed silver-platinum nanoparticles (AgPt NP) with different metal composition from Ag10Pt90 to Ag90Pt10 in steps of 20 mol% were synthesized. The biological effects of AgPt NP, including cellular uptake, cell viability, osteogenic differentiation and osteoclastogenesis as well as the antimicrobial activity towards Staphylococcus aureus and Escherichia coli were analyzed in comparison to pure Ag NP and pure Pt NP. The uptake of NP into human mesenchymal stem cells was confirmed by cross-sectional focused-ion beam preparation and observation by scanning and transmission electron microscopy in combination with energy-dispersive x-ray analysis. Lower cytotoxicity and antimicrobial activity were observed for AgPt NP compared to pure Ag NP. Thus, an enhanced Ag ion release due to a possible sacrificial anode effect was not achieved. Nevertheless, a Ag content of at least 50 mol% was sufficient to induce bactericidal effects against both Staphylococcus aureus and Escherichia coli. In addition, a Pt-related (≥50 mol% Pt) osteo-promotive activity on human mesenchymal stem cells was observed by enhanced cell calcification and alkaline phosphatase activity. In contrast, the osteoclastogenesis of rat primary precursor osteoclasts was inhibited. In summary, these results demonstrate a combinatory osteo-promotive and antimicrobial activity of bimetallic Ag50Pt50 NP. © 2019 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-6528/ab172b

• 2019 • 123	Cold spray deposition of Cr2AlC MAX phase for coatings and bond-coat layers Go, T. and Sohn, Y.J. and Mauer, G. and Vaßen, R. and Gonzalez-Julian, J. Journal of the European Ceramic Society 39 860-867 (2019) Highly pure Cr2AlC powders were synthesized and deposited for the first time by cold spray technology on stainless steel substrates. The Cr2AlC coatings were relative dense, up to 91%, and present high purity (> 98%) since only small traces of Cr2Al, Al2O3 and Cr2O3 were detected by XRD, SEM and EDX. The microstructure of the coatings is homogeneous, although some preferential orientation in the basal plane was observed by XRD pole figures. The adhesion between the coating and the substrate is strong, and compressive residual stresses up to 300 MPa in the coating were determined by XRD. Furthermore, a conventional YSZ Thermal Barrier Coating (TBCs) was deposited by Atmospheric Plasma Spray (APS) on top of the cold sprayed Cr2AlC coating in order to demonstrate the processing feasibility of Cr2AlC MAX phases as a bond-coat layer. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.jeurceramsoc.2018.11.035

• 2019 • 122	Comparative study of different anisotropy and potential formulations of phase-field models for dendritic solidification Kundin, J. and Steinbach, I. Computational Materials Science 170 (2019) Phase-field model formulations with double well and double obstacle potentials, and different anisotropy models are investigated with respect to their potential to simulate (i) tip growth on a quantitative level, (ii) well resolved side-branching. The dilute binary alloy Al-4 at%Cu is used as a model alloy. The effects of the numerical resolution (the ratio of the capillary length to the grid spacing) on the growth velocity are studied by means of convergence tests for isothermal and directional solidification in comparison to the theoretical values calculated by the Green-function method (A. Karma, W.J. Rappel, Phys. Rev. E 57 (1998) 4323). An interface stability parameter is introduced as a measure for the estimation of the maximum value of the grid spacing for effective simulations. We show that predominantly the side-branching occurs at numerical resolution lower than the limit value needed to produce correct results in accordance to the convergence analysis. The best results for dendrite growth at a relevant numerical resolution are obtained for the double well potential. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.commatsci.2019.109197

• 2019 • 121	Current-induced domain wall oscillations in a nanowire imaged by time-resolved photoemission electron microscopy Khan, M.I. and Cramm, S. and Bürgler, D.E. and Parlak, U. and Nemšák, S. and Gottlob, D.M. and Hackl, J. and Doğanay, H. and Schneider, C.M. Journal of Magnetism and Magnetic Materials 476 538-545 (2019) We study reversible domain wall motion in half-ring Ni 80 Fe 20 nanowires on a nanosecond (ns) timescale in a truly current-induced pump-probe experiment using an energy filtered, aberration-corrected photoemission electron microscope. The X-ray magnetic circular dichroism signal is probed at different time delays before, during and after the current pulse in a stroboscopic mode with circularly polarized synchrotron radiation in the energy range of the Fe L 3 -edge (707 eV). We observe lateral domain wall oscillations with a frequency of ∼0.4 GHz. Comparing the results to a proposed string model, we find that the domain wall oscillations can be described as string-like asymmetric oscillations. © 2019
  	view abstract	doi: 10.1016/j.jmmm.2019.01.003

• 2019 • 120	Discovery of ω -free high-temperature Ti-Ta- X shape memory alloys from first-principles calculations Ferrari, A. and Paulsen, A. and Langenkämper, D. and Piorunek, D. and Somsen, C. and Frenzel, J. and Rogal, J. and Eggeler, G. and Drautz, R. Physical Review Materials 3 (2019) The rapid degradation of the functional properties of many Ti-based alloys is due to the precipitation of the ω phase. In the conventional high-temperature shape memory alloy Ti-Ta, the formation of this phase compromises completely the shape memory effect, and high (>100°C) transformation temperatures cannot be maintained during cycling. A solution to this problem is the addition of other elements to form Ti-Ta-X alloys, which often modifies the transformation temperatures; due to the largely unexplored space of possible compositions, very few elements are known to stabilize the shape memory effect without decreasing the transformation temperatures below 100°C. In this study, we use transparent descriptors derived from first-principles calculations to search for new ternary Ti-Ta-X alloys that combine stability and high temperatures. We suggest four alloys with these properties, namely Ti-Ta-Sb, Ti-Ta-Bi, Ti-Ta-In, and Ti-Ta-Sc. Our predictions for the most promising of these alloys, Ti-Ta-Sc, are subsequently fully validated by experimental investigations, the alloy Ti-Ta-Sc showing no traces of ω phase after cycling. Our computational strategy is transferable to other materials and may contribute to suppress ω phase formation in a large class of alloys. ©2019 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.3.103605

• 2019 • 119	Effects of AlN and BCN thin film multilayer design on the reaction time of Ni/Ni-20Cr thin film thermocouples on thermally sprayed Al2O3 Tillmann, W. and Kokalj, D. and Stangier, D. and Schöppner, V. and Malatyali, H. Sensors (Switzerland) 19 (2019) Thin film thermocouples are widely used for local temperature determinations of surfaces. However, depending on the environment in which they are used, thin film thermocouples need to be covered by a wear or oxidation resistant top layer. With regard to the utilization in wide-slit nozzles for plastic extrusion, Ni/Ni-20Cr thin film thermocouples were manufactured using directcurrent (DC) magnetron sputtering combined with Aluminiumnitride (AlN) and Boron- Carbonitride (BCN) thin films. On the one hand, the deposition parameters of the nitride layers were varied to affect the chemical composition and morphology of the AlN and BCN thin films. On the other hand, the position of the nitride layers (below the thermocouple, above the thermocouple, around the thermocouple) was changed. Both factors were investigated concerning the influence on the Seebeck coefficient and the reaction behaviour of the thermocouples. Therefore, the impact of the nitride thin films on the morphology, physical structure, crystallite size, electrical resistance and hardness of the Ni and Ni-20Cr thin films is analysed. The investigations reveal that the Seebeck coefficient is not affected by the different architectures of the thermocouples. Nevertheless, the reaction time of the thermocouples can be significantly improved by adding a thermal conductive top coat over the thin films, whereas the top coat should have a coarse structure and low nitrogen content. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.
  	view abstract	doi: 10.3390/s19153414

• 2019 • 118	Effects of femtosecond laser shock peening in distilled water on the surface characterizations of NiTi shape memory alloy Wang, H. and Pöhl, F. and Yan, K. and Decker, P. and Gurevich, E.L. and Ostendorf, A. Applied Surface Science 471 869-877 (2019) NiTi shape memory alloy was processed by femtosecond laser shock peening (FLSP) without protective coating in distilled water to modify its surface characterizations. The surface topography, microhardness, microstructure and scratch testing were studied before and after FLSP treatment. The experimental results show that FLSP with different laser scanning speeds and passes can change the surface roughness and microhardness due to laser ablation and high pressure of shock wave. The average microhardness value of the specimens FLSPed in distilled water increased. Grain refinement was observed in the surface layer of FLSPed NiTi alloy. The scratch testing revealed that FLSP process can decrease the frictional force and coefficient of friction, and it also demonstrated that the FLSP technique is beneficial to enhance the surface wear property of NiTi alloy. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apsusc.2018.12.087

• 2019 • 117	Electron-phonon coupling and superconductivity-induced distortion of the phonon lineshape in V3Si Sauer, A. and Zocco, D.A. and Said, A.H. and Heid, R. and Böhmer, A. and Weber, F. Physical Review B 99 (2019) Phonon measurements in the A15-type superconductors were complicated in the past because of the unavailability of large single crystals for inelastic neutron scattering, e.g., in the case of Nb3Sn, or unfavorable neutron scattering properties in the case of V3Si. Hence, only few studies of the lattice dynamical properties with momentum resolved methods were published, in particular below the superconducting transition temperature Tc. Here, we overcome these problems by employing inelastic x-ray scattering and report a combined experimental and theoretical investigation of lattice dynamics in V3Si with the focus on the temperature-dependent properties of low-energy acoustic phonon modes in several high-symmetry directions. We paid particular attention to the evolution of the soft phonon mode of the structural phase transition observed in our sample at Ts=18.9K, i.e., just above the measured superconducting phase transition at Tc=16.8K. Theoretically, we predict lattice dynamics including electron-phonon coupling based on density-functional-perturbation theory and discuss the relevance of the soft phonon mode with regard to the value of Tc. Furthermore, we explain superconductivity-induced anomalies in the lineshape of several acoustic phonon modes using a model proposed by Allen et al, [Phys. Rev. B 56, 5552 (1997)10.1103/PhysRevB.56.5552]. © 2019 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.99.134511

• 2019 • 116	Enhanced propylene oxide selectivity for gas phase direct propylene epoxidation by lattice expansion of silver atoms on nickel nanoparticles Yu, B. and Ayvalı, T. and Raine, E. and Li, T. and Li, M.M.-J. and Zheng, J. and Wu, S. and Bagabas, A.A. and Tsang, S.C.E. Applied Catalysis B: Environmental 243 304-312 (2019) A series of surfactant-free nickel-core and silver-shell (Ni@Ag) nanoparticles encapsulated within the mesopores of SBA-15 were synthesized and tested as catalysts for direct propylene oxidation by molecular oxygen. The influences of temperature, Gas Hour Space Velocity (GHSV) and Ni/Ag ratio on catalytic activity were systematically investigated. Among the prepared samples, Ni1Ag0.4/SBA-15 exhibited the best catalytic performance with selectivity of 70.7% and PO production rate of 4.4 nmol/g/s under 1 bar at 220 °C with GHSV of 192 h−1. High selectivity was attributed to longer Ag-Ag interatomic distance obtained by careful engineering the thickness of Ag shell over preformed Ni nanoparticles. In addition, all prepared new Ni@Ag core-shell catalysts presented excellent stability, which could maintain the conversion and selectivity for at least 10 h. These results suggest that new designs based on Ag surface atoms tailoring might pave the way to highly efficient and robust Ag catalysts for direct propylene oxidation using molecular oxygen as sole oxidant. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apcatb.2018.10.061

• 2019 • 115	Epitaxial strain adaptation in chemically disordered FeRh thin films Witte, R. and Kruk, R. and Wang, D. and Schlabach, S. and Brand, R.A. and Gruner, M.E. and Wende, H. and Hahn, H. Physical Review B 99 (2019) Strain and strain adaptation mechanisms in modern functional materials are of crucial importance for their performance. Understanding these mechanisms will advance innovative approaches for material properties engineering. Here we study the strain adaptation mechanism in a thin film model system as a function of epitaxial strain. Chemically disordered FeRh thin films are deposited on W-V buffer layers, which allow for large variation of the preset lattice constants, e.g., epitaxial boundary condition. It is shown by means of high-resolution x-ray reciprocal space maps and transmission electron microscopy that the system reacts with a tilting mechanism of the structural units in order to adapt to the lattice constants of the buffer layer. This response is explained by density functional theory calculations, which evidence an energetic minimum for structures with a distortion of c/a≈0.87. The experimentally observed tilting mechanism is induced by this energy gain and allows the system to remain in the most favorable structure. In general, it is shown that the use of epitaxial model heterostructures consisting of alloy buffer layers of fully miscible elements and the functional material of interest allows to study strain adaptation behaviors in great detail. This approach makes even small secondary effects observable, such as the directional tilting of the structural domains identified in the present case study. © 2019 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.99.134109

• 2019 • 114	Facile Protocol for Alkaline Electrolyte Purification and Its Influence on a Ni-Co Oxide Catalyst for the Oxygen Evolution Reaction Spanos, I. and Tesch, M.F. and Yu, M. and Tüysüz, H. and Zhang, J. and Feng, X. and Müllen, K. and Schlögl, R. and Mechler, A.K. ACS Catalysis 9 8165-8170 (2019) We report a simple and effective electrochemical method to remove Fe impurities from commercial KOH electrolyte. We therefore utilize a MoS2 catalyst deposited on porous Ni foam as both the anode and cathode in a two-electrode electrolysis setup. After 12 h of constant galvanostatic electrolysis at 100 mA, the Fe impurities from the KOH electrolyte were successfully removed, as confirmed by means of inductively coupled plasma optical emission spectroscopy analysis. In the purified KOH, a Ni-Co3O4 composite oxide catalyst showed no Fe-induced activation. In contrast, we directly observed the uptake of Fe on the Ni-Co3O4 catalyst from the nontreated electrolyte during catalyst operation using a coupled spectroelectrochemical setup. Interestingly, we further identified an influence on the dissolution behavior of Ni and Co in the presence of Fe impurities. Whereas hitherto mainly the activation effect of Fe impurities has been discussed, we hereby show that they additionally suppress corrosion under reaction conditions. Using our fast and low-cost method for the purification of large amounts of electrolyte, catalyst materials can be widely studied without these additional effects induced by Fe impurities in commercial KOH. © 2019 American Chemical Society.
  	view abstract	doi: 10.1021/acscatal.9b01940

• 2019 • 113	Fe/Co/Ni mixed oxide nanoparticles supported on oxidized multi-walled carbon nanotubes as electrocatalysts for the oxygen reduction and the oxygen evolution reactions in alkaline media Kazakova, M.A. and Morales, D.M. and Andronescu, C. and Elumeeva, K. and Selyutin, A.G. and Ishchenko, A.V. and Golubtsov, G.V. and Dieckhöfer, S. and Schuhmann, W. and Masa, J. Catalysis Today (2019) Fabrication of efficient and cost-effective bifunctional oxygen electrocatalysts for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) remains a challenge for the development of rechargeable metal-air batteries and unitized regenerative fuel cells technologies. Herein, we report high-performance bifunctional ORR/OER electrocatalysts consisting of mixed transition metal (Fe, Co, Ni) oxide nanoparticles supported on oxidized multi-walled carbon nanotubes (MWCNT). Investigation of the ORR and OER activity of samples with different metal compositions showed that trimetallic/MWCNT composites having Fe:Ni:Co = x:x:(1-2x) ratios, with 0.25 ≤ x ≤ 0.4, exhibit highest bifunctional activity in terms of the reversible ORR/OER overvoltage at a given current density. Moreover, the trimetallic catalysts exhibited improved selectivity with respect to the reduction of O 2 to OH − compared to the bimetallic Fe-Ni, Fe-Co and Co-Ni catalysts, thus revealing synergistic interactions among the metal oxide components. Correlation of the electrocatalytic activity with the structure of the composites is discussed for the most representative cases. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.cattod.2019.02.047

• 2019 • 112	First-principles characterization of reversible martensitic transformations Ferrari, A. and Sangiovanni, D.G. and Rogal, J. and Drautz, R. Physical Review B 99 (2019) Reversible martensitic transformations (MTs) are the origin of many fascinating phenomena, including the famous shape memory effect. In this work, we present a fully ab initio procedure to characterize MTs in alloys and to assess their reversibility. Specifically, we employ ab initio molecular dynamics data to parametrize a Landau expansion for the free energy of the MT. This analytical expansion makes it possible to determine the stability of the high- and low-temperature phases, to obtain the Ehrenfest order of the MT, and to quantify its free energy barrier and latent heat. We apply our model to the high-temperature shape memory alloy Ti-Ta, for which we observe remarkably small values for the metastability region (the interval of temperatures in which the high- and low-temperature phases are metastable) and for the barrier: these small values are necessary conditions for the reversibility of MTs and distinguish shape memory alloys from other materials. © 2019 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevB.99.094107

• 2019 • 111	Imaging individual solute atoms at crystalline imperfections in metals Katnagallu, S. and Stephenson, L.T. and Mouton, I. and Freysoldt, C. and Subramanyam, A.P.A. and Jenke, J. and Ladines, A.N. and Neumeier, S. and Hammerschmidt, T. and Drautz, R. and Neugebauer, J. and Vurpillot, F. and Raabe, D. ... New Journal of Physics 21 (2019) 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 FIM with time-of-flight mass-spectrometry (tof-ms). Elemental identification and correlation to FIM images enabled by data mining of combined tof-ms delivers a truly analytical-FIM (A-FIM). Contrast variations due to different chemistries is also interpreted from density-functional theory (DFT). A-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-Re binary alloy 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. © 2019 The Author(s). Published by IOP Publishing Ltd on behalf of the Institute of Physics and Deutsche Physikalische Gesellschaft.
  	view abstract	doi: 10.1088/1367-2630/ab5cc4

• 2019 • 110	Improved adhesion of a-C and a-C:H films with a CrC interlayer on 16MnCr5 by HiPIMS-pretreatment Tillmann, W. and Lopes Dias, N.F. and Stangier, D. and Maus-Friedrichs, W. and Gustus, R. and Thomann, C.A. and Moldenhauer, H. and Debus, J. Surface and Coatings Technology 375 877-887 (2019) Ensuring a high adhesion of amorphous carbon films to steel substrates remains a challenging task, sustaining continuous research efforts to improve the adhesion strength. Besides the interlayer system and the substrate material, surface pretreatments have a significant impact on the adhesion behavior. Within this context, the influence of the High Power Impulse Magnetron Sputtering (HiPIMS) pretreatment on the adhesion of magnetron sputtered hydrogenfree (a-C) and hydrogenated (a-C:H) amorphous carbon films with a chromium carbide (CrC) interlayer on 16MnCr5 steel is investigated. The plasma treatment consisted of 30 min Ar ion etching as well as a sequential 5 min of HiPIMS-pretreatment with a Cr cathode. Subsequently this pretreatment was compared to a procedure without utilizing the HiPIMS technique. The impact of the HiPIMS-pretreatment on the structure of the film was systematically analyzed by taking the CrC interlayer as well as the entire film structure into consideration. The adhesion strength of the a-C and a-C:H films is significantly improved by the formation of a Cr HiPIMS-nanolayer in the substrate/film interface. In scratch tests, the critical load Lc3 for a total film delamination increases from 43 ± 4 to 59 ± 3 N and from 48 ± 2 to 64 ± 3 N for the a-C and a-C:H film. The improved adhesion behavior of the carbon films is ascribed to the increased adhesion of the CrC interlayer, which did not delaminate when scratched with a load up to 159 ± 18 N. Complementary Rockwell indentation tests reveal that the HiPIMS-pretreatment improves the adhesion class from HF6 to HF4 and from HF5 to HF3 for a-C and a-C:H. The enhanced adhesion is essential to exploit the properties of a-C and a-C:H films in applications with high loads. In conclusion, the HiPIMS-pretreatment has proven to be a promising technique to increase the adhesion strength of carbon films. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.surfcoat.2019.07.076

• 2019 • 109	Influence of Ag on antibacterial performance, microstructure and phase transformation of NiTi shape memory alloy coatings Momeni, S. and Tillmann, W. Vacuum 164 242-245 (2019) Shape memory binary NiTi and ternary NiTiAg coatings were deposited by means of magnetron sputtering technique. The results show how simultaneous sputtering of Ag can affect the microstructure, phase transformation behavior and antibacterial properties of NiTi coatings. © 2019 Elsevier Ltd
  	view abstract	doi: 10.1016/j.vacuum.2019.02.051

