- Ruhr-Universität Bochum

For the development of a wearable artificial kidney (WAK) that uses a small dialysate volume that is continuously regenerated, it is essential that urea, one of the main uremic retention solutes, is removed. Despite advances in sorbent technology or electro-oxidation no safe, efficient and selective method for urea removal has been reported that allows miniaturization of the artificial kidney to wearable proportions. Here we have developed a flow cell for light-driven, photo-electrocatalytic (PEC) urea removal for use in a WAK. We use a photo-active material (hematite) coated with a catalyst (NiOOH) as working electrode for selective urea oxidation and a silver-chloride (AgCl) cathode. The use of the AgCl counter electrodes eliminates the need for an external bias voltage, and allows operation under light illumination only. Using LED illumination (460 nm) we show that urea is selectively oxidized over chloride. N2 formation is confirmed by gas-phase analysis of the headspace of the sample vial, using mass spectrometry. Other nitrogen containing products include nitrite but importantly ammonia and nitrate are not detected. Using the PEC concept a urea removal rate of 2.5 μmol/cm2h (or 0.15 mg/cm2h) has been achieved. Extrapolating our results to an upscaled system, a surface area of 0.5 m2 would enable efficient removal of the daily produced amount of urea (∼300 mmol) urea within 24 h, when driven by LED illumination only. © 2023 The Authors

The magnetic order for several compositions of CaK(Fe 1-x Mn x )4As4 has been studied by nuclear magnetic resonance (NMR), Mössbauer spectroscopy, and neutron diffraction. Our observations for the Mn-doped 1144 compound are consistent with the hedgehog spin vortex crystal (hSVC) order which has previously been found for Ni-doped CaKFe4As4 . The hSVC state is characterized by the stripe-type propagation vectors (π0) and (0π) just as in the doped 122 compounds. The hSVC state preserves tetragonal symmetry at the Fe site, and only this SVC motif with simple antiferromagnetic (AFM) stacking along c is consistent with all our observations using NMR Mössbauer spectroscopy, and neutron diffraction. We find that the hSVC state in the Mn-doped 1144 compound coexists with superconductivity, and by combining the neutron scattering and Mössbauer spectroscopy data we can infer a quantum phase transition, hidden under the superconducting dome, associated with the suppression of the AFM transition temperature (T N) to zero for x ≈ 0.01. In addition, unlike several 122 compounds and Ni-doped 1144, the ordered magnetic moment is not observed to decrease at temperatures below the superconducting transition temperature (T c). © 2023 The Author(s). Published by IOP Publishing Ltd.

Ion-induced secondary electron emission at a target surface is an essential mechanism for laboratory plasmas, i.e. magnetron sputtering discharges. Electron emission, however, is strongly affected by the target condition itself such as oxidation. Data of oxidized targets, however, are very sparse and prone to significant systematic errors, because they were often determined by modeling the complex behavior of the plasma. Thus, it is difficult to isolate the process of ion-induced electron emission from all other plasma-surface-interactions. By utilizing ion beams, the complex plasma environment is avoided and electron yields are determined with higher accuracy. In this study, ion-induced secondary electron emission coefficients (SEECs) of clean, untreated (air-exposed), and intentionally oxidized copper and nickel surfaces were investigated in such a particle beam experiment. Pristine and oxidized metal foils were exposed to beams of singly charged argon ions with energies of 0.2 keV-10 keV. After the ion beam treatment, the surface conditions were analyzed by ex-situ X-ray photoelectron spectroscopy measurements. Further, a model for the electron emission of a partly oxidized surface is presented, which is in agreement with the experimental data. It was found, that oxidized and untreated/air-exposed surfaces do not show the same SEEC: for intentionally oxidized targets, the electron yields were smaller by a factor of 2 than for untreated/air-exposed surfaces. SEECs of oxides were found to be between the values for clean and for untreated metal surfaces. Further, the SEEC was at maximum for untreated/air-exposed surfaces and at minimum for clean surfaces; the electron yields of untreated/air-exposed and clean surfaces were in agreement with values reported in the literature. © 2022 The Author(s). Published by IOP Publishing Ltd.

Creating high surface area nanocatalysts that contain stacking faults is a promising strategy to improve catalytic activity. Stacking faults can tune the reactivity of the active sites, leading to improved catalytic performance. The formation of branched metal nanoparticles with control of the stacking fault density is synthetically challenging. In this work, we demonstrate that varying the branch width by altering the size of the seed that the branch grows off is an effective method to precisely tune the stacking fault density in branched Ni nanoparticles. A high density of stacking faults across the Ni branches was found to lower the energy barrier for Ni2+/Ni3+oxidation and result in enhanced activity for electrocatalytic oxidation of 5-hydroxylmethylfurfural. These results show the ability to synthetically control the stacking fault density in branched nanoparticles as a basis for enhanced catalytic activity. © 2022 American Chemical Society. All rights reserved.