• 2019 • 108	Influence of composition and precipitation evolution on damage at grain boundaries in a crept polycrystalline Ni-based superalloy Kontis, P. and Kostka, A. and Raabe, D. and Gault, B. Acta Materialia 166 158-167 (2019) The microstructural and compositional evolution of intergranular carbides and borides prior to and after creep deformation at 850 °C in a polycrystalline nickel-based superalloy was studied. Primary MC carbides, enveloped within intergranular γ′ layers, decomposed resulting in the formation of layers of the undesirable η phase. These layers have a composition corresponding to Ni3Ta as measured by atom probe tomography and their structure is consistent with the D024 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, M5B3 borides were found to be microstructurally stable after creep and without substantial compositional changes. Borides at 850 °C were found to coarsen, resulting in some cases into 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. © 2018 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2018.12.039

• 2019 • 107	Influence of phase decomposition on mechanical behavior of an equiatomic CoCuFeMnNi high entropy alloy MacDonald, B.E. and Fu, Z. and Wang, X. and Li, Z. and Chen, W. and Zhou, Y. and Raabe, D. and Schoenung, J. and Hahn, H. and Lavernia, E.J. Acta Materialia 181 25-35 (2019) Phase decomposition is commonly observed experimentally in single-phase high entropy alloys (HEAs). Hence, it is essential for the consideration of HEAs for structural applications to study and understand the nature of phase decomposition in HEAs, particularly the influence it has on mechanical behavior. This paper describes the phase decomposition in the equiatomic CoCuFeMnNi HEA and how the reported secondary phases influence mechanical behavior. Thermomechanical processing, followed by systematic post deformation annealing treatments, revealed the formation of two distinct secondary phases within the equiatomic face-centered cubic (FCC) matrix phase. Low temperature annealing treatments at 600 °C and below led to the nucleation of Fe-Co rich ordered B2 precipitates that contributed precipitation hardening while sufficiently small in size, on the order of 140 nm in diameter. At temperatures <800 °C Cu segregation, due to its immiscibility with the other constituents, eventually forms a Cu-rich disordered FCC phase that is determined to increase the yield strength of the alloy while reducing the ductility, likely attributable to the presence of additional interfaces. The thermal stability and chemistry of these phases are compared to those predicted on the basis of calculated phase diagram (CALPHAD) analyses. © 2019 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2019.09.030

• 2019 • 106	Influence of SMA-induced stress on shape memory alloy metal matrix composites manufactured by continuous composite extrusion Dahnke, C. and Pottmeyer, F. and Pinter, P. and Weidenmann, K.A. and Tekkaya, A.E. Smart Materials and Structures 28 (2019) In shape memory alloy metal matrix composites manufactured by continuous composite extrusion the strategies of active property tuning and active strain energy tuning are used for the improvement of the mechanical properties of the components. Due to the thermal activation of the embedded NiTi wires (SM495), compressive stresses are transferred to the surrounding aluminum matrix (AA6060). At elevated temperatures tensile tests, three-point-bending tests and notch impact test show the influence of temperature, prestrain and reinforcing volume on the component performance. In tensile testing, a simultaneous increase of strength and ductility can be found, leading to an increase of the energy abortion capacity. Results of the three-point-bending test and notch impact test also show an increase of the required work depending on the thermomechanical treatment of the specimens. © 2019 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-665X/ab2d6a

• 2019 • 105	Iron Aluminides Palm, M. and Stein, F. and Dehm, G. Annual Review of Materials Research 49 297-326 (2019) The iron aluminides discussed here are Fe-Al-based alloys, in which the matrix consists of the disordered bcc (Fe,Al) solid solution (A2) or the ordered intermetallic phases FeAl (B2) and Fe3Al (D03). These alloys possess outstanding corrosion resistance and high wear resistance and are lightweight materials relative to steels and nickel-based superalloys. These materials are evoking new interest for industrial applications because they are an economic alternative to other materials, and substantial progress in strengthening these alloys at high temperatures has recently been achieved by applying new alloy concepts. Research on iron aluminides started more than a century ago and has led to many fundamental findings. This article summarizes the current knowledge of this field in continuation of previous reviews. © 2019 by Annual Reviews. All rights reserved.
  	view abstract	doi: 10.1146/annurev-matsci-070218-125911

• 2019 • 104	Large thermopower anisotropy in PdCo O2 thin films Yordanov, P. and Sigle, W. and Kaya, P. and Gruner, M.E. and Pentcheva, R. and Keimer, B. and Habermeier, H.-U. Physical Review Materials 3 (2019) Motivated by recent theoretical studies predicting a large thermopower anisotropy in the layered delafossite PdCoO2, we have used pulsed laser deposition to synthesize thin films on (0001)-oriented and offcut Al2O3 substrates. By combining transport measurements on films with different offcut angles, tensor rotation relations, and an iterative fit procedure for the transport parameters, we have determined the resistivity and the thermopower along the main crystallographic axes in the temperature range 300-815 K. The data reveal a small positive Seebeck coefficient along the delafossite planes and a large negative Seebeck coefficient perpendicular to the planes, in excellent agreement with density functional calculations in the presence of moderate Coulomb correlations. The methodology introduced here is generally applicable for measurements of the thermoelectric properties of materials with highly anisotropic electronic structures. © 2019 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.3.085403

• 2019 • 103	Magnetically and optically tunable terahertz radiation from Ta/NiFe/Pt spintronic nanolayers generated by femtosecond laser pulses Adam, R. and Chen, G. and Bürgler, D.E. and Shou, T. and Komissarov, I. and Heidtfeld, S. and Hardtdegen, H. and Mikulics, M. and Schneider, C.M. and Sobolewski, R. Applied Physics Letters 114 (2019) We generate terahertz (THz) transients by illuminating a few-nanometer-thick Ta/NiFe/Pt nanolayers with a train of linearly polarized 100-fs-wide laser pulses. The transients are ∼1-ps-wide free-space propagating bursts of electromagnetic radiations with amplitudes that are magnetically and optically tunable. Their spectral frequency content extends up to 5 THz, and the 3-dB cutoff is at 0.85 THz. The observed transient electromagnetic signals originate from the NiFe/Pt bilayer, and their amplitude dependence on the external magnetic field, applied in the sample plane, very closely follows the static magnetization versus magnetic field dependence of the NiFe film. For the same laser power, excitation with highly energetic, blue light generates THz transients with amplitudes approximately three times larger than the ones resulting from excitation by infrared light. In both cases, the transients exhibit the same spectral characteristics and are linearly polarized in the perpendicular direction to the sample magnetization. The polarization direction can be tuned by rotation of the magnetic field around the laser light propagation axis. The characteristics of our THz spintronic emitter signals confirm that THz transient generation is due to the inverse spin Hall effect in the Pt layer and demonstrate that ferromagnet/metal nanolayers excited by femtosecond laser pulses can serve as efficient sources of magnetically and optically tunable, polarized transient THz radiation. © 2019 Author(s).
  	view abstract	doi: 10.1063/1.5099201

• 2019 • 102	New flat-punch indentation creep testing approach for characterizing the local creep properties at high temperatures Matschkal-Amberger, D. and Kolb, M. and Neumeier, S. and Gao, S. and Hartmaier, A. and Durst, K. and Göken, M. Materials and Design 183 (2019) An indentation creep testing approach has been developed which allows measuring creep properties at high temperatures. In contrast to existing indentation or impression creep experiments, the approach described here allows to achieve a quite high spatial resolution, as flat punch indenters with a diameter of only 20 μm are used. First indentation creep tests have been performed on single crystalline nickel and nickel binary solid solution alloys with Re, Ta or W as alloying elements, respectively. The indentation creep tests have been carried out at a temperature of 650 °C and stress levels in the range of 85 to 400 MPa. Using crystal plasticity finite element modeling, the indentation creep response is converted into equivalent uniaxial creep properties. It is shown that the conversion parameters, evaluated for differently oriented single crystals, can be chosen independently of the creep rate exponent in the power law creep regime. It is found that the indentation creep results agree well with conventional uniaxial creep tests. Furthermore, the results show that Ta is the most effective solid solution strengthener of all tested solid-solution strengtheners at 650 °C because of the large atomic size mismatch, followed by W and Re. © 2019 The Authors
  	view abstract	doi: 10.1016/j.matdes.2019.108090

• 2019 • 101	On the effects of microstructure on the mechanical properties of open-pore Al–11Zn foams Matz, A.M. and Matz, B.S. and Parsa, A.B. and Jost, N. and Eggeler, G. Materials Science and Engineering A 759 552-564 (2019) The mechanical properties of investment casted open-pore metal foams have been investigated on the example of the binary alloy Al–11Zn. The samples were subjected to different cooling conditions subsequent to casting and to different homogenization and ageing treatments. Variation in cooling was done either by quenching the mold in water or slowly cooling it in air. Homogenization and ageing varied in terms of temperature and time. The effects of the different treatments were investigated through microstructural and mechanical characterization methods. Using TEM, we found that the presence of GP zones and their morphological arrangement are the main factors dominating the mechanical performance. Micro- and nanoindentation testing of single foam struts reveal maximum hardness H when room temperature ageing was applied. Ageing at a temperature of 150 °C results in the lowest H in the present study; that is approximately 2/3 of the hardness achieved when ageing at room temperature. This can also be confirmed by the strength of non-porous bulk material obtained by tensile tests, which further show an increase in ductility up to a factor of 5 due to ageing at elevated temperatures. By compression testing of open-pore Al–11Zn foams, we notice that the presence of the microstructural effects varies in extent as a function of the strain ε. At low strains, we observe differences in mechanical performance to a high extent, becoming less with increasing compaction of the samples until they behave as non-porous bulk material. Based on these findings, we deduce a strong interaction of the structural morphology of the foam and its microstructure that determines the mechanical properties dominated by strength and ductility of the base material. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.msea.2019.05.087

• 2019 • 100	On the evolution of dislocation cell structures in two Al-alloys (Al-5Mg and Al-11Zn) during reciprocal sliding wear at high homologous temperatures Parsa, A.B. and Walter, M. and Theisen, W. and Bürger, D. and Eggeler, G. Wear 1-12 (2019) The formation of dislocation substructures in up to 10 µm deep subsurface regions of two aluminium alloys, Al-5Mg and Al-11Zn, was investigated under conditions of high homologous temperature reciprocal sliding wear (HT-RSW). Under creep conditions, Al-5Mg shows a solid solution type of inverse primary creep. In contrast, Al-11Zn creeps obstacle controlled and exhibits normal primary creep. These two materials were subjected to reciprocal sliding wear at 200 and 300 °C for 100 and 1000 cycles. Flat polished disks were exposed to the 1 mm reciprocal movements of a spherical aluminium oxide counterbody under normal forces of 5 and 10 N at an oscillation frequency of 1 Hz. Using focused ion beam (FIB) micromachining thin electron transparent foils were prepared from the surface regions of the as received and worn material states. Transmission electron microscopy (TEM) was used to study the evolution of nano and micro grain sizes in the surface regions. Despite the different creep behavior, the two materials behave similar under conditions of reciprocal sliding wear. The results obtained in the present work show that subgrain sizes decrease with increasing numbers of wear cycles and increasing normal forces. Subgrain sizes also increase with increasing temperature. At 300 °C, dynamic recrystallization was observed in both Al-alloys. The results of the present work are discussed in the light of previous results reported in the literature. Areas in need of further work are highlighted. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.wear.2018.10.018

• 2019 • 99	On the influence of the heat treatment on microstructure formation and mechanical properties of near-α Ti-Fe alloys Sandlöbes, S. and Korte-Kerzel, S. and Raabe, D. Materials Science and Engineering A 748 301-312 (2019) We study the microstructure formation and mechanical properties of Ti-1Fe (wt%) and Ti-3Fe (wt%) alloys for different heat treatments in the β-phase and α + β-phase regions. By applying different heat treatment routes, we observe different microstructure formation mechanisms causing a wide range of mechanical properties from high strength (1.3 GPa) and low ductility (2%) to intermediate strength (700 MPa) and high ductility (30%) in these simple binary alloys. We performed microstructure characterizsation using scanning electron microscopy, transmission electron microscopy and atom probe tomography to show that the alloying content and heat treatment significantly affect the local martensitic and / or diffusional phase transformations causing the substantial changes in the mechanical behavior. © 2018
  	view abstract	doi: 10.1016/j.msea.2018.12.071

• 2019 • 98	On the role of cobalt carbidization in higher alcohol synthesis over hydrotalcite-based Co-Cu catalysts Nebel, J. and Schmidt, S. and Pan, Q. and Lotz, K. and Kaluza, S. and Muhler, M. Chinese Journal of Catalysis 40 1731-1740 (2019) Co-Cu-based catalysts are widely applied in higher alcohol synthesis (HAS) from synthesis gas. Although the nature of the active sites is still not fully understood, the formation of Co2C under HAS conditions seems to play a major role. A CO pretreatment procedure was developed allowing a systematic investigation of the influence of cobalt carbidization on the structural properties and catalytic performance of the catalysts. By exposing the catalyst to a CO-containing atmosphere prior to HAS, Co enrichment of the catalyst surface occurred followed by carbide formation. This surface modification decreased the formation of hydrocarbons and enhanced the formation of C2+OH. The catalyst pretreated with CO at 20 bar achieved the highest selectivity to ethanol and the lowest hydrocarbon selectivity. © 2019 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences
  	view abstract	doi: 10.1016/S1872-2067(19)63344-9

• 2019 • 97	On the role of nitrogen on hydrogen environment embrittlement of high-interstitial austenitic CrMnC(N) steels Egels, G. and Fussik, R. and Weber, S. and Theisen, W. International Journal of Hydrogen Energy 44 32323-32331 (2019) This work investigates the susceptibility of high-interstitial CrMn austenitic stainless steel CN0.96 to hydrogen environment embrittlement. In this context, an N-free model alloy of CN0.96 steel was designed, produced, and characterized. Both steels were subjected to tensile tests in air and in a high-pressure hydrogen gas atmosphere. Both steels undergo severe hydrogen embrittlement. The CN0.96 steel shows trans- and intergranular failure in hydrogen, whereas the N-free model alloy shows exclusively intergranular failure. The different failure modes could be related to different deformation modes that are induced by the presence or absence of N, respectively. In the CN0.96 steel, N promotes planar dislocation slip. Due to the absence of N in the model alloy, localized slip is less pronounced and mechanical twinning is a more preferred deformation mechanism. The embrittlement of the model alloy could therefore be related to mechanisms that are known from hydrogen embrittlement of twinning-induced plasticity steels. © 2019 Hydrogen Energy Publications LLC
  	view abstract	doi: 10.1016/j.ijhydene.2019.10.109

• 2019 • 96	One-step synthesis of Fe-Au core-shell magnetic-plasmonic nanoparticles driven by interface energy minimization Tymoczko, A. and Kamp, M. and Rehbock, C. and Kienle, L. and Cattaruzza, E. and Barcikowski, S. and Amendola, V. Nanoscale Horizons 4 1326-1332 (2019) Directing the assembly of atoms into core-shell particles generally requires elegant but sophisticated procedures. Here we show how the thermodynamic driving force to minimization of surface and interface energy can be exploited to produce colloidal Fe-Au core-shell nanoparticles in one step and with a yield approaching 99.7% in mass. This is obtained by laser ablation with nanosecond pulses of thin bimetallic films immersed in acetone. The Fe-Au core-shell nanoparticles show magnetic and plasmonic properties, and a surface available to bioconjugation and analytical assays. This laser assisted synthetic method represents a step forward in the facile preparation of core-shell nanospheres with multiple appealing functionalities. © 2019 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c9nh00332k

• 2019 • 95	Oxygen-mediated deformation and grain refinement in Cu-Fe nanocrystalline alloys Guo, J. and Duarte, M.J. and Zhang, Y. and Bachmaier, A. and Gammer, C. and Dehm, G. and Pippan, R. and Zhang, Z. Acta Materialia 166 281-293 (2019) Light elements play a crucial role on the microstructure and properties of conventional alloys and steels. Oxygen is one of the light elements which is inevitably introduced into nanocrystalline alloys during manufacturing. Here, we report that severe plastic deformation can fragment the oxides formed in powder processing and eventually cause oxygen dissolution in the matrix. A comparative investigation on Cu-Fe nanocrystalline alloys generated from different initial materials, blended powders and arc-melted bulk materials which have different oxygen contents, reveals that fragmented oxides at grain boundaries effectively decrease the grain boundary mobility, markedly facilitating grain refinement. In contrast, those oxygen atoms dissolved as interstitials in the Cu-Fe matrix lead to lattice expansion and significant decrease of stacking fault energy locally as validated by density functional theory. Such oxygen-mediated microstructure gives rise to enhanced strength and superior structural stability. The remarkable tailoring effect of oxygen can be employed to engineer nanocrystalline materials with desired properties for different applications. © 2018 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2018.12.040

• 2019 • 94	Phase Formation during Heat Treatment of Zn- and ZnAlMg-Coated Steels at 400 and 750 °C Windmann, M. and Barthen, M. and Opitz, T. and Hahn, I. and Röttger, A. and Theisen, W. Steel Research International (2019) In contrast to a cold-forming process, a tempered forming process is able to deform high-strength steel used for manufacturing automotive bodyworks in a more economic manner. Cold-formed steel sheets are commonly coated with a Zn or ZnAlMg layer for cathodic corrosion protection. The tempering process would lead to diffusion processes at the steel/coating interface, which is accompanied by the formation of new phases in the coatings. This publication focuses on phase formation in Zn and ZnAlMg coatings on steel sheets, which are heat-treated at 400 and 750 °C. the authors find that the pure Zn coating remains in the solid state and transforms into the intermetallic δ phase (FeZn 10 ) during heat treatment at 400 °C. The coating melts during heating to 750 °C, but remains in the solid state after transformation into the Γ phase (Fe 4 Zn 9 ) and α-Fe. In the ZnAlMg coating, minor iron diffusion occurs at a temperature of 400 °C. Within a dwell time of 600 s, intermetallic Fe–Zn phases are not formed. During heat treatment at 750 °C, phase formation in the ZnAlMg coating is very similar to that in the pure Zn coating, during which Γ (Fe 4 Zn 9 ) and α-Fe are formed. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/srin.201800588

• 2019 • 93	Powder metallurgic fabricated plug targets for the synthesis of AlCrSiWN multicomponent coating systems Tillmann, W. and Fehr, A. and Stangier, D. International Journal of Refractory Metals and Hard Materials 85 (2019) Monolithic and alloyed targets, conventionally produced by means of melt metallurgy, have been established as conventional target material designs for physical vapor depositions (PVD). However, integrating refractory metals into the sputtering material, leads to restrictions concerning the solubility and phase formation in the target compound. In this context, plug targets are commonly used to deposit multinary coatings with a desired chemical composition. However, producing plugs by means of melt metallurgy restricts the types and amounts of integrated elements. Since current PVD coating concepts aim at an extension of the functionality spectrum by element doping, new target concepts are required. The use of several monolithic targets is one method to produce coatings combining various elements within one coating. Yet depending on the target setup, this approach can result in a nanolaminar coating deposition. To circumvent this, a new production route, which ensures the integration of sintered CrSiW plugs in a monolithic aluminum target, is examined in this study. Two coating deposititons, each with an Al(CrSiW)20 and an Al(CrSiW)48 plug target, were performed by means of direct current (DC) magnetron sputtering and compared with a reference coating, which was synthesized using an AlCr20 target. The dense morphology of AlCrN was significantly changed to a more columnar structure due to slight additions of silicon and tungsten. High aluminum contents in AlCrN and AlCrSiWN, in turn, resulted in a distinct enhancement of the mechanical properties. © 2019 Elsevier Ltd
  	view abstract	doi: 10.1016/j.ijrmhm.2019.105081

• 2019 • 92	Quasi-Fermi-Level Splitting of Cu -Poor and Cu -Rich CuIn S2 Absorber Layers Lomuscio, A. and Rödel, T. and Schwarz, T. and Gault, B. and Melchiorre, M. and Raabe, D. and Siebentritt, S. Physical Review Applied 11 (2019) Cu(In,Ga)S2-based solar cells are interesting tandem partners for Si or chalcopyrite solar cells, but suffer from a low open-circuit voltage. Recently, record efficiencies have been achieved by using higher growth temperatures for the absorber. To understand the effect of higher growth temperatures, we investigate the structural and electronic properties of CuInS2 absorbers. By investigating the absorber alone as opposed to complete solar cells, we can separate changes in the absorber from effects of the interface properties. We show that the quasi-Fermi-level splitting, which indicates the maximum open-circuit voltage an absorber is capable of, increases with higher growth temperature. The quasi-Fermi-level splitting is limited by a deep defect, the concentration of which decreases with higher growth temperature and is less prominent in Cu-rich films. Thus, we demonstrate that the open-circuit voltage of CuInS2-based solar cells is limited to below 850 mV by the absorber itself, independent of the interface. In contrast to the changes in the electronic properties, the structural properties are rather independent of temperature within the range investigated but are significantly influenced by the composition. © 2019 authors. Published by the American Physical Society.
  	view abstract	doi: 10.1103/PhysRevApplied.11.054052

• 2019 • 91	Realizing facile regeneration of spent NaBH4 with Mg-Al alloy Zhong, H. and Ouyang, L. and Zeng, M. and Liu, J. and Wang, H. and Shao, H. and Felderhoff, M. and Zhu, M. Journal of Materials Chemistry A 7 10723-10728 (2019) The regeneration of sodium borohydride (NaBH4) is crucial to form a closed cycle after it either supplies hydrogen energy via a hydrolysis process or provides energy through electron transfer at the anode of direct borohydride fuel cells (DBFCs). In both of these cases, the spent fuels are NaB(OH)4 from NaBO2 aqueous solution. However, the current regeneration process from (NaB(OH)4)·xH2O to form NaBH4 by reduction reaction and calcination at high temperature with metal hydrides as reducing agents is very expensive. In this work, we developed a simple regeneration process via ball milling with Mg-Al alloys as the reducing agent for NaB(OH)4 under an argon atmosphere. Under optimized conditions, a high yield of about 72% of NaBH4 could be obtained. Mechanistic study showed that all the hydrogen atoms from NaB(OH)4 remain in NaBH4 and no additional hydrogen sources are needed for the reduction process. The inexpensive Mg-Al alloy works as a reducing agent transforming the H+ to H- in NaBH4. This approach demonstrates a ∼20-fold cost reduction compared with the method using metal hydrides. This opens the door to the commercial implementation of simple ball milling processes for the regeneration of spent NaBH4 from NaB(OH)4 with cheap reducing agents. © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c9ta00769e

• 2019 • 90	Role of Boron and Phosphorus in Enhanced Electrocatalytic Oxygen Evolution by Nickel Borides and Nickel Phosphides Masa, J. and Andronescu, C. and Antoni, H. and Sinev, I. and Seisel, S. and Elumeeva, K. and Barwe, S. and Marti-Sanchez, S. and Arbiol, J. and Roldan Cuenya, B. and Muhler, M. and Schuhmann, W. ChemElectroChem 6 235-240 (2019) The modification of nickel with boron or phosphorus leads to significant enhancement of its electrocatalytic activity for the oxygen evolution reaction (OER). However, the precise role of the guest elements, B and P, in enhancing the OER of the host element (Ni) remains unclear. Herein, we present insight into the role of B and P in enhancing electrocatalysis of oxygen evolution by nickel borides and nickel phosphides. The apparent activation energy, Ea*, of electrocatalytic oxygen evolution on Ni2P was 78.4 kJ/mol, on Ni2B 65.4 kJ/mol, and on Ni nanoparticles 94.0 kJ/mol, thus revealing that both B and P affect the intrinsic activity of nickel. XPS data revealed shifts of −0.30 and 0.40 eV in the binding energy of the Ni 2p3/2 peak of Ni2B and Ni2P, respectively, with respect to that of pure Ni at 852.60 eV, thus indicating that B and P induce opposite electronic effects on the surface electronic structure of Ni. The origin of enhanced activity for oxygen evolution cannot, therefore, be attributed to such electronic modification or ligand effect. Severe changes induced on the nickel lattice, specifically, the Ni-Ni atomic order and interatomic distances (strain effect), by the presence of the guest atoms seem to be the dominant factors responsible for enhanced activity of oxygen evolution in nickel borides and nickel phosphides. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/celc.201800669

• 2019 • 89	Segregation tendency of Heusler alloys Sokolovskiy, V.V. and Gruner, M.E. and Entel, P. and Acet, M. and Çaklr, A. and Baigutlin, D.R. and Buchelnikov, V.D. Physical Review Materials 3 (2019) Segregation in a series of Ni2Mn1+x(In,Sn,Ga,Al)1-x and Mn2Ni1+x(Ga, Al) as well as Ni2+xMn1-xGa Heusler alloys is studied by first-principles calculations. We show that Mn-rich Ni2Mn1+x(In,Sn,Al)1-x compounds are at low temperatures unstable in the whole concentration range against decomposition into a dual-phase system consisting of an L21-cubic Ni2MnX phase with ferromagnetic order and an L10-tetragonal NiMn phase ordered antiferromagnetically. In contrast, Ni2Mn1+xGa1-x and Mn2Ni1+x(Ga,Al)1-x are stable in the narrow concentration range near the 2-1-1 stoichiometry. This concentration range depends on the presence of a martensitic transformation and becomes wider with increasing energy difference between austenite and martensite phases in a parent system. We find that ferromagnetic Ni-rich Ni2+xMn1-xGa is stable in the concentration range 0<x≤0.6. © 2019 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevMaterials.3.084413

• 2019 • 88	Selective acid leaching: A simple way to engineer cobalt oxide nanostructures for the electrochemical oxygen evolution reaction Yu, M. and Belthle, K.S. and Tüysüz, C. and Tüysüz, H. Journal of Materials Chemistry A 7 23130-23139 (2019) Developing a simple and cost-effective strategy to construct earth-abundant catalysts is in high demand for diverse applications. Herein, a general and facile strategy is developed to engineer cobalt oxide nanostructures via selective acid leaching for the electrochemical oxygen evolution reaction (OER). A leaching process is implemented to selectively remove CoMoO4 by treating mixed Co-Mo oxides in diluted hydrochloric acid solution, resulting in the formation of sub-5 nm particles and a threefold increase in the specific surface area (up to 150 m2 g-1). The leached oxides exhibit superior OER activity to pristine oxides as a result of (i) a larger surface area, (ii) phase purification to expose more active Co3O4 species to the reactant, and (iii) faster charge transfer kinetics for the OER. This strategy can be also applied to a broader range of earth-abundant metals, where a second metal (Li, Ca, and Mg) is selectively leached out, which results in a material with a larger surface area and enhanced catalytic performance for the OER. Moreover, various metal oxides with a high surface area, such as NiO and Fe2O3, can be prepared via this simple synthetic method. This work will pave a new practical way for the production of high surface area catalysts for diverse applications. © The Royal Society of Chemistry 2019.
  	view abstract	doi: 10.1039/c9ta07835e

• 2019 • 87	Strength of hydrogen-free and hydrogen-doped Ni 50 Ti 50 shape memory platelets Weiser, A. and Buršíková, V. and Jarý, M. and Dymáček, P. and Dugáček, J. and Frenzel, J. and Čermák, J. and Dlouhý, A. Scripta Materialia 162 151-155 (2019) Small-punch and nano-indentation tests were used for the first time to probe strength of 500 μm thin Ni 50 Ti 50 shape memory platelets in their hydrogen-free and hydrogen-doped states. Results show excellent reproducibility and suggest that hydrogen penetrates the alloy more efficiently during the cathodic charging at ambient temperatures as compared to heat treatments in a controlled hydrogen atmosphere. Hydrogen content exceeding 100 wtppm results in a retransformation from the B19′ martensite to the R lattice and causes a systematic drop of the rupture strength. The retransformation events in thin surface lamellae were documented by the transmission electron microscopy. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.scriptamat.2018.10.044

• 2019 • 86	Strength of hydrogen-free and hydrogen-doped Ni50Ti50 shape memory platelets Weiser, A. and Buršíková, V. and Jarý, M. and Dymáček, P. and Dugáček, J. and Frenzel, J. and Čermák, J. and Dlouhý, A. Scripta Materialia 162 151-155 (2019) Small-punch and nano-indentation tests were used for the first time to probe strength of 500 μm thin Ni50Ti50 shape memory platelets in their hydrogen-free and hydrogen-doped states. Results show excellent reproducibility and suggest that hydrogen penetrates the alloy more efficiently during the cathodic charging at ambient temperatures as compared to heat treatments in a controlled hydrogen atmosphere. Hydrogen content exceeding 100 wtppm results in a retransformation from the B19′ martensite to the R lattice and causes a systematic drop of the rupture strength. The retransformation events in thin surface lamellae were documented by the transmission electron microscopy. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.scriptamat.2018.10.044

• 2019 • 85	Synergistic Effects of Mo2C-NC@CoxFey Core–Shell Nanoparticles in Electrocatalytic Overall Water Splitting Reaction Wang, S. and Bendt, G. and Saddeler, S. and Schulz, S. Energy Technology 7 (2019) Transition metals (TMs) are highly investigated as nonprecious electrocatalysts for hydrogen evolution (HER) and oxygen evolution (OER) reactions. There is a strong demand for highly efficient and inexpensive catalysts for overall water splitting. Herein, the bimetallic CoxFey alloy nanoparticles encapsulated in a N-doped graphene shell containing molybdenum carbide (Mo2C) nanoparticles are synthesized by the pyrolysis of cobalt ferrite (CoxFe3−xO4) nanoparticles coated by melamine-formaldehyde resin cross-linked with molybdic acid. Molybdic acid not only serves as precursor for the formation of highly dispersed Mo2C nanoparticles in the N-doped graphene shell but also enhances the thermal stability of the organic shell, resulting in the formation of smaller CoxFey cores. The formation of Mo2C nanoparticles in the graphene shell is promoted by the CoxFe3−xO4 core. Interestingly, the synergistic presence of Mo2C nanoparticles not only enhances the HER activity of the material but also renders a partial breakage of the graphene shell, which increases the surface concentration of OER-active Co and therefore enhances the OER activity. The as-prepared TM-based materials serve as bifunctional catalysts for the overall water splitting and exhibit improved electrocatalytic performances compared to standard cells based on precious metals, with the potentials of 1.53 and 1.60 V at 10 and 20 mA cm−2 in alkaline media, respectively. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/ente.201801121

• 2019 • 84	Synthesis of Mixed AuZn Nanoparticles by Spark Discharge Technique Kala, S. and Kruis, F.E. MRS Advances 4 1621-1629 (2019) In this study, feasibility of spark discharge technique to generate mixed metal nanoparticles is demonstrated. Two immiscible metals Au and Zn are selected to prepare AuZn mixed nanoparticles. Ignition of spark between Au and Zn electrodes under normal pressure, in the presence of carrier gas, leads to formation of mixed nanoparticles by condensation and nucleation. Online particle size-distribution is monitored by a scanning mobility particle sizer on changing carrier gas flow rate and capacitor charging current during co-sparking between Au and Zn electrodes. The technique provides flexibility to generate binary mixture of AuZn nanoparticles in the size range of 10-80 nm. Distribution of Au and Zn in the prepared mixed nanoparticles is mapped by scanning electron microscopy and high resolution electron microscopy. © Materials Research Society 2019.
  	view abstract	doi: 10.1557/adv.2019.221

• 2019 • 83	Synthesis, microstructure, and hardness of rapidly solidified Cu-Cr alloys Garzón-Manjón, A. and Christiansen, L. and Kirchlechner, I. and Breitbach, B. and Liebscher, C.H. and Springer, H. and Dehm, G. Journal of Alloys and Compounds 794 203-209 (2019) Cu-Cr alloys with ∼32 at.% Cr were rapidly solidified by splat quenching or laser melting techniques with the intention to form a very fine grained, non-equilibrium nanostructure similar to those obtained by severe plastic deformation or thin film deposition. The rapidly solidified Cu-Cr alloys were analyzed by X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Both synthesis techniques lead to a similar two-phase microstructure with a nearly pure fcc Cu matrix with μm grain sizes and bcc Cr particles highly supersaturated with Cu. Splat quenching provides finer bcc particles with dimensions of less than 50 nm compared to laser melting with particle sizes of 100–2000 nm. In case of laser melting, (14 ± 2) at.% Cu are contained in the bcc phase, while splat quenching freezes (20 ± 2) at.% Cu in the bcc particles. The microstructures are discussed and compared to the non-equilibrium microstructures reported in literature using severe plastic deformation and thin films deposition. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.jallcom.2019.04.209

• 2019 • 82	Temperature and load-ratio dependent fatigue-crack growth in the CrMnFeCoNi high-entropy alloy Thurston, K.V.S. and Gludovatz, B. and Yu, Q. and Laplanche, G. and George, E.P. and Ritchie, R.O. Journal of Alloys and Compounds 794 525-533 (2019) Multiple-principal element alloys known as high-entropy alloys have rapidly been gaining attention for the vast variety of compositions and potential combinations of properties that remain to be explored. Of these alloys, one of the earliest, the ‘Cantor alloy’ CrMnFeCoNi, displays excellent damage-tolerance with tensile strengths of ∼1 GPa and fracture toughness values in excess of 200 MPa√m; moreover, these mechanical properties tend to further improve at cryogenic temperatures. However, few studies have explored its corresponding fatigue properties. Here we expand on our previous study to examine the mechanics and mechanisms of fatigue-crack propagation in the CrMnFeCoNi alloy (∼7 μm grain size), with emphasis on long-life, near-threshold fatigue behavior, specifically as a function of load ratio at temperatures between ambient and liquid-nitrogen temperatures (293 K–77 K). We find that ΔKth fatigue thresholds are decreased with increasing positive load ratios, R between 0.1 and 0.7, but are increased at decreasing temperature. These effects can be attributed to the role of roughness-induced crack closure, which was estimated using compliance measurements. Evidence of deformation twinning at the crack tip during fatigue-crack advance was not apparent at ambient temperatures but seen at higher stress intensities (ΔK ∼ 20 MPa√m) at 77 K by post mortem microstructural analysis for tests at R = 0.1 and particularly at 0.7. Overall, the fatigue behavior of this alloy was found to be superior, or at least comparable, to conventional cryogenic and TWIP steels such as 304 L or 316 L steels and Fe-Mn steels; these results coupled with the remarkable strength and fracture toughness of the Cantor alloy at low temperatures indicate significant promise for the utility of this material for applications at cryogenic environments. © 2019
  	view abstract	doi: 10.1016/j.jallcom.2019.04.234

• 2019 • 81	Templated Dealloying: Designing Ultrastructures by Memory Effect Kamp, M. and Tymoczko, A. and Schürmann, U. and Jakobi, J. and Rehbock, C. and Barcikowski, S. and Kienle, L. Crystal Growth and Design 19 4957-4963 (2019) Tailoring the morphology of nanoporous structures widens the scope of applications in catalysis and sensing. The synthesis of versatile nanoporous morphologies with the spatial distribution of porosity is permitted by the dealloying of unique, metastable Au-Fe alloy template nanoparticles generated by laser ablation in liquids. This approach opens the door to a novel process, which involves a special transformation mechanism, including oxidation and Kirkendall effect, which is decisive for the stabilization of hollow structures with the spatial distribution of porosity and represents a memory effect of morphology. Within this work, nanoporous Au particles, hollow nanoporous Au shells with the spatial distribution of porosity, and yolk-shell-like Au nanoparticles encapsulated in ultrathin Au shells are synthesized. A distinct variation of crystallinity and an increased lattice strain is observed, which implies an improved catalytic activity for oxidation reactions. © 2019 American Chemical Society.
  	view abstract	doi: 10.1021/acs.cgd.9b00175

• 2019 • 80	Thermally stable iridium contacts to highly doped p-In0:53Ga0:47As for indium phosphide double heterojunction bipolar transistors Brahem, M. and Mogilatenko, A. and Stoppel, D. and Berger, D. and Hochheim, S. and Rentner, D. and Ostermay, I. and Reiner, M. and Boppel, S. and Nosaeva, K. and Weimann, N. Microelectronic Engineering 215 (2019) We report on surface pretreatment for ohmic contacts to p-doped In0.53Ga0.47 As with improved thermal stability. It is found that the cleaning of In0.53Ga0.47 As surface by ammonium sulfide or sulfuric acid offers the optimum surface treatment prior to metal deposition. Contacts using an iridium contact layer and palladium diffusion barrier were fabricated and compared to a conventional platinum-based contact Pt/Ti/Pt/Au. Pt-based metal stack suffered from void formation and high reactivity with the semiconductor when annealed at 240 °C for a few hours, as examined by transmission electron microscopy. As a result, the Pt-based stack exhibited strong deterioration of the resistivity. On the other hand, the Ir contact maintained its integrity during thermal stress. The improved contact exhibited a void and reaction-free microstructure and offered stable resistivity values with annealing. © 2019 Elsevier B.V.
  	view abstract	doi: 10.1016/j.mee.2019.111017

• 2019 • 79	Thermodynamic assessment of the Co-Ta system Wang, P. and Koßmann, J. and Kattner, U.R. and Palumbo, M. and Hammerschmidt, T. and Olson, G.B. Calphad: Computer Coupling of Phase Diagrams and Thermochemistry 64 205-212 (2019) The Co-Ta system has been reviewed and the thermodynamic description was re-assessed in the present work. DFT (density functional theory) calculations considering spin polarization were performed to obtain the energies for all end-member configurations of the C14, C15, C36 and μ phases for the evaluation of the Gibbs energies of these phases. The phase diagram calculated with the present description agrees well with the experimental and theoretical data. Considering the DFT results was essential for giving a better description of the μ phase at lower temperatures. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.calphad.2018.12.002

• 2019 • 78	Thermodynamics of grain boundary segregation, interfacial spinodal and their relevance for nucleation during solid-solid phase transitions Kwiatkowski da Silva, A. and Kamachali, R.D. and Ponge, D. and Gault, B. and Neugebauer, J. and Raabe, D. Acta Materialia 168 109-120 (2019) Grain boundary segregation, embrittlement and phase nucleation are interconnected phenomena that are often treated separately, which is partly due to limitations of the current models to predict grain boundary segregation in non-ideal solid solutions. Here, a simple model is introduced to predict grain boundary segregation in solid solutions by coupling available bulk thermodynamic data with a mean-field description of the grain boundary character. The model is confronted with experimental results obtained in Fe-Mn alloys analysed by atom probe tomography. This model successfully predicts a first order transition or a discontinuous jump in the composition of the grain boundary which kinetically implies the formation of spinodal Mn fluctuations that tend to grow further with time within the segregated region. The increase in solute concentration at the grain boundary leads to an increase of the enthalpy of the boundary and to its embrittlement at lower temperatures. Once austenite is formed, the amount of segregated solute Mn on the grain boundaries is drastically reduced and the toughness of the grain boundary is increased. © 2019 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2019.02.005

• 2019 • 77	Thermomechanical behavior of shape memory alloy metal matrix composite actuator manufactured by composite extrusion Dahnke, C. and Reeb, A. and Pottmeyer, F. and Weidenmann, K.A. and Tekkaya, A.E. Smart Materials and Structures 28 (2019) Continuous composite extrusion represents a new possibility for the manufacturing of shape memory alloy metal matrix composites (SMA-MMC). During the process SMA wires are embedded into aluminum or magnesium profiles by means of modified porthole dies. Due to the high flexibility regarding the profile geometry, the materials as well as number, thickness and position of the SMA elements, the process can be used for the generation of a profile integrated bending function. The bending function of the actuator profile depends on the temperature and is thermally activated. The parameters influencing the behavior of the manufactured composited actuators are experimentally investigated. It is found that the radius of curvature mainly depends on the recovery stress and the eccentric position of the SMA wire as well as on the bending stiffness of the actuator profile. The bending mechanism and the experimental results are described by the use of an analytical model as well as a finite element analysis. Based on the results the analytical model is used for the targeted design of a profile with multiple embedded NiTi wires, which is able to perform a repeatable, pure elastic deflection within a defined temperature range between room temperature and 75 °C. © 2019 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-665X/ab0ef5

• 2019 • 76	Ultra-fast sintered functionally graded Fe/W composites for the first wall of future fusion reactors Heuer, S. and Lienig, T. and Mohr, A. and Weber, T. and Pintsuk, G. and Coenen, J.W. and Gormann, F. and Theisen, W. and Linsmeier, C. Composites Part B: Engineering 164 205-214 (2019) Aiming at the realisation of nuclear fusion reactors, the joining of W and steel parts is currently examined. Based on proposals to implement functionally graded steel/W materials (FGMs) in the joint to cope with thermal stresses, the present contribution introduces a novel fabrication method for steel/W FGMs. Electro Discharge Sintering (EDS) was used to consolidate Fe/W powders within milliseconds at atmosphere. Due to the short process time, the formation of detrimental intermetallic Fe-W precipitates is limited compared to established fabrication methods. The current work first presents results of the Fe/W powder processing, then a feasibility study regarding the fabrication of homogeneous and graded Fe/W composites with W volume fractions of 0, 25, 50 and 75 % via EDS is presented. Lastly, the composites are characterised microstructurally, thermo-physically, and mechanically in detail. © 2018
  	view abstract	doi: 10.1016/j.compositesb.2018.11.078