Electrode erosion through continual long-timescale operation (60 min) of identical twin surface dielectric barrier discharges (twin SDBDs) powered either by a microsecond (μs) or a nanosecond timescale (ns) voltage source is investigated. The twin SDBDs are characterized using current-voltage measurements, optical emission spectroscopy, and phase integrated ICCD imaging. The temporally and spatially averaged gas temperature, consumed electric power, and effective discharge parameters (reduced electric field, and electron density) are measured. The μs twin SDBD is shown to operate in a filamentary mode while the ns twin SDBD is shown to operate in a more homogeneous mode (i.e. non filamentary). Despite a similarity of the effective discharge parameters in both the μs and ns twin SDBD, erosion of the nickel coated electrodes caused by operation of the twin SDBD differs strongly. Only the formation of a moderate number of nickel oxide species is observed on the surface of the ns twin SDBD electrodes. In contrast, the nickel coated electrodes are locally melted and considerably higher densities of oxides are observed around the eroded areas of the μs twin SDBD, due to the filamentary nature of the discharge. © 2022 The Author(s). Published by IOP Publishing Ltd.

Deformation twinning is rarely found in bulk face-centered cubic (FCC) alloys with very high stacking fault energy (SFE) under standard loading conditions. Here, based on results from bulk quasi-static tensile experiments, we report deformation twinning in a micrometer grain-sized compositionally complex steel (CCS) with a very high SFE of ~79 mJ/m2, far above the SFE regime for twinning (<~50 mJ/m2) reported for FCC steels. The dual-nanoprecipitation, enabled by the compositional degrees of freedom, contributes to an ultrahigh true tensile stress up to 1.9 GPa in our CCS. The strengthening effect enhances the flow stress to reach the high critical value for the onset of mechanical twinning. The formation of nanotwins in turn enables further strain hardening and toughening mechanisms that enhance the mechanical performance. The high stress twinning effect introduces a so far untapped strengthening and toughening mechanism, for enabling the design of high SFEs alloys with improved mechanical properties. © 2022, The Author(s).

Low temperature (1023 K) high stress (800 MPa) tensile creep behavior of the superalloy single crystal ERBO-1 (CMSX-4 type) is investigated. Three loading directions are compared: precise [001] and 15 ° deviations from [001] towards [111] and [011]. It is found that creep rates ε˙ scale as ε˙[001]→[111]>ε˙[001]>ε˙[001]→[011]already in the early stages of creep (ε≤1%), where dislocation network formation and planar fault intersections cannot rationalize the observed rate effects. An analysis based on Peach-Köhler force calculations suggests, that fast creep rates are observed, when dislocations from two octahedral systems, which are required to react and form the leading part of a planar fault ribbon in the γ’-phase, experience similar driving forces. Creep data, micromechanical calculations and TEM results are in good qualitative agreement. From a technological point of view, the results show that while 15 ° deviations from [001] towards [011] can be tolerated, deviations towards [111] must be avoided. © 2021

Ni-Mn-based Heusler alloys have a high technical potential related to a large change of magnetization at the structural phase transition. These alloys show a subtle dependence of magnetic properties and structural phase stability on composition and substitution by 3d elements and although they have been extensively investigated, there are still ambiguities in the published results and their interpretation. To shed light on the large spread of reported properties, we perform a comprehensive study by means of density functional theory calculations. We focus on Cr and Co co-substitution whose benefit has been predicted previously for the expensive Ni-Mn-In-based alloy and study the more abundant iso-electronic counterpart Ni-Mn-Ga. We observe that substituting Ni partially by Co and/or Cr enhances the magnetization of the Heusler alloy and at the same time reduces the structural transition temperature. Thereby, Cr turns out to be more efficient to stabilize the ferromagnetic alignment of the Mn spins by strong antiferromagnetic interactions between Mn and Cr atoms. In a second step, we study Cr on the other sublattices and observe that an increase in the structural transition temperature is possible, but depends critically on the short-range order of Mn and Cr atoms. Based on our results, we are able to estimate composition dependent magnetic phase diagrams. In particular, we demonstrate that neither the atomic configuration with the lowest energy nor the results based on the coherent potential approximation are representative for materials with a homogeneous distribution of atoms and we also predict a simple method for fast screening of different concentrations which can be viewed as a blueprint for the study of high entropy alloys. Our results help to explain the large variation of experimentally found materials properties. © 2021 The Author(s). Published by IOP Publishing Ltd.