• 2019 • 75	X-ray powder diffraction to analyse bimetallic core-shell nanoparticles (gold and palladium; 7-8 nm) Rostek, A. and Loza, K. and Heggen, M. and Epple, M. RSC Advances 9 26628-26636 (2019) A comparative X-ray powder diffraction study on poly(N-vinyl pyrrolidone) (PVP)-stabilized palladium and gold nanoparticles and bimetallic Pd-Au nanoparticles (both types of core-shell nanostructures) was performed. The average diameter of Au and Pd nanoparticles was 5 to 6 nm. The two types of core-shell particles had a core diameter of 5 to 6 nm and an overall diameter of 7 to 8 nm, i.e. a shell thickness of 1 to 2 nm. X-ray powder diffraction on a laboratory instrument was able to distinguish between a physical mixture of gold and palladium nanoparticles and bimetallic core-shell nanoparticles. It was also possible to separate the core from the shell in both kinds of bimetallic core-shell nanoparticles due to the different domain size and because it was known which metal was in the core and which was in the shell. The spherical particles were synthesized by reduction with glucose in aqueous media. After purification by multiple centrifugation steps, the particles were characterized with respect to their structural, colloid-chemical, and spectroscopic properties, i.e. particle size, morphology, and internal elemental distribution. Dynamic light scattering (DLS), differential centrifugal sedimentation (DCS), atomic absorption spectroscopy (AAS), ultraviolet-visible spectroscopy (UV-vis), high-angle annular dark field imaging (HAADF), and energy-dispersed X-ray spectroscopy (EDX) were applied for particle characterization. This journal is © The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c9ra05117a

• 2018 • 74	A variable pole magnet Çakir, A. and Krenke, T. and Farle, M. and Acet, M. Journal of Physics Condensed Matter 30 (2018) The off-stoichiometric antiferromagnetic Heusler alloy Fe50Mn45Ga5 decomposes and forms ferromagnetic Fe50Mn25Ga25 precipitates embedded in an antiferromagnetic Fe50Mn50 matrix when temper-annealed at temperatures T > 550 K. The ferromagnetism of the precipitates is soft so that the magnetization direction of the non-interacting precipitates in a macroscopic material can be manipulated by locally applied fields so that even two similar poles can form at the ends of a centimeter-long bar. The cause for the soft magnetic behavior is due to the weak AF exchange anisotropy of the cubic Fe50Mn50 matrix and the precipitate. © 2018 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-648X/aaa5f5

• 2018 • 73	An examination of interactions between temperature, pressure, sintering time, and Si/W ratio on the sintering behavior of CrSiW Tillmann, W. and Fehr, A. and Ferreira, M. and Stangier, D. International Journal of Refractory Metals and Hard Materials 73 146-156 (2018) A Statistic Design of Experiments (DoE) was implemented with the aim to systematically investigate sintering parameter interactions of hot pressed 80Cr10Si10W. By varying the temperature between 999 and 1200 °C at pressures ranging from 2 to 8 MPa for 6.6 to 23.4 min, an initial examination of the ternary system is realized. The overall objective of this study is to minimize the porosity and to foster a diffusion of the elements. The investigations revealed that high temperatures (>1000 °C) and pressures (>6 MPa) support the diffusion between chromium and silicon while tungsten particles accumulate at the grain boundaries of silicon. XRD analyses confirmed the existence of a c-CrSi3 phase. The setup of the DoE, which promises the highest densification, was subsequently used to examine the influence of the silicon and tungsten content on the porosity according to the pattern 80Cr(20-x)Si(x)W for 0 ≥ x ≥ 20 (in wt%). This approach generated the lowest porosity (3.2 ± 0.93 area%) for 80Cr20W and led to homogenous particle distributions. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.ijrmhm.2018.02.012

• 2018 • 72	Antibacterial Efficacy of Sacrifical Anode Thin Films Combining Silver with Platinum Group Elements within a Bacteria-Containing Human Plasma Clot Abuayyash, A. and Ziegler, N. and Gessmann, J. and Sengstock, C. and Schildhauer, T.A. and Ludwig, Al. and Köller, M. Advanced Engineering Materials 20 (2018) Silver (Ag) dots arrays (64 and 400 dots per mm2) are fabricated on a continuous platinum (Pt), palladium (Pd), or iridium (Ir) thin film (sacrifical anode systems for Ag) and for comparison on titanium (Ti) film (non-sacrifical anode system for Ag) by sputter deposition and photolithographic patterning. The samples are embedded within a tissue-like plasma clot matrix containing Staphylococcus aureus (S. aureus), cultivated for 24 h. Bacterial growth is analyzed by fluorescence microscopy. Among platinum group sacrifical anode elements and a dense Ag sample, only the high Ag ion releasing Ag–Ir system is able to inhibit the bacterial growth within the adjacent plasma clot matrix. This study demonstrates that the antibacterial efficiency of Ag coatings is reduced under tissue-like conditions. However, the new sacrificial anode based Ag–Ir system can overcome this limitation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/adem.201700493

• 2018 • 71	Characterizing solute hydrogen and hydrides in pure and alloyed titanium at the atomic scale Chang, Y. and Breen, A.J. and Tarzimoghadam, Z. and Kürnsteiner, P. and Gardner, H. and Ackerman, A. and Radecka, A. and Bagot, P.A.J. and Lu, W. and Li, T. and Jägle, E.A. and Herbig, M. and Stephenson, L.T. and Moody, M.P. and... Acta Materialia 150 273-280 (2018) Ti and its alloys have a high affinity for hydrogen and are typical hydride formers. Ti-hydride are brittle phases which probably cause premature failure of Ti-alloys. Here, we used atom probe tomography and electron microscopy to investigate the hydrogen distribution in a set of specimens of commercially pure Ti, model and commercial Ti-alloys. Although likely partly introduced during specimen preparation with the focused-ion beam, we show formation of Ti-hydrides along α grain boundaries and α/β phase boundaries in commercial pure Ti and α+β binary model alloys. No hydrides are observed in the α phase in alloys with Al addition or quenched-in Mo supersaturation. © 2018 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2018.02.064

• 2018 • 70	Coherently strained [Fe-Co(C)/Au-Cu]n multilayers: A path to induce magnetic anisotropy in Fe-Co films over large thicknesses Giannopoulos, G. and Salikhov, R. and Varvaro, G. and Psycharis, V. and Testa, A.M. and Farle, M. and Niarchos, D. Journal of Physics D: Applied Physics 51 (2018) Among novel critical-element-free materials for permanent magnets, the nearly equiatomic Fe-Co alloy has recently attracted a great deal of attention as a large magneto-crystalline anisotropy can be induced by straining the Fe-Co unit cell. In thin film systems, the use of a suitable underlayer allows a tetragonal reconstruction of the Fe-Co to be triggered up to a critical thickness of few nanometers, above which the crystal structure relaxes to the magnetically soft cubic phase. Scaling-up the thickness of the metastable tetragonal Fe-Co phase is of crucial significance for different nanoscale applications, such as magnetic micro- and nano-electromechanical systems. To suppress the strain relaxation occurring at high thicknesses, we explored a novel approach based on Fe-Co(C)/Au-Cu multilayer films, where both Au-Cu interlayers and carbon (C) doping were used to stabilize the strained Fe-Co tetragonal phase over large thicknesses. Both doped and un-doped multilayer structures show a coherently strained regime, persisting up to a thickness of 60 nm, which leads, possibly in combination with the surface anisotropy induced at the Au-Cu interfaces, to the appearance of a large out-of-plane anisotropy (up to 0.4 MJ m-3), thus suggesting the potential of such an approach to develop critical-element-free thin film permanent magnets for a variety of nanoscale applications. © 2018 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-6463/aaa41c

• 2018 • 69	Compositional evolution of long-period stacking ordered structures in magnesium studied by atom probe tomography Kim, J.-K. and Guo, W. and Choi, P.-P. and Raabe, D. Scripta Materialia 156 55-59 (2018) Mg alloys containing long-period stacking ordered (LPSO) structures are strong and ductile compared to conventional Mg alloys. We study here the compositional evolution of LPSO structures in a Mg97Y2Zn1 (at.%) alloy upon annealing at 500 °C using atom probe tomography. In the material annealed for 2.5 h, the Zn/Y ratio of the building blocks in the interdendritic LPSO phase (0.73) is close to the stoichiometric composition of Y8Zn6 L12 clusters while that in plate-type LPSO structures (0.66) slightly deviates from the ideal value. The Y/Zn enrichment in LPSO structures in the α-Mg matrix slightly decreases with increasing annealing time. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.scriptamat.2018.07.017

• 2018 • 68	Computationally Efficient Phase-field Simulation Studies Using RVE Sampling and Statistical Analysis Schwarze, C. and Darvishi Kamachali, R. and Kühbach, M. and Mießen, C. and Tegeler, M. and Barrales-Mora, L. and Steinbach, I. and Gottstein, G. Computational Materials Science 147 204-216 (2018) For large-scale phase-field simulations, the trade-off between accuracy and computational cost as a function of the size and number of simulations was studied. For this purpose, a large reference representative volume element (RVE) was incrementally subdivided into smaller solitary samples. We have considered diffusion-controlled growth and early ripening of δ′ (Al3Li) precipitate in a model Al-Li system. The results of the simulations show that decomposition of reference RVE can be a valuable computational technique to accelerate simulations without a substantial loss of accuracy. In the current case study, the precipitate number density was found to be the key controlling parameter. For a pre-set accuracy, it turned out that large-scale simulations of the reference RVE can be replaced by simulating a combination of smaller solitary samples. This shortens the required simulation time and improves the memory usage of the simulation considerably, and thus substantially increases the efficiency of massive parallel computation for phase-field applications. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.commatsci.2018.02.005

• 2018 • 67	Control of Cooperativity through a Reversible Structural Phase Transition in MoMo-Methyl/Cu(111) Kollamana, J. and Wei, Z. and Lyu, L. and Zimmer, M. and Dietrich, F. and Eul, T. and Stöckl, J. and Maniraj, M. and Ponzoni, S. and Cinchetti, M. and Stadtmüller, B. and Gerhards, M. and Aeschlimann, M. Advanced Functional Materials 28 (2018) The bimetallic molecular compound Dimolybdenum tetraacetate (MoMo-Methyl) is grown on a Cu(111) surface with submonolayer coverage. Scanning tunneling microscopy experiments reveal that the compound forms two different structural phases on the Cu surface, whose ratio can be reversibly controlled by changing the sample temperature. The so-called chain-phase is characterized by tilted MoMo dimers bonded to the Cu surface via the methyl groups. In the so-called mesh-phase, on the other hand, the molecules adsorb in a flat lying adsorption configuration with one of the Mo-atoms in direct contact with the Cu surface. Crucially, the different structural properties of the two phases reflect the different inter- and intramolecular interactions between the Mo metal centers, as well as the different interactions between Mo and the Cu surface atoms. In this way, the structural changes result in a modification of the cooperative effects in the system. Therefore, it is proposed that the observed reversible structural phase transition could be used to control the strength of cooperative effects in MoMo-Methyl on Cu(111). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/adfm.201703544

• 2018 • 66	Crystallographic characterization of laser-generated, polymer-stabilized 4 nm silver-gold alloyed nanoparticles Prymak, O. and Jakobi, J. and Rehbock, C. and Epple, M. and Barcikowski, S. Materials Chemistry and Physics 207 442-450 (2018) Monometallic silver and gold nanoparticles and bimetallic silver-gold (AgAu) nanoparticles were prepared by laser ablation in liquids in the atomic composition range of Ag:Au from 0:100 to 100:0 with steps of 10 at% and colloidally stabilized with poly(N-vinylpyrrolidone) (PVP). As metallic bulk targets for laser ablation, pure silver, pure gold, and alloyed AgAu foils with the desired composition were used. Size separation by centrifugation and freeze-drying gave monodisperse spherical nanoparticles with a diameter of 4 nm as determined by differential centrifugal sedimentation (DCS) and transmission electron microscopy (TEM). A crystallographic characterization of the nanoparticles was carried out by X-ray powder diffraction (XRD) and Rietveld refinement, leading to highly precise cubic lattice parameters (fcc crystal system) and crystallite sizes. For comparison, the same analysis including the determination of the microstrain was carried out for the bulk target materials (AgAu alloys in the full concentration range). Both nanoparticles and bulk target materials obeyed Vegard's rule, with only slight deviations. The fact that the crystallite size as determined by XRD was identical to the hydrodynamic diameter by DCS and the Feret diameter by TEM indicates that the particles consist of only one domain, i.e. they are single crystals. The combination of UV-vis spectroscopy with energy-dispersive X-ray spectroscopy (EDX) as line scan along the nanoparticle showed a homogenous distribution of the gold and silver inside the nanoparticles, indicating solid solution alloys, in contrast to what was observed earlier for chemically prepared AgAu nanoparticles by reduction of metal ions in water. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.matchemphys.2017.12.080

• 2018 • 65	CuPd Mixed-Metal HKUST-1 as a Catalyst for Aerobic Alcohol Oxidation Guo, P. and Froese, C. and Fu, Q. and Chen, Y.-T. and Peng, B. and Kleist, W. and Fischer, R.A. and Muhler, M. and Wang, Y. Journal of Physical Chemistry C 122 21433-21440 (2018) Metal-organic frameworks (MOFs) featuring isolated coordinatively unsaturated metal sites (CUS) have enormous potential as single-site catalysts. In particular, mixed-metal MOFs may exhibit unique catalytic properties compared to their monometallic counterparts. Herein, we report a thorough fundamental study on the mixed-metal CuPd-HKUST-1 ([Cu 3-x Pd x (BTC) 2 ] n ; BTC = 1,3,5-benzenetricarboxylate) including the two-step synthesis, characterization, and catalytic performance evaluation. The combined results from a multitechnique approach provide solid evidence that the chemical properties of HKUST-1 can be tuned via successful incorporation of Pd-CUS into the framework, leading to the formation of new Cu-Pd and/or Pd-Pd dimers. The introduction of Pd occurs exclusively at the metal nodes in a controlled manner while retaining the structural integrity. The incorporated Pd ions have an oxidation state of +2, whereas no PdO or metallic Pd nanoparticles embedded inside MOFs are detected. These mixed-metal CuPd-MOFs exhibit superior catalytic activity and selectivity for the aerobic oxidation of benzyl alcohol to benzaldehyde, and the doped Pd 2+ -CUS species are identified as isolated single-active sites. © 2018 American Chemical Society.
  	view abstract	doi: 10.1021/acs.jpcc.8b05882

• 2018 • 64	Development of high modulus steels based on the Fe – Cr – B system Baron, C. and Springer, H. and Raabe, D. Materials Science and Engineering A 724 142-147 (2018) We present a novel alloy design strategy for cost-efficient high modulus steels with an increased stiffness / mass density ratio. The concept is based on the liquid metallurgy synthesis of Fe – Cr – B based alloys, straightforward processability, and well tuneable mechanical properties via plain heat treatments. The base alloy Fe – 18 Cr – 1.6 B (wt%) contained 14–17 vol% of (Cr,Fe)2B particles of ellipsoidal morphology in a ferritic matrix. Hot rolled materials revealed a specific modulus of 32.8 GPa g−1 cm3, exceeding that of conventional Fe-Cr steels by almost 30%. Mechanical properties obtained are comparable to TiB2 based high modulus steels. Addition of 1 wt% Cu to the base alloy did not interact with the formation, fraction, size and morphology of (Cr,Fe)2B particles, and allowed to mildly increase the strength values by ageing treatments, however at the price of a reduction of the specific modulus. C additions of 0.2 wt% did not affect the (Cr,Fe)2B particle microstructure greatly, but free C dissolved in the matrix enables for the first time to utilize the wide range of microstructures and mechanical properties of established C-containing high strength steels also in high modulus steels. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.msea.2018.03.082

• 2018 • 63	Electrocatalytic Nanoparticles That Mimic the Three-Dimensional Geometric Architecture of Enzymes: Nanozymes Benedetti, T.M. and Andronescu, C. and Cheong, S. and Wilde, P. and Wordsworth, J. and Kientz, M. and Tilley, R.D. and Schuhmann, W. and Gooding, J.J. Journal of the American Chemical Society 140 13449-13455 (2018) Enzymes are characterized by an active site that is typically embedded deeply within the protein shell thus creating a nanoconfined reaction volume in which high turnover rates occur. We propose nanoparticles with etched substrate channels as a simplified enzyme mimic, denominated nanozymes, for electrocatalysis. We demonstrate increased electrocatalytic activity for the oxygen reduction reaction using PtNi nanoparticles with isolated substrate channels. The PtNi nanoparticles comprise an oleylamine capping layer that blocks the external surface of the nanoparticles participating in the catalytic reaction. Oxygen reduction mainly occurs within the etched channels providing a nanoconfined reaction volume different from the bulk electrolyte conditions. The oxygen reduction reaction activity normalized by the electrochemically active surface area is enhanced by a factor of 3.3 for the nanozymes compared to the unetched nanoparticles and a factor of 2.1 compared to mesoporous PtNi nanoparticles that possess interconnecting pores. © Copyright 2018 American Chemical Society.
  	view abstract	doi: 10.1021/jacs.8b08664

• 2018 • 62	Elemental partitioning and site-occupancy in γ/γ′ forming Co-Ti-Mo and Co-Ti-Cr alloys Im, H.J. and Makineni, S.K. and Gault, B. and Stein, F. and Raabe, D. and Choi, P.-P. Scripta Materialia 154 159-162 (2018) We report on the sub-nanometer scale characterization of Co-12Ti-4Mo and Co-12Ti-4Cr (at.%) model alloys. Atom probe tomography reveals that Co and Cr partition to γ, whereas Ti and Mo to γ′. Additions of Mo and Cr to the reference Co-12Ti system lead to strong increases in γ′ volume fraction by about 25% and 12%, respectively. Element-specific spatial distribution maps along the [001] direction of the L12-ordered γ′ phase reveal that both Mo and Cr preferentially replace Ti on its sublattice. The remaining excess Ti is available for formation of additional γ′, resulting in enhanced γ′ volume fractions. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.scriptamat.2018.05.041

• 2018 • 61	Elemental segregation to twin boundaries in a MnAl ferromagnetic Heusler alloy Palanisamy, D. and Raabe, D. and Gault, B. Scripta Materialia 155 144-148 (2018) Electron microscopy and atom probe tomography were combined to investigate the crystallography and chemistry of a single twin boundary (TB) in a rare-earth-free ferromagnetic MnAl Heusler alloy. The results establish a significant segregation of Mn along the twin boundaries. An enrichment of approx. ~8 at.% Mn was measured along the twin boundary with a confined depletion outside the twin boundary, suggesting short range solute diffusion occurring during massive transformation. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.scriptamat.2018.06.037

• 2018 • 60	Fabrication of perovskite-based porous nanotubes as efficient bifunctional catalyst and application in hybrid lithium-oxygen batteries Gong, H. and Wang, T. and Guo, H. and Fan, X. and Liu, X. and Song, L. and Xia, W. and Gao, B. and Huang, X. and He, J. Journal of Materials Chemistry A 6 16943-16949 (2018) The design of efficient oxygen electrocatalysts is extremely important and urgent for much energy storage and conversion equipment. Among these, the high energy densities of lithium-oxygen batteries (LOBs) have driven us to explore bifunctional catalysts. Compared with non-aqueous LOBs, which have been blamed for poor cycling stability due to their undesirable side reaction, hybrid LOBs have been considered an alternative solution due to their high electrochemical reversibility and safeness. Here, one-dimensional hierarchical mesoporous/macroporous LaMn0.7Co0.3O3-x nanotubes were synthesized through an electrospinning method combined with an annealing treatment. With the suitable heat treatment and rational doping with elemental Co, the LMCO-800 sample shows a well-designed hierarchical porous nanotube structure and possess great bifunctional electrocatalytic performance. The linear sweep voltammetry (LSV) curves show that the half-wave potential (E1/2) of the LMCO-800 sample is 0.72 V (vs. RHE) and the average electron transfer number (n) is calculated to be 3.8. Moreover, the successful doping of elemental Co into the LMCO-800 nanotubes can shorten the average distance of the Mn-Mn atoms and promote the formation of O-O bonds, contributing to the enhanced OER performance. The high specific surface area and one-dimensional nanotubes can greatly benefit oxygen diffusion, facilitate electrolyte infiltration and improve electron transfer. Consequently, the as-assembled hybrid lithium-oxygen batteries with an LMCO-800 cathode exhibit superior cycling stability. © 2018 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c8ta04599b

• 2018 • 59	From Quasicrystals to Crystals with Interpenetrating Icosahedra in Ca-Au-Al: In Situ Variable-Temperature Transformation Pham, J. and Meng, F. and Lynn, M.J. and Ma, T. and Kreyssig, A. and Kramer, M.J. and Goldman, A.I. and Miller, G.J. Journal of the American Chemical Society 140 1337-1347 (2018) The irreversible transformation from an icosahedral quasicrystal (i-QC) CaAu4.39Al1.61 to its cubic 2/1 crystalline approximant (CA) Ca13Au56.31(3)Al21.69 (CaAu4.33(1)Al1.67, Pa3 (No. 205); Pearson symbol: cP728; a = 23.8934(4)), starting at ∼570 °C and complete by ∼650 °C, is discovered from in situ, high-energy, variable-temperature powder X-ray diffraction (PXRD), thereby providing direct experimental evidence for the relationship between QCs and their associated CAs. The new cubic phase crystallizes in a Tsai-type approximant structure under the broader classification of polar intermetallic compounds, in which atoms of different electronegativities, viz., electronegative Au + Al vs electropositive Ca, are arranged in concentric shells. From a structural chemical perspective, the outermost shell of this cubic approximant may be described as interpenetrating and edge-sharing icosahedra, a perspective that is obtained by splitting the traditional structural description of this shell as a 92-atom rhombic triacontahedron into an 80-vertex cage of primarily Au [Au59.86(2)Al17.14□3.00] and an icosahedral shell of only Al [Al10.5□1.5]. Following the proposal that the cubic 2/1 CA approximates the structure of the i-QC and on the basis of the observed transformation, an atomic site analysis of the 2/1 CA, which shows a preference to maximize the number of heteroatomic Au-Al nearest neighbor contacts over homoatomic Al-Al contacts, implies a similar outcome for the i-QC structure. Analysis of the most intense reflections in the diffraction pattern of the cubic 2/1 CA that changed during the phase transformation shows correlations with icosahedral symmetry, and the stability of this cubic phase is assessed using valence electron counts. According to electronic structure calculations, a cubic 1/1 CA, "Ca24Au88Al64" (CaAu3.67Al2.67) is proposed. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/jacs.7b10358

• 2018 • 58	Glycerol Oxidation Using MgO- and Al2O3-supported Gold and Gold–Palladium Nanoparticles Prepared in the Absence of Polymer Stabilizers Dodekatos, G. and Abis, L. and Freakley, S.J. and Tüysüz, H. and Hutchings, G.J. ChemCatChem 10 1351-1359 (2018) Au and AuPd nanoparticles supported on MgO and Al2O3 were employed for the selective aqueous phase oxidation of glycerol under basic conditions. Catalysts were prepared by sol-immobilization without the addition of a stabilizing agent such as polyvinyl alcohol (PVA), which is generally added to stabilize the noble metal sol prior to immobilization. The obtained materials prepared with and without stabilizing agent were active for glycerol oxidation and showed similar catalytic performances—implying that the stabilizing polymer is not required to obtain active materials. Depending on the support used, it was possible to tailor the selectivity towards the desired oxidation products by using catalysts prepared with or without stabilizing agent. PVA-free Au/γ-Al2O3 exhibited a remarkably high selectivity towards tartronic acid (40 % at 97 % conversion), which was not observed for Au/γ-Al2O3 prepared with PVA (27 % at isoconversion). Selective glycerol oxidation performed under base-free conditions over AuPd/MgO catalysts also corroborated the previous results that the presence of a stabilizing polymer is not required to prepare active catalysts by sol-immobilization. Thus, a facile way to circumvent the inherent drawbacks encountered by the use of polymer stabilizers during catalyst preparation is presented herein. Experimental results suggest that the presence of the polymer stabilizers can affect the reaction pathways and control selectivity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/cctc.201800074

• 2018 • 57	Hedgehog Spin-Vortex Crystal Antiferromagnetic Quantum Criticality in CaK (Fe1-xNix)4As4 Revealed by NMR Ding, Q.-P. and Meier, W.R. and Cui, J. and Xu, M. and Böhmer, A.E. and Bud'Ko, S.L. and Canfield, P.C. and Furukawa, Y. Physical Review Letters 121 (2018) Two ordering states, antiferromagnetism and nematicity, have been observed in most iron-based superconductors (SCs). In contrast to those SCs, the newly discovered SC CaK(Fe1-xNix)4As4 exhibits an antiferromagnetic (AFM) state, called hedgehog spin-vortex crystal (SVC) structure, without nematic order, providing the opportunity for the investigation into the relationship between spin fluctuations and SC without any effects of nematic fluctuations. Our As75 nuclear magnetic resonance studies on CaK(Fe1-xNix)4As4 (0≤x≤0.049) revealed that CaKFe4As4 is located close to a hidden hedgehog SVC AFM quantum-critical point (QCP). The magnetic QCP without nematicity in CaK(Fe1-xNix)4As4 highlights the close connection of spin fluctuations and superconductivity in iron-based SCs. The advantage of stoichiometric composition also makes CaKFe4As4 an ideal platform for further detailed investigation of the relationship between magnetic QCP and superconductivity in iron-based SCs without disorder effects. © 2018 American Physical Society.
  	view abstract	doi: 10.1103/PhysRevLett.121.137204

• 2018 • 56	How the crystal structure and phase segregation of Au-Fe alloy nanoparticles are ruled by the molar fraction and size Tymoczko, A. and Kamp, M. and Prymak, O. and Rehbock, C. and Jakobi, J. and Schürmann, U. and Kienle, L. and Barcikowski, S. Nanoscale 10 16434-16437 (2018) The application of an Au-Fe nanoalloy is determined by its internal phase structure. Our experimental and theoretical findings explain how the prevalence of either a core-shell or a disordered solid solution structure is ruled by the target composition and the particle diameter. Furthermore, we found metastable phases not predefined by the bulk phase diagram. © The Royal Society of Chemistry 2018.
  	view abstract	doi: 10.1039/c8nr03962c

• 2018 • 55	Hysteresis Design of Magnetocaloric Materials—From Basic Mechanisms to Applications Scheibel, F. and Gottschall, T. and Taubel, A. and Fries, M. and Skokov, K.P. and Terwey, A. and Keune, W. and Ollefs, K. and Wende, H. and Farle, M. and Acet, M. and Gutfleisch, O. and Gruner, M.E. Energy Technology 6 1397-1428 (2018) Magnetic refrigeration relies on a substantial entropy change in a magnetocaloric material when a magnetic field is applied. Such entropy changes are present at first-order magnetostructural transitions around a specific temperature at which the applied magnetic field induces a magnetostructural phase transition and causes a conventional or inverse magnetocaloric effect (MCE). First-order magnetostructural transitions show large effects, but involve transitional hysteresis, which is a loss source that hinders the reversibility of the adiabatic temperature change ΔTad. However, reversibility is required for the efficient operation of the heat pump. Thus, it is the mastering of that hysteresis that is the key challenge to advance magnetocaloric materials. We review the origin of the large MCE and of the hysteresis in the most promising first-order magnetocaloric materials such as Ni–Mn-based Heusler alloys, FeRh, La(FeSi)13-based compounds, Mn3GaC antiperovskites, and Fe2P compounds. We discuss the microscopic contributions of the entropy change, the magnetic interactions, the effect of hysteresis on the reversible MCE, and the size- and time-dependence of the MCE at magnetostructural transitions. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
  	view abstract	doi: 10.1002/ente.201800264

• 2018 • 54	Influence of composition and crystal structure on the fracture toughness of NbCo2 Laves phase studied by micro-cantilever bending tests Luo, W. and Kirchlechner, C. and Fang, X. and Brinckmann, S. and Dehm, G. and Stein, F. Materials and Design 145 116-121 (2018) Cubic and hexagonal NbCo2 Laves phases are known to have composition dependent hardness and yield strength. However, it is unknown whether this dependence is also reflected in their fracture toughness values. In order to elucidate the fracture behavior, single-crystalline micro-cantilevers of the cubic and hexagonal NbCo2 Laves phases having different compositions were fabricated in the diffusion layers grown by the diffusion couple technique. Micro-cantilever bending tests were performed to study the composition- and crystal-structure-dependence of the fracture toughness. To exclude the influence of micro-cantilever geometry, pentagonal and rectangular beams were tested and found to result in the same fracture toughness value. The present results reveal that neither a change of the crystal structure nor a change in chemical composition has a significant influence on the fracture toughness of NbCo2 Laves phase. © 2018 Elsevier Ltd
  	view abstract	doi: 10.1016/j.matdes.2018.02.045

• 2018 • 53	Influence of Cr-Content on the thermoelectric and mechanical properties of NiCr thin film thermocouples synthesized on thermally sprayed Al2O3 Tillmann, W. and Kokalj, D. and Stangier, D. and Schöppner, V. and Benis, H.B. and Malatyali, H. Thin Solid Films 663 148-158 (2018) Ni/Ni-Cr thin film thermocouples were deposited by means of DC magnetron sputtering for the application in plastic extrusion dies. In order to ensure the application of the thermocouples on complex surfaces, a thermally sprayed Al2O3 layer was used between the substrate and the thin films for thermal insulation and electrical isolation. The study includes the deposition, characterization, calibration, and validation of thin film thermocouples. The influence of the composition (10 at.-%, 20 at.-% and 30 at.-% Cr) was analyzed concerning mechanical and electrical properties. It was found out that the electrical resistance increases with the temperature and the Cr-content due to a decreasing crystallite size. By means of a scratch-tester and nanoindentation, a higher scratch load and hardness were observed for larger Cr-contents on the thermally sprayed Al2O3 coating. Despite the composition, the influence of the size as well as the thickness of the thermocouples were analyzed regarding the Seebeck coefficient. Independent from the size and Cr-content, all thermocouples feature a comparable Seebeck coefficient of about 40 μV/K. This high coefficient is similar to that of wire thermocouples, showing a low number of defects in the thin films. The ceramic coating features a thermal insulation of about 20 °C at 200 °C, allowing a more accurate measurement of the ambient medium. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.tsf.2018.08.023

• 2018 • 52	Influence of Temperature and Electrolyte Concentration on the Structure and Catalytic Oxygen Evolution Activity of Nickel–Iron Layered Double Hydroxide Andronescu, C. and Seisel, S. and Wilde, P. and Barwe, S. and Masa, J. and Chen, Y.-T. and Ventosa, E. and Schuhmann, W. Chemistry - A European Journal 24 13773-13777 (2018) NiFe layered double hydroxide (LDH) is inarguably the most active contemporary catalyst for the oxygen evolution reaction under alkaline conditions. However, the ability to sustain unattenuated performance under challenging industrial conditions entailing high corrosivity of the electrolyte (≈30 wt. % KOH), high temperature (>80 °C) and high current densities (>500 mA cm−2) is the ultimate criterion for practical viability. This work evaluates the chemical and structural stability of NiFe LDH at conditions akin to practical electrolysis, in 30 % KOH at 80 °C, however, without electrochemical polarization, and the resulting impact on the OER performance of the catalyst. Post-analysis of the catalyst by means of XRD, TEM, FT-IR, and Raman spectroscopy after its immersion into 7.5 m KOH at 80 °C for 60 h revealed a transformation of the structure from NiFe LDH to a mixture of crystalline β-Ni(OH)2 and discrete predominantly amorphous FeOOH containing minor non-homogeneously distributed crystalline domains. These structural and compositional changes led to a drastic loss of the OER activity. It is therefore recommended to study catalyst stability at industrially relevant conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/chem.201803165

• 2018 • 51	Microstructure and mechanical properties in the thin film system Cu-Zr Oellers, T. and Raghavan, R. and Chakraborty, J. and Kirchlechner, C. and Kostka, A. and Liebscher, C.H. and Dehm, G. and Ludwig, Al. Thin Solid Films 645 193-202 (2018) A composition-spread Cu-Zr thin film library with Zr contents from 2.5 up to 6.5 at.% was synthesized by magnetron sputtering on a thermally oxidized Si wafer. The compositional and microstructural variations of the Cu-Zr thin film across the composition gradient were examined using energy dispersive X-ray spectroscopy, X-ray diffraction, and high-resolution scanning and transmission electron microscopy of cross-sections fabricated by focused ion beam milling. Composition-dependent hardness and elastic modulus values were obtained by nanoindentation for measurement areas with discrete Zr contents along the composition gradient. Similarly, the electrical resistivity was investigated by 4-point resistivity measurements to study the influence of Zr composition and microstructural changes in the thin film. Both, the mechanical and electrical properties reveal a significant increase in hardness and resistivity with increasing Zr content. The trends of the mechanical and functional properties are discussed with respect to the local microstructure and composition of the thin film library. © 2017
  	view abstract	doi: 10.1016/j.tsf.2017.10.030

• 2018 • 50	Multiscale Characterization of Microstructure in Near-Surface Regions of a 16MnCr5 Gear Wheel After Cyclic Loading Medghalchi, S. and Jamebozorgi, V. and Bala Krishnan, A. and Vincent, S. and Salomon, S. and Basir Parsa, A. and Pfetzing, J. and Kostka, A. and Li, Y. and Eggeler, G. and Li, T. JOM 1-7 (2018) The dependence of the microstructure on the degree of deformation in near-surface regions of a 16MnCr5 gear wheel after 2.1 × 106 loading cycles has been investigated by x-ray diffraction analysis, transmission electron microscopy, and atom probe tomography. Retained austenite and large martensite plates, along with elongated lamella-like cementite, were present in a less deformed region. Comparatively, the heavily deformed region consisted of a nanocrystalline structure with carbon segregation up to 2 at.% at grain boundaries. Spheroid-shaped cementite, formed at the grain boundaries and triple junctions of the nanosized grains, was enriched with Cr and Mn but depleted with Si. Such partitioning of Cr, Mn, and Si was not observed in the elongated cementite formed in the less deformed zone. This implies that rolling contact loading induced severe plastic deformation as well as a pronounced annealing effect in the active contact region of the toothed gear during cyclic loading. © 2018 The Minerals, Metals & Materials Society
  	view abstract	doi: 10.1007/s11837-018-2931-z

• 2018 • 49	NiTi-Based Elastocaloric Cooling on the Macroscale: From Basic Concepts to Realization Kirsch, S.-M. and Welsch, F. and Michaelis, N. and Schmidt, M. and Wieczorek, A. and Frenzel, J. and Eggeler, G. and Schütze, A. and Seelecke, S. Energy Technology 6 1567-1587 (2018) Solid-state cooling is an environmentally friendly, no global warming potential alternative to vapor compression-based systems. Elastocaloric cooling based on NiTi shape memory alloys exhibits excellent cooling capabilities. Due to the high specific latent heats activated by mechanical loading/unloading, large temperature changes can be generated in the material. The small required work input enables a high coefficient of performance. An overview of elastocaloric cooling from basic principles, such as elastocaloric cooling cycles, material characterization, modeling, and optimization, to the design of elastocaloric cooling devices is presented. Current work performed within the DFG (Deutsche Forschungsgemeinschaft) Priority Program SPP 1599 “Ferroic Cooling”, which is focused on the development and realization of a continuously operating elastocaloric cooling device, is highlighted. The cooling device operates in a rotatory mode with wires under tensile loading. The design allows maximization of cooling power by suitable wire diameter scaling as well as efficiency optimization by implementing a novel drive concept. Finally, computer-aided design (CAD) models of the discussed solid-state air cooling device are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/ente.201800152

• 2018 • 48	On the Electropolishing Mechanism of Nickel Titanium in Methanolic Sulfuric acid − An Electrochemical Impedance Study Fushimi, K. and Neelakantan, L. and Eggeler, G. and Hassel, A.W. Physica Status Solidi (A) Applications and Materials Science 215 (2018) Electropolishing of NiTi shape memory alloys is possible in methanolic 3 m H2SO4. The electro-dissolution behavior of NiTi in methanolic 3 m H2SO4 is ascertained in terms of Nyquist plots using electrochemical impedance spectroscopy (EIS) under limiting current flow (mass transfer control) condition. The electro-dissolution behavior is studied under convective conditions using a rotating disc electrode. The influence of changes in rotation rate, applied potential, and temperature are determined. This study demonstrates that electro-dissolution under mass transfer condition follows a compact salt-film mechanism. In order to quantitatively characterize the salt film formed during electropolishing, EIS is performed under stationary conditions. The increase in applied voltage causes an increase in polarization resistance and decrease in capacitance of the interface film. © 2018 The Authors. Published by Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/pssa.201800011

• 2018 • 47	Operando Raman spectroscopy on CO2 methanation over alumina-supported Ni, Ni3Fe and NiRh0.1 catalysts: Role of carbon formation as possible deactivation pathway Mutz, B. and Sprenger, P. and Wang, W. and Wang, D. and Kleist, W. and Grunwaldt, J.-D. Applied Catalysis A: General 556 160-171 (2018) The methanation of CO2, as a part of the power-to-gas concept, was studied under various industrially relevant feed compositions with a focus on the formation and influence of carbonaceous species. For this purpose, 5 wt.% Ni/Al2O3, 5 wt.% Ni3Fe/Al2O3 and 3.4 wt.% NiRh0.1/Al2O3 catalysts were prepared and characterized by X-ray diffraction (XRD), temperature-programmed reduction (TPR), scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS). During the methanation of CO2, the Ni3Fe catalyst emerged as the most active and selective catalyst in the mid-temperature regime (300–350 °C). At 400 °C, all three tested catalysts showed high conversion of CO2 (67–75%; Ni > Ni3Fe > NiRh0.1) and selectivity towards CH4 (95–98%). Operando Raman spectroscopy was applied to elucidate the possible influence of carbonaceous species on the performance of the catalysts. Notably, no carbon deposition was observed under various feed compositions, even in CO2 or CO2/CH4 mixtures, e.g. as provided by biogas plants. Only in pure CH4 atmosphere an intensive carbon deposition with graphitic structure occurred as uncovered by operando Raman spectroscopy. Experiments in the lab-scale reactor and a spectroscopic microreactor could be correlated and revealed a strong catalytic deactivation of the carbon covered catalysts including a pronounced shift of the selectivity towards CO. The initial activity could be recovered after reactivation in H2 at elevated temperatures, which led to a removal of the deposits especially from the metal particles. Raman spectroscopy, supported by the results from high-resolution transmission electron microscopy (HRTEM) and EELS, revealed that carbon remained on the support material. The latter did not have any significant influence on the catalytic activity and could be removed in an oxidizing atmosphere. © 2018
  	view abstract	doi: 10.1016/j.apcata.2018.01.026

• 2018 • 46	Optimization of the deposition parameters of Ni-20Cr thin films on thermally sprayed Al2O3 for sensor application Tillmann, W. and Kokalj, D. and Stangier, D. Surface and Coatings Technology 344 223-232 (2018) Ni-Cr (80–20 at.-%) thin films were synthesized by means of DC magnetron sputtering on thermally sprayed Al2O3 insolating coatings. In view of the application as a thin-film thermocouple, the ceramic layer provides an electrical as well a thermal insulation. The thin film must feature a good adhesion as well as a good electrical conductivity to be suitable as a thin-film thermocouple. Design of Experiments was utilized to determine if deposition parameters including the bias-voltage, heating power, and chamber pressure have a significant influence regarding critical scratch load, hardness to Young's modulus ratio, and electrical resistance. It was found out that the bias-voltage is the most important influencing factor. In order to extract the significant parameters, the morphology and topography were analyzed by means of SEM. The structural properties were obtained by means of XRD on an atomic level, using synchrotron radiation. Mechanical properties, such as the hardness and Young's modulus, as well the scratch load were evaluated using nanoindentation and a scratch-tester. To verify the findings, an optimized thin film was deposited, which showed an increased layer adhesion and a significantly lower electrical resistance. © 2018 Elsevier B.V.
  	view abstract	doi: 10.1016/j.surfcoat.2018.03.029

• 2018 • 45	Oxygen-Insensitive Aggregates of Pt(II) Complexes as Phosphorescent Labels of Proteins with Luminescence Lifetime-Based Readouts Delcanale, P. and Galstyan, A. and Daniliuc, C.G. and Grecco, H.E. and Abbruzzetti, S. and Faust, A. and Viappiani, C. and Strassert, C.A. ACS Applied Materials and Interfaces 10 24361-24369 (2018) The synthesis and photophysical properties of a tailored Pt(II) complex are presented. The phosphorescence of its monomeric species in homogeneous solutions is quenched by interaction with the solvent and therefore absent even upon deoxygenation. However, aggregation-induced shielding from the environment and suppression of rotovibrational degrees of freedom trigger a phosphorescence turn-on that is not suppressed by molecular oxygen, despite possessing an excited-state lifetime ranging in the microsecond scale. Thus, the photoinduced production of reactive oxygen species is avoided by the suppression of diffusion-controlled Dexter-type energy transfer to triplet molecular oxygen. These aggregates emit with the characteristic green luminescence profile of monomeric complexes, indicating that Pt-Pt or excimeric interactions are negligible. Herein, we show that these aggregates can be used to label a model biomolecule (bovine serum albumin) with a microsecond-range luminescence. The protein stabilizes the aggregates, acting as a carrier in aqueous environments. Despite spectral overlaps, the green phosphorescence can be separated by time-gated detection from the dominant autofluorescence of the protein arising from a covalently bound green fluorophore that emits in the nanosecond range. Interestingly, the aggregates also acted as energy donors able to sensitize the emission of a fraction of the fluorophores bound to the protein. This resulted in a microsecond-range luminescence of the fluorescent acceptors and a shortening of the excited-state lifetime of the phosphorescent aggregates. The process that can be traced by a 1000-fold increase in the acceptor's lifetime mirrors the donor's triplet character. The implications for phosphorescence lifetime imaging are discussed. © 2018 American Chemical Society.
  	view abstract	doi: 10.1021/acsami.8b02709

• 2018 • 44	Segregation Phenomena in Size-Selected Bimetallic CuNi Nanoparticle Catalysts Pielsticker, L. and Zegkinoglou, I. and Divins, N.J. and Mistry, H. and Chen, Y.-T. and Kostka, A. and Boscoboinik, J.A. and Cuenya, B.R. Journal of Physical Chemistry B 122 919-926 (2018) Surface segregation, restructuring, and sintering phenomena in size-selected copper-nickel nanoparticles (NPs) supported on silicon dioxide substrates were systematically investigated as a function of temperature, chemical state, and reactive gas environment. Using near-ambient pressure (NAP-XPS) and ultrahigh vacuum X-ray photoelectron spectroscopy (XPS), we showed that nickel tends to segregate to the surface of the NPs at elevated temperatures in oxygen- or hydrogen-containing atmospheres. It was found that the NP pretreatment, gaseous environment, and oxide formation free energy are the main driving forces of the restructuring and segregation trends observed, overshadowing the role of the surface free energy. The depth profile of the elemental composition of the particles was determined under operando CO2 hydrogenation conditions by varying the energy of the X-ray beam. The temperature dependence of the chemical state of the two metals was systematically studied, revealing the high stability of nickel oxides on the NPs and the important role of high valence oxidation states in the segregation behavior. Atomic force microscopy (AFM) studies revealed a remarkable stability of the NPs against sintering at temperatures as high as 700 °C. The results provide new insights into the complex interplay of the various factors which affect alloy formation and segregation phenomena in bimetallic NP systems, often in ways different from those previously known for their bulk counterparts. This leads to new routes for tuning the surface composition of nanocatalysts, for example, through plasma and annealing pretreatments. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acs.jpcb.7b06984

• 2018 • 43	Temperature-Dependent Ultrastructure Transformation of Au-Fe Nanoparticles Investigated by in Situ Scanning Transmission Electron Microscopy Kamp, M. and Tymoczko, A. and Schürmann, U. and Jakobi, J. and Rehbock, C. and Rätzke, K. and Barcikowski, S. and Kienle, L. Crystal Growth and Design 18 5434-5440 (2018) Three-dimensional morphology changes of bimetallic nanoparticles (NPs) with nominal composition Au50Fe50 and Au20Fe80, generated by pulsed laser ablation in liquid, are monitored in situ and ex situ via scanning transmission electron microscopy and electron tomography. The samples are made up of a chemically segregated core-shell (CS) NPs structure, with an Au-rich shell and Fe-rich core, and solid solution (SS) NPs in the pristine state. Further, the examinations reveal information about a sequence of characteristic changes from the pristine metastable and intermediate ultrastructures up to thermodynamically stable products. In the case of the Au20Fe80 sample, a metastable spherical CS morphology is transformed at equilibrium conditions into a cube-shaped Fe-rich core faceted by truncated Au-rich pyramids. For the Au50Fe50 sample, the Au-rich shell is solved into the Fe-rich core, and chemically homogeneous (SS) NPs are formed. Interestingly, this transformation was proven to occur via an intermediate ultrastructure with lamellar segregation, not previously reported as a transient state during in situ heating. On the basis of these observations, a correlation between the composition and the morphology at equilibrium is suggested, in accordance with the bulk phase diagram of Au-Fe. At the same time, our examinations directly prove that laser ablation synthesis creates nonequilibrium NP morphologies, frozen in metastable, spherical core-shell particles. Copyright © 2018 American Chemical Society.
  	view abstract	doi: 10.1021/acs.cgd.8b00809

• 2018 • 42	Understanding the Effect of Au in Au-Pd Bimetallic Nanocrystals on the Electrocatalysis of the Methanol Oxidation Reaction Kelly, C.H.W. and Benedetti, T.M. and Alinezhad, A. and Schuhmann, W. and Gooding, J.J. and Tilley, R.D. Journal of Physical Chemistry C 122 21718-21723 (2018) Pd or Pt alloyed with a secondary metal are the typical catalysts at the anode for the direct oxidation of methanol. The secondary metal is employed to diminish deactivation commonly ascribed to CO poisoning. Here we investigate the origin of the improved performance of Au-Pd core-shell and alloy nanocrystals as electrocatalysts for the methanol oxidation reaction (MOR), relative to Pd alone. Monodisperse Au-Pd core-shell nanocrystals were synthesized using H2 as a mild reducing agent followed by annealing under a 5% H2 atmosphere to produce the Au-Pd alloys. The nanocrystals were characterized using high-resolution electron microscopy to confirm their structures. The core-shell and alloy nanocrystals showed an improvement in specific activity with respect to pure Pd nanocrystals. Importantly, the stability was also improved by the inclusion of Au for both nanocrystals, being 2.7× higher for the alloy than for the core-shell after 30 min, while the activity is completely lost for the Pd nanocrystals within 10 min. We show that there is no evidence of CO formation for any of the Pd-based catalysts in an alkaline environment. The origin of the improvement in terms of both activity and stability results from positive shifts in the PdO formation/reduction potential caused by the presence of Au, which results in more Pd sites available for the MOR. © 2018 American Chemical Society.
  	view abstract	doi: 10.1021/acs.jpcc.8b05407

• 2017 • 41	A novel type of Co–Ti–Cr-base γ/γ′ superalloys with low mass density Zenk, C.H. and Povstugar, I. and Li, R. and Rinaldi, F. and Neumeier, S. and Raabe, D. and Göken, M. Acta Materialia 135 244-251 (2017) A γ′ strengthened Co–Ti–Cr superalloy is presented with a mass density ∼14 % below that of typical Co–Al–W-based alloys. The lattice misfit is sufficiently low to form coherent cuboidal γ′ precipitates. Atom probe tomography shows that Cr partitions to the γ phase, but increases the γ′ volume fraction compared to a binary Co-Ti alloy to more than 60 %. The solubility of Cr in the γ′ phase is significantly higher than expected from previously published values. The γ′ solvus temperature is above 1100 °C. The yield strength shows a distinct increase above 600 °C surpassing that of Co–9Al–8W (at.%) and conventional Co-base superalloys, even more so when it is normalized by the mass density. © 2017 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2017.06.024

• 2017 • 40	Doubling of the magnetic energy product in ferromagnetic nanowires at ambient temperature by capping their tips with an antiferromagnet Wang, F.Z. and Salikhov, R. and Spasova, M. and Liébana-Viñas, S. and Bran, C. and Chen, Y.-S. and Vazquez, M. and Farle, M. and Wiedwald, U. Nanotechnology 28 (2017) We present an approach to prepare free-standing tips of micrometer-long nanowires electrodeposited in anodic aluminum oxide nanopores. Such open tips can be further processed, e.g. for vertical interconnects of functional layers or for tailoring the magnetization reversal of ferromagnetic nanowires. The magnetic switching of nanowires is usually initiated by vortex or domain formation at the nanowire tips. We show that coating the tips of Fe30Co70 nanowires (diameter 40 nm, length 16 μm) with thin antiferromagnetic Fe50Mn50 capping layers (thickness ≈10 nm) leads to magnetic hardening with a more than doubled energy product at ambient temperature. © 2017 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-6528/aa77b7

• 2017 • 39	Elastically confined martensitic transformation at the nano-scale in a multifunctional titanium alloy Wang, H.L. and Hao, Y.L. and He, S.Y. and Li, T. and Cairney, J.M. and Wang, Y.D. and Wang, Y. and Obbard, E.G. and Prima, F. and Du, K. and Li, S.J. and Yang, R. Acta Materialia 135 330-339 (2017) A martensitic transformation (MT) is a typical first-order diffusionless crystal structural change with strong autocatalysis like avalanche at a speed of sound propagation. This unique characteristic, however, is undetectable in some multifunctional titanium alloys. Recently, a nano-scale elastically confined MT mechanism was proposed because a nano-scale Nb modulation in a Ti-Nb based alloy was observed. Here we analyze the elastic confinement in details and its induced novel properties in a wide temperature range. The statistical analyses of atom probe tomography (APT) data confirm the existence of the nano-scale Nb concentration modulation. The synchrotron X-ray diffraction (SXRD) profiles demonstrate that the nano-scale Nb modulation causes weak diffuse scattering, as evidenced by the extreme broad diffraction bands. The tensile tests find a critical temperature of ∼150 K, where the critical stress to induce the MT and Young's modulus reach the minimum and the superelastic strain reaches the maximum (∼4.5%) and keeps constant as the temperature decreases further to <4.2 K. To reveal these abnormal behaviors of the MT, the Born criterion governing the elastic stability of cubic crystal is modified by introducing an elastic confinement term and a new Clausius-Clapeyron relationship is established to evaluate the elastically confined MT. The results are consistent with the experimental findings, including the solely stress-induced (no thermally induced) reversibility. © 2017 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2017.06.040

• 2017 • 38	Electron-induced photon emission above the quantum cutoff due to time-energy uncertainty Ekici, E. and Kapitza, P. and Bobisch, C.A. and Möller, R. Optics Letters 42 4585-4588 (2017) The light emission from a tunneling junction induced by tunneling electrons has been studied around the cutoff at hν eVt. The emitted photons are found to exceed the excitation energy provided by the energy of the tunneling electrons. The experiments have been performed by a low-temperature scanning tunneling microscope at 80 K for an Ag(111) surface and an Ag-covered PtIr tip. A detailed analysis of the emission spectra reveals that the findings cannot be explained by the thermal broadening of the electron Fermi distribution alone. However, a correct description is found if a finite lifetime of the excited states in the range of 30–80 fs is included. © 2017 Optical Society of America.
  	view abstract	doi: 10.1364/OL.42.004585

• 2017 • 37	Electronic and molecular structure relations in diiron compounds mimicking the [FeFe]-hydrogenase active site studied by X-ray spectroscopy and quantum chemistry Kositzki, R. and Mebs, S. and Schüth, N. and Leidel, N. and Schwartz, L. and Karnahl, M. and Wittkamp, F. and Daunke, D. and Grohmann, A. and Apfel, U.-P. and Gloaguen, F. and Ott, S. and Haumann, M. Dalton Transactions 46 12544-12557 (2017) Synthetic diiron compounds of the general formula Fe2(μ-S2R)(CO)n(L)6-n (R = alkyl or aromatic groups; L = CN- or phosphines) are versatile models for the active-site cofactor of hydrogen turnover in [FeFe]-hydrogenases. A series of 18 diiron compounds, containing mostly a dithiolate bridge and terminal ligands of increasing complexity, was characterized by X-ray absorption and emission spectroscopy in combination with density functional theory. Fe K-edge absorption and Kβ main-line emission spectra revealed the varying geometry and the low-spin state of the Fe(i) centers. Good agreement between experimental and calculated core-to-valence-excitation absorption and radiative valence-to-core-decay emission spectra revealed correlations between spectroscopic and structural features and provided access to the electronic configuration. Four main effects on the diiron core were identified, which were preferentially related to variation either of the dithiolate or of the terminal ligands. Alteration of the dithiolate bridge affected mainly the Fe-Fe bond strength, while more potent donor substitution and ligand field asymmetrization changed the metal charge and valence level localization. In contrast, cyanide ligation altered all relevant properties and, in particular, the frontier molecular orbital energies of the diiron core. Mutual benchmarking of experimental and theoretical parameters provides guidelines to verify the electronic properties of related diiron compounds. © 2017 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c7dt02720f

• 2017 • 36	Gold-Palladium Bimetallic Catalyst Stability: Consequences for Hydrogen Peroxide Selectivity Pizzutilo, E. and Freakley, S.J. and Cherevko, S. and Venkatesan, S. and Hutchings, G.J. and Liebscher, C.H. and Dehm, G. and Mayrhofer, K.J.J. ACS Catalysis 7 5699-5705 (2017) During application, electrocatalysts are exposed to harsh electrochemical conditions, which can induce degradation. This work addresses the degradation of AuPd bimetallic catalysts used for the electrocatalytic production of hydrogen peroxide (H2O2) by the oxygen reduction reaction (ORR). Potential-dependent changes in the AuPd surface composition occur because the two metals have different dissolution onset potentials, resulting in catalyst dealloying. Using a scanning flow cell (SFC) with an inductively coupled plasma mass spectrometer (ICP-MS), simultaneous Pd and/or Au dissolution can be observed. Thereafter, three accelerated degradation protocols (ADPs), simulating different dissolution regimes, are employed to study the catalyst structure degradation on the nanoscale with identical location (IL) TEM. When only Pd or both Au and Pd dissolve, the composition changes rapidly and the surface becomes enriched with Au, as observed by cyclic voltammetry and elemental mapping. Such changes are mirrored by the evolution of electrocatalytic performances toward H2O2 production. Our experimental findings are finally summarized in a dissolution/structure/selectivity mechanism, providing a clear picture of the degradation of bimetallic catalyst used for H2O2 synthesis. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acscatal.7b01447

• 2017 • 35	High-throughput study of binary thin film tungsten alloys Nikolić, V. and Wurster, S. and Savan, A. and Ludwig, Al. and Pippan, R. International Journal of Refractory Metals and Hard Materials 69 40-48 (2017) Combinatorial magnetron co-sputtering from elemental sources was applied to produce W-alloy thin film composition spread materials libraries with well-defined, continuous composition gradients (film thicknesses between 1 and 2.5 μm). Three systems were studied: W-Fe (0–7 at.%), W-Ti (0–15 at.%) and W-Ir (0–12 at.%). High-throughput characterization of the materials libraries comprised of chemical, morphological and microstructural analyses. Scanning electron microscope investigations revealed that the films have a columnar structure of inverted cone-like units separated by voided boundaries, with a strong correlation to the alloying element content. Significant morphological changes occurred with an increase in the amount of the added element; W films with lower at.% of the alloying element had higher density and tighter grain boundaries, altering towards an increased amount of voids as the concentration of the alloying element increased. Electron backscatter diffraction scanning was used to determine microstructural components (grain size, grain shape, texture evolution), in dependence on the concentration of the alloying element. © 2017 Elsevier Ltd
  	view abstract	doi: 10.1016/j.ijrmhm.2017.07.017

• 2017 • 34	In-situ tracking the structural and chemical evolution of nanostructured CuCr alloys Zhang, Z. and Guo, J. and Dehm, G. and Pippan, R. Acta Materialia 138 42-51 (2017) We report the thermal stability of supersaturated CuCr nanocrystallines alloys at the atomic resolution using modern spherical aberration-corrected transmission electron microscopy (TEM) via performing in-situ structural and spectroscopy experiments. It is found that CuCr nanocrystallines are not only subjected to a structural change but also undergo a chemical evolution upon annealing. Chemical destabilization of supersaturated CuCr nanocrystallines occurs at a quite low temperature. Heating triggers a rapid separation of Cu and Cr grains at the forced intermixing zone, accompanied by an obvious decrease of average interface width whereas the grain growth is not significant. Elemental profiles and images recorded in real time reveal that the local compositions vary with heating, which in turn permits to derive the concentration of excess vacancy generated by deformation and observe its evolution with temperature, further to analyze the dynamic behavior in nanocrystalline materials. Electronic structure changes at the interface forced intermixing zone are revealed by the fine structure analysis. The study uncovers the interplay between the thermal stability and chemical decomposition process of bulk nanostructured materials in real-time. © 2017
  	view abstract	doi: 10.1016/j.actamat.2017.07.039

• 2017 • 33	Iron-Induced Activation of Ordered Mesoporous Nickel Cobalt Oxide Electrocatalyst for the Oxygen Evolution Reaction Deng, X. and Öztürk, S. and Weidenthaler, C. and Tüysüz, H. ACS Applied Materials and Interfaces 9 21225-21233 (2017) Herein, ordered mesoporous nickel cobalt oxides prepared by the nanocasting route are reported as highly active oxygen evolution reaction (OER) catalysts. By using the ordered mesoporous structure as a model system and afterward elevating the optimal catalysts composition, it is shown that, with a simple electrochemical activation step, the performance of nickel cobalt oxide can be significantly enhanced. The electrochemical impedance spectroscopy results indicated that charge transfer resistance increases for Co3O4 spinel after an activation process, while this value drops for NiO and especially for CoNi mixed oxide significantly, which confirms the improvement of oxygen evolution kinetics. The catalyst with the optimal composition (Co/Ni 4/1) reaches a current density of 10 mA/cm2 with an overpotential of a mere 336 mV and a Tafel slope of 36 mV/dec, outperforming benchmarked and other reported Ni/Co-based OER electrocatalysts. The catalyst also demonstrates outstanding durability for 14 h and maintained the ordered mesoporous structure. The cyclic voltammograms along with the electrochemical measurements in Fe-free KOH electrolyte suggest that the activity boost is attributed to the generation of surface Ni(OH)2 species that incorporate Fe impurities from the electrolyte. The incorporation of Fe into the structure is also confirmed by inductively coupled plasma optical emission spectrometry. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acsami.7b02571

• 2017 • 32	Material Testing and Chip Formation Simulation for Different Heat Treated Workpieces of 51CrV4 Steel Zabel, A. and Rödder, T. and Tiffe, M. Procedia CIRP 58 181-186 (2017) The heat treatment has a major impact on the mechanical properties of steel alloys and therefore on the condition of a machining processes. In this paper, the low alloy steel 51CrV4 with different heat treatments is investigated in terms of its mechanical properties under high dynamic conditions using a Split Hopkinson Pressure Bar (SHPB) and by means of orthogonal cutting tests. The latter provide a detailed insight in the ongoing processes during chip formation by analyzing the present microstructure of the generated chips. Furthermore, the obtained data from the SHPB tests is used as an input for material models applied for the simulation of chip formation with the Finite-Element-Method. The results reveal fundamental differences in the chip formation mechanisms between the differently heat treated workpiece materials. © 2017 The Authors.
  	view abstract	doi: 10.1016/j.procir.2017.03.218

• 2017 • 31	Micromagnetic Simulations for Coercivity Improvement Through Nano-Structuring of Rare-Earth-Free L10-FeNi Magnets Kovacs, A. and Fischbacher, J. and Oezelt, H. and Schrefl, T. and Kaidatzis, A. and Salikhov, R. and Farle, M. and Giannopoulos, G. and Niarchos, D. IEEE Transactions on Magnetics 53 (2017) In this paper, we investigate the potential of tetragonal L10-ordered FeNi as the candidate phase for rare-earth-free permanent magnets considering anisotropy values from recently synthesized, partially ordered FeNi thin films. In particular, we estimate the maximum energy product (BH)max of L10-FeNi nanostructures using micromagnetic simulations. The maximum energy product is limited due to the small coercive field of partially ordered L10-FeNi. Nano-structured magnets consisting of 128 equi-axed, platelet-like, and columnar-shaped grains show a theoretical maximum energy product of 228, 208, and 252 kJm $^{-3}$ , respectively. © 1965-2012 IEEE.
  	view abstract	doi: 10.1109/TMAG.2017.2701418

• 2017 • 30	On the competition between the stress-induced formation of martensite and dislocation plasticity during crack propagation in pseudoelastic NiTi shape memory alloys Ungár, T. and Frenzel, J. and Gollerthan, S. and Ribárik, G. and Balogh, L. and Eggeler, G. Journal of Materials Research 1-10 (2017) The present work addresses the competition between dislocation plasticity and stress-induced martensitic transformations in crack affected regions of a pseudoelastic NiTi miniature compact tension specimen. For this purpose X-ray line profile analysis was performed after fracture to identify dislocation densities and remnant martensite volume fractions in regions along the crack path. Special emphasis was placed on characterizing sub fracture surface zones to obtain depth profiles. The stress affected zone in front of the crack-tip is interpreted in terms of a true plastic zone associated with dislocation plasticity and a pseudoelastic zone where stress-induced martensite can form. On unloading, most of the stress-induced martensite transforms back to austenite but a fraction of it is stabilized by dislocations in both, the irreversible martensite and the surrounding austenite phase. The largest volume fraction of the irreversible or remnant martensite along with the highest density of dislocations in this phase was found close to the primary crack-tip. With increasing distance from the primary crack-tip both, the dislocation density and the volume fraction of irreversible martensite decrease to lower values. Copyright © Materials Research Society 2017
  	view abstract	doi: 10.1557/jmr.2017.267

• 2017 • 29	Partial recrystallization of gum metal to achieve enhanced strength and ductility Zhang, J.-L. and Tasan, C.C. and Lai, M.J. and Yan, D. and Raabe, D. Acta Materialia 135 400-410 (2017) Here we present a microstructure design approach which leads to partial recrystallization and nano-precipitation within the same single-step heat treatment. This produces a dual-constituent microstructure in Ti-Nb based gum metal, which consists of nano-ω-particle-rich ultrafine recrystallized grain chains embedded in ω-lean subgrain-containing recovered zones. This partially recrystallized microstructure exhibits an improved strength-ductility combination that surpasses the inverse strength-ductility relationship exhibited by materials with similar composition. The strengthening effects due to precipitates and grain refinement were studied by nanoindentation. The deformation mechanisms of the partially recrystallized material were investigated by in-situ scanning electron microscope tensile tests, micro-strain mapping and post-mortem microstructure characterization. The improved mechanical properties are attributed to the high yield strength of the recrystallized grains and the sequential activation of dislocation slip and dislocation channeling. © 2017 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2017.06.051

• 2017 • 28	Potential of an alumina-supported Ni3Fe catalyst in the methanation of CO2: Impact of alloy formation on activity and stability Mutz, B. and Belimov, M. and Wang, W. and Sprenger, P. and Serrer, M.A. and Wang, D. and Pfeifer, P. and Kleist, W. and Grunwaldt, J.-D. ACS Catalysis 7 6802-6814 (2017) A promising bimetallic 17 wt % Ni3Fe catalyst supported on γ-Al2O3 was prepared via homogeneous deposition-precipitation for the application in the methanation of CO2 to gather more detailed insight into the structure and performance of the catalyst compared to state-of-the-art methanation systems. X-ray diffraction (XRD) analysis, detailed investigations using scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy analysis (EDX) of single particles as well as larger areas, high-resolution transmission electron microscopy (HRTEM) imaging, temperature-programmed reduction (H2-TPR), and in-depth interpretation of Raman bands led to the conclusion that a high fraction of the Ni and Fe formed the desired Ni3Fe alloy resulting in small and well-defined nanoparticles with 4 nm in size and a dispersion of 24%. For comparison, a monometallic catalyst with similar dispersion using the same preparation method and analysis was prepared. Using a fixed-bed reactor, the Ni3Fe catalyst showed better low-temperature performance compared to a monometallic Ni reference catalyst, especially at elevated pressures. Longterm experiments in a microchannel packed bed reactor under industrially relevant reaction conditions in competition with a commercial Ni-based methanation catalyst revealed an improved performance of the Ni3Fe system at 358°C and 6 bar involving enhanced conversion of CO2 to 71%, selectivity to CH4 > 98%, and most notably a high stability. Deactivation occurred only at lower temperatures, which was related to carbon deposition due to an increased CO production. Kinetic measurements were compared with literature models derived for Ni/Al2O3 catalysts, which fit well but underestimate the performance of the Ni3Fe system, emphasizing the synergetic effect of Ni and Fe. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acscatal.7b01896

• 2017 • 27	Spinel-Structured ZnCr2O4 with Excess Zn Is the Active ZnO/Cr2O3 Catalyst for High-Temperature Methanol Synthesis Song, H. and Laudenschleger, D. and Carey, J.J. and Ruland, H. and Nolan, M. and Muhler, M. ACS Catalysis 7 7610-7622 (2017) A series of ZnO/Cr2O3 catalysts with different Zn:Cr ratios was prepared by coprecipitation at a constant pH of 7 and applied in methanol synthesis at 260-300 °C and 60 bar. The X-ray diffraction (XRD) results showed that the calcined catalysts with ratios from 65:35 to 55:45 consist of ZnCr2O4 spinel with a low degree of crystallinity. For catalysts with Zn:Cr ratios smaller than 1, the formation of chromates was observed in agreement with temperature-programmed reduction results. Raman and XRD results did not provide evidence for the presence of segregated ZnO, indicating the existence of Zn-rich nonstoichiometric Zn-Cr spinel in the calcined catalyst. The catalyst with Zn:Cr = 65:35 exhibits the best performance in methanol synthesis. The Zn:Cr ratio of this catalyst corresponds to that of the Zn4Cr2(OH)12CO3 precursor with hydrotalcite-like structure obtained by coprecipitation, which is converted during calcination into a nonstoichiometric Zn-Cr spinel with an optimum amount of oxygen vacancies resulting in high activity in methanol synthesis. Density functional theory calculations are used to examine the formation of oxygen vacancies and to measure the reducibility of the methanol synthesis catalysts. Doping Cr into bulk and the (10-10) surface of ZnO does not enhance the reducibility of ZnO, confirming that Cr:ZnO cannot be the active phase. The (100) surface of the ZnCr2O4 spinel has a favorable oxygen vacancy formation energy of 1.58 eV. Doping this surface with excess Zn charge-balanced by oxygen vacancies to give a 60% Zn content yields a catalyst composed of an amorphous ZnO layer supported on the spinel with high reducibility, confirming this as the active phase for the methanol synthesis catalyst. © 2017 American Chemical Society.
  	view abstract	doi: 10.1021/acscatal.7b01822

• 2017 • 26	The roles of Co-precipitation pH, phase-purity and alloy formation for the ammonia decomposition activity of Ga-promoted Fe/MgO catalysts Rein, D. and Friedel Ortega, K. and Weidenthaler, C. and Bill, E. and Behrens, M. Applied Catalysis A: General 548 52-61 (2017) A series of mesoporous MgFe1.75Ga0.25O4 mixed spinel oxides obtained upon calcination of hydrotalcite-like precursors was investigated in the ammonia decomposition reaction at 1 atm after reduction in H2 atmosphere. The corresponding precursors were synthesized from metal salt solutions at five constant pH values in the range between 8.5 and 10.5 by co-precipitation in aqueous media to study the impact of pH variation on the catalyst's structure and activity. N2 physisorption, thermogravimetric analysis, powder X-ray diffraction, Mössbauer spectroscopy, and temperature programmed techniques (H2-TPR and NH3-TPD) were applied to gather information about the textural, (micro-)structural, and adsorption properties of the samples. While phase purity in the precursor and oxide stages is only observed for pH = 10, undesired by-phases (MgFe2O4 and/or Fe3O4) are additionally formed during co-precipitation at the remaining pH values. This is partly related to an incomplete precipitation of Mg2+ cations in less alkaline environments. In situ XRD measurements during reduction revealed that Fe-Ga alloys are formed between 500 and 600 °C. The absence of by-phases avoids the formation of α-Fe, thus improving the structural and compositional homogeneity of the nitridated samples. This beneficial effect is reflected by the low activation energy (70 kJ/mol) and the enhanced low temperature activity (<450 °C) of the phase pure material in the catalytic decomposition of ammonia. © 2017 Elsevier B.V.
  	view abstract	doi: 10.1016/j.apcata.2017.09.004

• 2017 • 25	The shear instability energy: A new parameter for materials design? Kanani, M. and Hartmaier, A. and Janisch, R. Modelling and Simulation in Materials Science and Engineering 25 (2017) Reliable and predictive relationships between fundamental microstructural material properties and observable macroscopic mechanical behaviour are needed for the successful design of new materials. In this study we establish a link between physical properties that are defined on the atomic level and the deformation mechanisms of slip planes and interfaces that govern the mechanical behaviour of a metallic material. To accomplish this, the shear instability energy Γ is introduced, which can be determined via quantum mechanical ab initio calculations or other atomistic methods. The concept is based on a multilayer generalised stacking fault energy calculation and can be applied to distinguish the different shear deformation mechanisms occurring at TiAl interfaces during finite-temperature molecular dynamics simulations. We use the new parameter Γ to construct a deformation mechanism map for different interfaces occurring in this intermetallic. Furthermore, Γ can be used to convert the results of ab initio density functional theory calculations into those obtained with an embedded atom method type potential for TiAl. We propose to include this new physical parameter into material databases to apply it for the design of materials and microstructures, which so far mainly relies on single-crystal values for the unstable and stable stacking fault energy. © 2017 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/1361-651X/aa865a

• 2017 • 24	The Space Confinement Approach Using Hollow Graphitic Spheres to Unveil Activity and Stability of Pt-Co Nanocatalysts for PEMFC Pizzutilo, E. and Knossalla, J. and Geiger, S. and Grote, J.-P. and Polymeros, G. and Baldizzone, C. and Mezzavilla, S. and Ledendecker, M. and Mingers, A. and Cherevko, S. and Schüth, F. and Mayrhofer, K.J.J. Advanced Energy Materials 7 (2017) The performance of polymer electrolyte fuel cells is strongly correlated to the electrocatalytic activity and stability. In particular, the latter is the result of an interplay between different degradation mechanisms. The essential high stability, demanded for real applications, requires the synthesis of advanced electrocatalysts that withstand the harsh operation conditions. In the first part of this study, the synthesis of oxygen reduction electrocatalysts consisting of Pt-Co (i.e., Pt5Co, Pt3Co, and PtCo) alloyed nanoparticles encapsulated in the mesoporous shell of hollow graphitic spheres (HGS) is reported. The mass activities of the activated catalysts depend on the initial alloy composition and an activity increase on the order of two to threefold, compared to pure Pt@HGS, is achieved. The key point of the second part is the investigation of the degradation of PtCo@HGS (showing the highest activity). Thanks to pore confinement, the impact of dissolution/dealloying and carbon corrosion can be studied without the interplay of other degradation mechanisms that would induce a substantial change in the particle size distribution. Therefore, impact of the upper potential limit and the scan rates on the dealloying and electrochemical surface area evolution can be examined in detail. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
  	view abstract	doi: 10.1002/aenm.201700835

• 2017 • 23	Thermally activated lightweight actuator based on hot extruded shape memory metal matrix composites (SMA-MMC) Dahnke, C. and Shapovalov, A. and Tekkaya, A.E. Procedia Engineering 207 1511-1516 (2017) Based on modified porthole dies, continuous composite extrusion allows the manufacturing of shape memory alloy metal matrix composites (SMA-MMC). In order to extend the functionality of SMA-MMC, the present work shows a new actuator concept based on integrated NiTi wires within an aluminum matrix. Due to an eccentric positioning of the wires as well as a prestraining, a bending moment is generated within the profile when the temperature is increased to a critical value. Depending on the process parameters, the occurring bending moment is able to cause an elastic or elastic-plastic deformation of the profile or specimen. © 2017 The Authors. Published by Elsevier Ltd.
  	view abstract	doi: 10.1016/j.proeng.2017.10.1083

• 2017 • 22	Unraveling compositional effects on the light-induced oxygen evolution in Bi(V-Mo-X)O4 material libraries Gutkowski, R. and Khare, C. and Conzuelo, F. and Kayran, Y.U. and Ludwig, Al. and Schuhmann, W. Energy and Environmental Science 10 1213-1221 (2017) The influence of co-deposited transition metals X (X = Ta, W, Nb) with various relative concentrations on the photoelectrochemical performance of BiVO4 is investigated. Thin film material libraries with well-defined composition gradients of Bi, V and two transition metals are fabricated by combinatorial sputter co-deposition. Materials with the highest photoelectrochemical performance are identified by high-throughput characterization of the Bi(V-Mo-X)O4 material libraries using an optical scanning droplet cell. Bi(V-Mo-W)O4 and Bi(V-Mo-Nb)O4 material libraries show the highest improvement in the photocurrent, with ten times higher photocurrents of up to 1 mA cm-2 compared to a BiVO4 reference material library. Deviations from the V:Bi equiatomic ratio lead to a decrease in the photocurrent for pristine monoclinic BiVO4. By the addition of transition metals this effect is minimized and no significant decrease in the photocurrent occurs up to 10 at% variation from the equiatomic V:Bi ratio. Excellent photoelectrochemical performance is reached under these conditions in regions with a V:Bi atomic ratio of 70:30 and co-deposited Nb concentrations of >10 at%. Scanning photoelectrochemical microscopy allows the evaluation of the correlation between the generated oxygen at a photoanode and the measured photocurrent. © 2017 The Royal Society of Chemistry.
  	view abstract	doi: 10.1039/c7ee00287d

• 2016 • 21	Mg-based compounds for hydrogen and energy storage Crivello, J.-C. and Denys, R.V. and Dornheim, M. and Felderhoff, M. and Grant, D.M. and Huot, J. and Jensen, T.R. and de Jongh, P. and Latroche, M. and Walker, G.S. and Webb, C.J. and Yartys, V.A. Applied Physics A: Materials Science and Processing 122 1-17 (2016) Magnesium-based alloys attract significant interest as cost-efficient hydrogen storage materials allowing the combination of high gravimetric storage capacity of hydrogen with fast rates of hydrogen uptake and release and pronounced destabilization of the metal–hydrogen bonding in comparison with binary Mg–H systems. In this review, various groups of magnesium compounds are considered, including (1) RE–Mg–Ni hydrides (RE = La, Pr, Nd); (2) Mg alloys with p-elements (X = Si, Ge, Sn, and Al); and (3) magnesium alloys with d-elements (Ti, Fe, Co, Ni, Cu, Zn, Pd). The hydrogenation–disproportionation–desorption–recombination process in the Mg-based alloys (LaMg12, LaMg11Ni) and unusually high-pressure hydrides synthesized at pressures exceeding 100 MPa (MgNi2H3) and stabilized by Ni–H bonding are also discussed. The paper reviews interrelations between the properties of the Mg-based hydrides and p–T conditions of the metal–hydrogen interactions, chemical composition of the initial alloys, their crystal structures, and microstructural state. © 2016, Springer-Verlag Berlin Heidelberg.
  	view abstract	doi: 10.1007/s00339-016-9601-1

• 2015 • 20	Ab initio study of compositional trends in solid solution strengthening in metals with low Peierls stresses Ma, D. and Friák, M. and Von Pezold, J. and Neugebauer, J. and Raabe, D. Acta Materialia 98 367-376 (2015) Abstract We identify and analyze general trends governing solid solution strengthening in binary alloys containing solutes across the Periodic table using quantum-mechanical calculations. Here we present calculations for the model system of Al binary solid solutions. The identified trends originate from an approximately parabolic dependence of two strengthening parameters to quantitatively predict the solid solution strengthening effect, i.e. the volume and slip misfit parameters. The volume misfit parameter shows a minimum (concave-up behavior) as a function of the solute element group number in the periodic table, whereas the slip misfit parameter shows a maximum (concave-down behavior). By analyzing reported data, a similar trend is also found in Ni and Mg (basal slip) binary systems. Hence, these two strengthening parameters are strongly anti-correlated, which can be understood in terms of the Fermi level shift in the framework of free electron model. The chemical trends identified in this study enable a rapid and efficient identification of the solutes that provide optimum solid-solution strengthening. The approach described here may thus serve as basis for ab initio guided metallurgical materials design. © 2015 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2015.07.054

• 2015 • 19	Incorporating the CALPHAD sublattice approach of ordering into the phase-field model with finite interface dissipation Zhang, L. and Stratmann, M. and Du, Y. and Sundman, B. and Steinbach, I. Acta Materialia 88 156-169 (2015) A new approach to incorporate the sublattice models in the CALPHAD (CALculation of PHAse Diagram) formalism directly into the phase-field formalism is developed. In binary alloys, the sublattice models can be classified into two types (i.e., "Type I" and "Type II"), depending on whether a direct one-to-one relation between the element site fraction in the CALPHAD database and the phase concentration in the phase-field model exists (Type I), or not (Type II). For "Type II" sublattice models, the specific site fractions, corresponding to a given mole fraction, have to be established via internal relaxation between different sublattices. Internal minimization of sublattice occupancy and solute evolution during microstructure transformation leads, in general, to a solution superior to the separate solution of the individual problems. The present coupling technique is validated for Fe-C and Ni-Al alloys. Finally, the model is extended into multicomponent alloys and applied to simulate the nucleation process of VC monocarbide from austenite matrix in a steel containing vanadium. © 2014 Acta Materialia Inc.
  	view abstract	doi: 10.1016/j.actamat.2014.11.037

• 2015 • 18	On the widths of the hysteresis of mechanically and thermally induced martensitic transformations in Ni-Ti-based shape memory alloys Jaeger, S. and Maaß, B. and Frenzel, J. and Schmidt, M. and Ullrich, J. and Seelecke, S. and Schütze, A. and Kastner, O. and Eggeler, G. International Journal of Materials Research 106 1029-1039 (2015) It is well known that a good crystallographic compatibility between austenite and martensite in Ni-Ti-based shape memory alloys results in narrow thermal hystereses (e. g. Ball and James, Arch. Ration. Mech. Anal., 1987). The present work suggests that a good crystallographic fit is moreover associated with a small mechanical hysteresis width, observed during a forward and reverse stress-induced transformation. Furthermore, shape memory alloys with a good crystallographic fit show smaller transformation strains. The results obtained in the present study suggest that these correlations are generic and apply to binary Ni-Ti (with varying Ni contents) and quaternary Ni-Ti-Cu-X (X = Cr, Fe, V) alloys. For binary Ni-Ti, it was observed that Ni-rich compositions (good lattice fit) show a lower accummulation of irreversible strains during pseudoelastic cycling. © Carl Hanser Verlag GmbH & Co. KG.
  	view abstract	doi: 10.3139/146.111284

• 2015 • 17	Rapid theory-guided prototyping of ductile Mg alloys: From binary to multi-component materials Pei, Z. and Friák, M. and Sandlöbes, S. and Nazarov, R. and Svendsen, B. and Raabe, D. and Neugebauer, J. New Journal of Physics 17 (2015) In order to identify a method allowing for a fast solute assessment without lengthy ab initio calculations, we analyze correlations and anti-correlation between the stacking fault energies (SFEs), which were shown to be related to the macroscopic ductility in Mg alloys, and five material parameters of 18 different elemental solutes. Our analysis reveals that the atomic volume V of pure solutes, their electronegativity ν and bulk modulus B are either linearly or logarithmically related to the SFE. Comparing the impact of solutes with that of yttrium (that increases the ductility in Mg) we propose a single numerical quantity (called yttrium similarity index, YSI) that is based on these inter-relations. Subsequently, we evaluate this new figure of merit for 76 elements from the periodic table of elements in search for solutes reducing the SFE. Limiting ourselves first to binary Mg alloys, we hardly find any alternative solutes providing similar reduction as that due to rare-earth (RE) additions. Therefore, we extended our search to ternary Mg alloys. Assuming that the physical properties of solute combinations can be represented by their average values, 2850 solute combinations were checked and 133 solute pairs (not including any RE elements) have been found to have a YSI larger than 0.85. Quantum-mechanical calculations have been subsequently performed for 11 solute pairs with YSIs higher than 0.95 and they were all found to reduce the in excellent agreement with the predictions based on the YSI. © 2015 IOP Publishing Ltd and Deutsche Physikalische Gesellschaft.
  	view abstract	doi: 10.1088/1367-2630/17/9/093009

• 2015 • 16	Structural stability of Fe-based topologically close-packed phases Ladines, A.N. and Hammerschmidt, T. and Drautz, R. Intermetallics 59 59-67 (2015) Precipitates of topologically close-packed (TCP) phases play an important role in hardening mechanisms of high-performance steels. We analyze the influence of atomic size, electron count, magnetism and external stress on TCP phase stability in Fe-based binary transition metal alloys. Our density-functional theory calculations of structural stability are complemented by an analysis with an empirical structure map for TCP phases. The structural stability and lattice parameters of the Fe-Nb/Mo/V compounds are in good agreement with experiment. The average magnetic moments follow the Slater-Pauling relation to the average number of valence-electrons and can be rationalized in terms of the electronic density of states. The stabilizing effect of the magnetic energy, estimated by additional non-magnetic calculations, increases as the magnetic moment increases with band filling for the binary systems of Fe and early transition metals. For the case of Fe2Nb, we demonstrate that the influence of magnetism and external stress is sufficiently large to alter the energetic ordering of the closely competing Laves phases C14, C15 and C36. We find that the A15 phase is not stabilized by atomic-size differences, while the stability of C14 is increasing with increasing difference in atomic size. © 2014 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.intermet.2014.12.009

• 2015 • 15	The crystallographic template effect assisting the formation of stable α-Al2O3 during low temperature oxidation of Fe-Al alloys Brito, P. and Pinto, H. and Kostka, A. Corrosion Science (2015) The role of thermally grown α-Fe2O3 on the nucleation of α-Al2O3 during oxidation of binary Fe-Al alloys with 15 and 26 at.%Al at 700°C was investigated. Surface morphology of the oxide scales indicated direct nucleation of α-Al2O3 preferentially instead of conversion from metastable Al2O3 polymorphs. Oxide scale development over time was also monitored by use of synchrotron X-ray diffraction and Raman spectroscopy. The results showed that the α-Fe2O3 crystal lattice decreases in volume as oxidation progresses, which was found to be consistent with an Al3+ enrichment of α-Fe2O3 as confirmed by the change in relative intensity of α-Fe2O3 Raman peaks. © 2016 Elsevier Ltd.
  	view abstract	doi: 10.1016/j.corsci.2016.01.007

• 2014 • 14	Composition Dependence of Phase Stability, Deformation Mechanisms, and Mechanical Properties of the CoCrFeMnNi High-Entropy Alloy System Tasan, C.C. and Deng, Y. and Pradeep, K.G. and Yao, M.J. and Springer, H. and Raabe, D. JOM 66 1993-2001 (2014) The proposal of configurational entropy maximization to produce massive solid-solution (SS)-strengthened, single-phase high-entropy alloy (HEA) systems has gained much scientific interest. Although most of this interest focuses on the basic role of configurational entropy in SS formability, setting future research directions also requires the overall property benefits of massive SS strengthening to be carefully investigated. To this end, taking the most promising CoCrFeMnNi HEA system as the starting point, we investigate SS formability, deformation mechanisms, and the achievable mechanical property ranges of different compositions and microstructural states. A comparative assessment of the results with respect to room temperature behavior of binary Fe-Mn alloys reveals only limited benefits of massive SS formation. Nevertheless, the results also clarify that the compositional requirements in this alloy system to stabilize the face-centered cubic (fcc) SS are sufficiently relaxed to allow considering nonequiatomic compositions and exploring improved strength–ductility combinations at reduced alloying costs. © 2014, The Minerals, Metals & Materials Society.
  	view abstract	doi: 10.1007/s11837-014-1133-6

• 2014 • 13	Effect of ternary element addition on the corrosion behaviour of NiTi shape memory alloys Kassab, E. and Neelakantan, L. and Frotscher, M. and Swaminathan, S. and Maaß, B. and Rohwerder, M. and Gomes, J. and Eggeler, G. Materials and Corrosion 65 18-22 (2014) The goal of this study is to compare the corrosion behaviour of selected ternary nickel titanium (NiTi)-based alloys (Ni45Ti 50Cu5, Ni47Ti50Fe3 and Ni39Ti50Pd11) with a binary, pseudoelastic Ni50.7Ti49.3 alloy. We examine the influence of the ternary elements on the corrosion behaviour using standard electrochemical techniques. All measurements were done in a physiological solution (0.9% NaCl) simulating a body temperature of 37 ± 1 °C. The influence of Cu and Pd addition on the surface oxide film was characterised by X-ray photoelectron spectroscopy (XPS). The results revealed that, the localised corrosion resistance of these ternary alloys is lower than the binary NiTi alloy. By comparing the different NiTi-based alloys, the following relation has been proposed for their localised corrosion resistances: NiTiCu < NiTiFe < NiTiPd < NiTi. Depth profiling by XPS showed that the surface oxide film on all the investigated NiTi-based alloys is mainly of TiO2, however, the NiTiPd and NiTiCu alloys showed metallic ternary element distributed within TiO2 layer. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/maco.201206587

• 2014 • 12	Modelling of dendritic growth during alloy solidification under natural convection Zhu, M. and Sun, D. and Pan, S. and Zhang, Q. and Raabe, D. Modelling and Simulation in Materials Science and Engineering 22 (2014) A two-dimensional (2D) lattice Boltzmann method (LBM)-cellular automaton model is presented to investigate the dendritic growth of binary alloys in the presence of natural convection. The kinetic-based LBM is adopted to calculate the transport phenomena by the evolution of distribution functions of moving pseudo-particles. To numerically solve natural convection thermal and solute transport simultaneously, three sets of distribution functions are employed in conjunction with the lattice Bhatnagar-Gross-Krook scheme. Based on the LBM calculated local temperature and concentration at the solid/liquid interface, the kinetics of dendritic growth is determined according to a local solute equilibrium approach. Thus, the physics of a complete time-dependent interaction of natural convection, thermal and solutal transport, and dendritic growth during alloy solidification is embedded in the model. Model validation is performed by comparing the simulated results with literature data and analytical predictions. The model is applied to simulate dendritic growth in binary alloys under the influence of natural convection. The effects of Rayleigh numbers and initial undercooling on dendrite growth are investigated. The results show that natural buoyancy flow, induced by thermal and solutal gradients under gravity, transports the heat and solute from the lower region to the upper region. The dendritic growth is thus accelerated in the downward direction, whereas it is inhibited in the upward direction, yielding asymmetrical dendrite patterns. Increasing the Rayleigh number and undercooling will enhance and reduce, respectively, the influence of natural flow on the dendritic growth. © 2014 IOP Publishing Ltd.
  	view abstract	doi: 10.1088/0965-0393/22/3/034006

• 2014 • 11	On the functional degradation of binary titanium-tantalum high-temperature shape memory alloys - A new concept for fatigue life extension Niendorf, T. and Krooß, P. and Batyrsina, E. and Paulsen, A. and Frenzel, J. and Eggeler, G. and Maier, H.J. Functional Materials Letters 7 (2014) High-temperature shape memory alloys are promising candidates for actuator applications at elevated temperatures. Ternary nickel-titanium-based alloys either contain noble metals which are very expensive, or suffer from poor workability. Titanium-tantalum shape memory alloys represent a promising alternative if one can avoid the cyclic degradation due to the formation of the omega phase. The current study investigates the functional fatigue behavior of Ti-Ta and introduces a new concept providing for pronounced fatigue life extension. © 2014 The Authors.
  	view abstract	doi: 10.1142/S1793604714500428

• 2014 • 10	Recovery, recrystallization, grain growth and phase stability of a family of FCC-structured multi-component equiatomic solid solution alloys Wu, Z. and Bei, H. and Otto, F. and Pharr, G.M. and George, E.P. Intermetallics 46 131-140 (2014) The equiatomic high-entropy alloy FeNiCoCrMn is known to crystallize as a single phase with the face-centered cubic (FCC) crystal structure. To better understand this quinary solid solution alloy, we investigate various binary, ternary and quaternary alloys made from its constituent elements. Our goals are twofold: (i) to investigate which of these lower order systems also form solid solution alloys consisting of a single FCC phase, and (ii) to characterize their phase stability and recovery, recrystallization, and grain growth behaviors. X-ray diffraction (XRD) and scanning electron microscopy with backscattered electron images showed that three of the five possible quaternaries (FeNiCoCr, FeNiCoMn and NiCoCrMn), five of the ten possible ternaries (FeNiCo, FeNiCr, FeNiMn, NiCoCr, and NiCoMn), and two of the ten possible binaries (FeNi and NiCo) were single-phase FCC solid solutions in the cast and homogenized condition, whereas the others either had different crystal structures or were multi-phase. The single-phase FCC quaternary, FeNiCoCr, along with its equiatomic ternary and binary subsidiaries, were selected for further investigations of phase stability and the thermomechanical processing needed to obtain equiaxed grain structures. Only four of these subsidiary alloys - two binaries (FeNi and NiCo) and two ternaries (FeNiCo and NiCoCr) - were found to be single-phase FCC after rolling at room temperature followed by annealing for 1 h at temperatures of 300-1100 C. Pure Ni, which is FCC and one of the constituents of the quinary high-entropy alloy (FeNiCoCrMn), was also investigated for comparison with the higher order alloys. Among the materials investigated after thermomechanical processing (FeNiCoCr, FeNiCo, NiCoCr, FeNi, NiCo, and Ni), FeNiCo and Ni showed abnormal grain growth at relatively low annealing temperatures, while the other four showed normal grain growth behavior. The grain growth exponents for all five of the equiatomic alloys were found to be ∼0.25 (compared to ∼0.5 for unalloyed Ni), suggesting that solute drag may control grain growth in the alloys. For all five alloys, as well as for pure Ni, microhardness increases as the grain size decreases in a Hall-Petch type way. The ternary alloy NiCoCr was the hardest of the alloys investigated in this study, even when compared to the quaternary FeNiCoCr alloy. This suggests that solute hardening in equiatomic alloys depends not just on the number of alloying elements but also their type. © 2013 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.intermet.2013.10.024

• 2014 • 9	The thermodynamic assessment of the Au-In-Ga system Ghasemi, M. and Sundman, B. and Fries, S.G. and Johansson, J. Journal of Alloys and Compounds 600 178-185 (2014) The Au-In-Ga ternary phase diagram is of importance for understanding the involved thermodynamic processes during the growth of Au-seeded III-V heterostructure nanowires containing In and Ga (e.g. Au-seeded InAs/GaAs nanowires). In this work the Au-In-Ga system has been thermodynamically modeled using the CALPHAD technique based on a recent experimental investigation of the phase equilibria in the system. As a result, a set of self-consistent interaction parameters have been optimized that can reproduce most of the experimental results. © 2014 Elsevier B.V. All rights reserved.
  	view abstract	doi: 10.1016/j.jallcom.2014.02.071

• 2013 • 8	Atomic engineering of platinum alloy surfaces Li, T. and Bagot, P.A.J. and Marquis, E.A. and Edman Tsang, S.C. and Smith, G.D.W. Ultramicroscopy 132 205-211 (2013) A major practical challenge in heterogeneous catalysis is to minimize the loading of expensive platinum group metals (PGMs) without degrading the overall catalytic efficiency. Gaining a thorough atomic-scale understanding of the chemical/structural changes occurring during catalyst manufacture/operation could potentially enable the design and production of "nano-engineered" catalysts, optimized for cost, stability and performance. In the present study, the oxidation behavior of a Pt-31 at% Pd alloy between 673-1073. K is investigated using atom probe tomography (APT). Over this range of temperatures, three markedly different chemical structures are observed near the surface of the alloy. At 673. K, the surface oxide formed is enriched with Pd, the concentration of which rises further following oxidation at 773. K. During oxidation at 873. K, a thick, stable oxide layer is formed on the surface with a stoichiometry of PdO, beneath which a Pd-depleted (Pt-rich) layer exists. Above 873. K, the surface composition switches to enrichment in Pt, with the Pt content increasing further with increasing oxidation temperature. This treatment suggests a route for tuning the surfaces of Pt-Pd nanoparticles to be either Pd-rich or Pt-rich, simply by adjusting the oxidation temperatures in order to form two different types of core-shell structures. In addition, comparison of the oxidation behavior of Pt-Pd with Pt-Rh and Pd-Rh alloys demonstrates markedly different trends under the same conditions for these three binary alloys. © 2012.
  	view abstract	doi: 10.1016/j.ultramic.2012.10.012

• 2013 • 7	The influences of temperature and microstructure on the tensile properties of a CoCrFeMnNi high-entropy alloy Otto, F. and Dlouhý, A. and Somsen, C. and Bei, H. and Eggeler, G. and George, E.P. Acta Materialia 61 5743-5755 (2013) An equiatomic CoCrFeMnNi high-entropy alloy, which crystallizes in the face-centered cubic (fcc) crystal structure, was produced by arc melting and drop casting. The drop-cast ingots were homogenized, cold rolled and recrystallized to obtain single-phase microstructures with three different grain sizes in the range 4-160 μm. Quasi-static tensile tests at an engineering strain rate of 10-3 s-1 were then performed at temperatures between 77 and 1073 K. Yield strength, ultimate tensile strength and elongation to fracture all increased with decreasing temperature. During the initial stages of plasticity (up to ∼2% strain), deformation occurs by planar dislocation glide on the normal fcc slip system, {1 1 1}〈1 1 0〉, at all the temperatures and grain sizes investigated. Undissociated 1/2〈1 1 0〉 dislocations were observed, as were numerous stacking faults, which imply the dissociation of several of these dislocations into 1/6〈1 1 2〉 Shockley partials. At later stages (∼20% strain), nanoscale deformation twins were observed after interrupted tests at 77 K, but not in specimens tested at room temperature, where plasticity occurred exclusively by the aforementioned dislocations which organized into cells. Deformation twinning, by continually introducing new interfaces and decreasing the mean free path of dislocations during tensile testing ("dynamic Hall-Petch"), produces a high degree of work hardening and a significant increase in the ultimate tensile strength. This increased work hardening prevents the early onset of necking instability and is a reason for the enhanced ductility observed at 77 K. A second reason is that twinning can provide an additional deformation mode to accommodate plasticity. However, twinning cannot explain the increase in yield strength with decreasing temperature in our high-entropy alloy since it was not observed in the early stages of plastic deformation. Since strong temperature dependencies of yield strength are also seen in binary fcc solid solution alloys, it may be an inherent solute effect, which needs further study. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.actamat.2013.06.018

• 2011 • 6	Achieving small structures in thin NiTi sheets for medical applications with water jet and micro machining: A comparison Frotscher, M. and Kahleyss, F. and Simon, T. and Biermann, D. and Eggeler, G. Journal of Materials Engineering and Performance 20 776-782 (2011) NiTi shape memory alloys (SMA) are used for a variety of applications including medical implants and tools as well as actuators, making use of their unique properties. However, due to the hardness and strength, in combination with the high elasticity of the material, the machining of components can be challenging. The most common machining techniques used today are laser cutting and electrical discharge machining (EDM). In this study, we report on the machining of small structures into binary NiTi sheets, applying alternative processing methods being well-established for other metallic materials. Our results indicate that water jet machining and micro milling can be used to machine delicate structures, even in very thin NiTi sheets. Further work is required to optimize the cut quality and the machining speed in order to increase the cost-effectiveness and to make both methods more competitive. © ASM International.
  	view abstract	doi: 10.1007/s11665-010-9789-8

• 2011 • 5	Molecular dynamics simulation study of microstructure evolution during cyclic martensitic transformations Kastner, O. and Eggeler, G. and Weiss, W. and Ackland, G.J. Journal of the Mechanics and Physics of Solids 59 1888-1908 (2011) Shape memory alloys (SMA) exhibit a number of features which are not easily explained by equilibrium thermodynamics, including hysteresis in the phase transformation and reverse shape memory in the high symmetry phase. Processing can change these features: repeated cycling can train the reverse shape memory effect, while changing the amount of hysteresis and other functional properties. These effects are likely to be due to formations of localised defects and these can be studied by atomistic methods. Here we present a molecular dynamics simulation study of such behaviour employing a two-dimensional, binary LennardJones model. Our atomistic model exhibits a symmetry breaking, displacive phase transition from a high temperature, entropically stabilised, austenite-like phase to a low temperature martensite-like phase. The simulations show transformations in this model material proceed by non-diffusive nucleation and growth processes and produce distinct microstructures. We observe the generation of persistent lattice defects during forward-and-reverse transformations which serve as nucleation centres in subsequent transformation processes. These defects interfere the temporal and spatial progression of transformations and thereby affect subsequent product morphologies. During cyclic transformations we observe accumulations of lattice defects so as to establish new microstructural elements which represent a memory of the previous morphologies. These new elements are self-organised and they provide a basis of the reversible shape memory effect in the model material. © 2011 Elsevier Ltd.
  	view abstract	doi: 10.1016/j.jmps.2011.05.009

• 2011 • 4	On the stress-induced formation of R-phase in ultra-fine-grained Ni-rich NiTi shape memory alloys Olbricht, J. and Yawny, A. and Pelegrina, J.L. and Dlouhy, A. and Eggeler, G. Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 42 2556-2574 (2011) Phase transformations in binary ultra-fine-grained (UFG) pseudoelastic NiTi wires were studied in a wide temperature range using mechanical loading/unloading experiments, resistance measurements, differential scanning calorimetry (DSC), thermal infrared imaging, and transmission electron microscopy (TEM). The formation of R-phase can be detected in the mechanical experiments. It is shown that the stress-strain response of the R-phase can be isolated from the overall stress-strain data. The R-phase always forms prior to B19' when good pseudoelastic properties are observed. The stress-induced B2 to R-phase transition occurs in a homogeneous manner, contrary to the localized character of the B2/R to B19' transformations. The temperature dependence of the critical stress values for the formation of the martensitic phases shows a Clausius Clapeyron type of behavior with constants close to 6 MPa/K (B19') and 18 MPa/K (R-phase). A stress-temperature map is suggested that summarizes the experimentally observed sequences of elementary transformation/deformation processes. © The Minerals, Metals & Materials Society and ASM International 2011.
  	view abstract	doi: 10.1007/s11661-011-0679-y

• 2011 • 3	Segregation and stability in surface alloys: PdxRu 1-x/Ru(0001) and PtxRu1-x/Ru(0001) Bergbreiter, A. and Hoster, H.E. and Behm, R.J. ChemPhysChem 12 1148-1154 (2011) The stability of PdRu/Ru(0001) and PtRu/Ru(0001) surface alloys and the tendency for surface segregation of Pd and Pt subsurface guest metals in these surface alloys is studied by scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES). Atomic resolution STM imaging and AES measurements reveal that upon overgrowing the surface alloys with a 1-2 monolayer Ru film and subsequent annealing to the temperatures required for initial surface alloy formation, the Ru-covered Pd (Pt) atoms float back to the outermost layer. The lateral distribution of these species is also essentially identical to that of the initial surface alloys, before overgrowth by Ru. In combination, this clearly demonstrates that the surface alloys represent stable surface configurations, metastable only towards entropically favored bulk dissolution, and that there is a distinct driving force for surface segregation of these species. Consequences of these data on the mechanism for surface alloy formation are discussed. Floating in PtRu (PdRu) surface alloys on Ru(0001): The PtRu (PdRu)monolayer surface alloy layer is covered with the substrate metal Ru by means of physical vapour depositon. Subsequent annealing to temperatures necessary for surface alloy formation reconstitutes the original Pt (Pd) amount as well as the original atom distribution of the initial equilibrated alloy layer (see picture). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  	view abstract	doi: 10.1002/cphc.201001087

• 2011 • 2	TCP phase predictions in Ni-based superalloys: Structure maps revisited Seiser, B. and Drautz, R. and Pettifor, D.G. Acta Materialia 59 749-763 (2011) The traditional methods for predicting the occurrence of deleterious topologically close-packed (TCP) phases in Ni-based superalloys have been based on the PHACOMP and newPHACOMP methodologies. These schemes use the average number of holes Nh or the centre of gravity of the elemental d-bands Md to predict whether or not a given multicomponent alloy will be prone to TCP formation. However, as both these one-dimensional methodologies are well-known to fail with respect to new generations of alloys, a novel two-dimensional structure map (N,ΔV/V) is introduced where N is the average electron concentration and ΔV/V is a composition-dependent size-factor difference. This map is found to separate the experimental data on the TCP phases of binary A-B transition metal alloys into well-defined but sometimes overlapping regions corresponding to different structure types such as A15, σ, χ, R, P, δ, μ, M and Laves. Detailed investigations of ternary phase diagrams and multicomponent systems show that TCP phases, regardless of the number of constituents, are located in the same regions of the structure map that are favoured by the binary compounds of the same structure type. The structure map is then used in conjunction with CALPHAD computations of σ phase stability to show that the predictive power of newPHACOMP for the seven component Ni-Co-Cr-Ta-W-Re-Al system studied recently by Reed et al. [24] is indeed poor. This supports a growing consensus that robust methods of TCP phase prediction in multicomponent alloys will require the inclusion of reliable first-principles thermodynamic databases within the semi-empirical CALPHAD scheme. © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.actamat.2010.10.013

• 2010 • 1	L21-ordered Fe-Al-Ti alloys Krein, R. and Friak, M. and Neugebauer, J. and Palm, M. and Heilmaier, M. Intermetallics 18 1360-1364 (2010) Fe-Al-Ti alloys with the ordered L21-structure (Heusler phase) belong to the few Fe-Al-based alloys which show comparably high-strength at high temperatures, e.g. at 800 °C. However, like many other high-temperature materials based on intermetallics they show limited ductility even at high temperatures. In order to further explore the possibilities in increasing their strength and ductility, alloys with four different microstructures, i.e. single-phase L21, L21 with incoherent precipitates of TiB2 or Laves phase, and coherent L21 + A2, were produced. Also, the influence of alloying with Cr and B has been investigated. The Young's modulus of Fe-25Al-20Ti-4Cr (at.%) in dependence of temperature up to 900 °C has been determined and results of the compressive flow stress, creep strength and brittle-toductile transition temperatures (BDTT) are summarised and compared to those of binary Fe3Al (D03), Fe-Al-Ti-based alloys, and some commercial alloys. © 2010 Elsevier Ltd. All rights reserved.
  	view abstract	doi: 10.1016/j.intermet.2009.12.036