Alkaline anodic oxidation of glycerol suffers from facile C−C bond cleavage, especially when using non-precious metal electrocatalysts, which limits the yield of more valuable C3 oxygenates. Usually, a high C3 selectivity is a tradeoff with conversion for most catalysts. Thus, we used solketal as the reactant, which is acetal-protected glycerol with acetone. CV experiments showed that solketal is oxidized over nickel boride (NixB) at potentials where NiOOH is formed. Electrolysis over NixB in a thin-film spectroelectrochemical flow cell at 1.58 V vs. RHE to avoid pronounced oxygen evolution showed a stable current density of ca. 6 mA cm−2. Simultaneously recorded ATR-FTIR spectra revealed solketal conversion to solketalate and formate. Indeed, 59 % conversion and 77 % selectivity to glyceric acid were determined by HPLC after acidic cleavage of the acetal, resulting in a yield of 45 %. Therefore, solketal is a promising reactant for the selective electrosynthesis of glyceric acid. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH.

The gradient microstructures of surface layer in single crystal nickel-based superalloy were produced by creep-feed grinding. The mechanical properties (i.e., hardness, elastic modulus) and room-temperature (RT) creep behavior of such structures were evaluated using a nano-indentation technique. Results show that the gradient structures along depth from ground surface consisted of nanograins, submicron grains and lamellar-shape structures, and dislocation structures. Furthermore, it was found that the hardness and elastic modulus of gradient structures were higher by 8–10% than that of bulk material on average. However, the regions containing nanograins showed a remarkable increase in creep depth compared to bulk material, implying that the creep behavior of ground layer was changed unfavorably. The obtained stress exponents of gradient structures suggested that dislocation activities were the main mechanism for indentation creep deformation. © 2021 Elsevier B.V.

Physical properties of ten single-phase FCC CrxMn20Fe20Co20Ni40-x high-entropy alloys (HEAs) were investigated for 0 ≤ x ≤ 26 at%. The lattice parameters of these alloys were nearly independent of composition while solidus temperatures increased linearly by ∼30 K as x increased from 0 to 26 at.%. For x ≥ 10 at.%, the alloys are not ferromagnetic between 100 and 673 K and the temperature dependencies of their coefficients of thermal expansion and elastic moduli are independent of composition. Magnetic transitions and associated magnetostriction were detected below ∼200 K and ∼440 K in Cr5Mn20Fe20Co20Ni35 and Mn20Fe20Co20Ni40, respectively. These composition and temperature dependencies could be qualitatively reproduced by ab initio simulations that took into account a ferrimagnetic ↔ paramagnetic transition. Transmission electron microscopy revealed that plastic deformation occurs initially by the glide of perfect dislocations dissociated into Shockley partials on {111} planes. From their separations, the stacking fault energy (SFE) was determined, which decreases linearly from 69 to 23 mJ·m−2 as x increases from 14 to 26 at.%. Ab initio simulations were performed to calculate stable and unstable SFEs and estimate the partial separation distances using the Peierls-Nabarro model. While the compositional trends were reasonably well reproduced, the calculated intrinsic SFEs were systematically lower than the experimental ones. Our ab initio simulations show that, individually, atomic relaxations, finite temperatures, and magnetism strongly increase the intrinsic SFE. If these factors can be simultaneously included in future computations, calculated SFEs will likely better match experimentally determined SFEs. © 2022

Co-Ni-Ga shape memory alloys attracted scientific attention as promising candidate materials for damping applications at elevated temperatures, owing to excellent superelastic properties featuring a fully reversible stress-strain response up to temperatures as high as 500 °C. In the present work, the effect of aging treatments conducted in a wide range of aging temperatures and times, i.e. at 300–400 °C for 0.25–8.5 h, was investigated. It is shown that critical features of the martensitic transformation are strongly affected by the heat treatments. In particular, the formation of densely dispersed γ’-nanoparticles has a strong influence on the martensite variant selection and the morphology of martensite during stress-induced martensitic transformation. Relatively large, elongated particles promote irreversibility. In contrast, small spheroidal particles are associated with excellent functional stability during cyclic compression loading of 〈001〉-oriented single crystals. In addition to mechanical experiments, a detailed microstructural analysis was performed using in situ optical microscopy and neutron diffraction. Fundamental differences in microstructural evolution between various material states are documented and the relations between thermal treatment, microstructure and functional properties are explored and rationalized. © 2022 Acta Materialia Inc.

Electrocatalytic oxidation of glycerol (GOR) as the anode reaction in water electrolysis facilitates the production of hydrogen at the cathode at a substantially lower cell voltage compared with the oxygen evolution reaction. It simultaneously provides the basis for the production of value-added compounds at the anode. We investigate earth-abundant transition-metal oxide nanoparticles (Fe, Ni, Mn, Co) embedded in multiwalled carbon nanotubes as GOR catalysts. Out of the four investigated composites, the Ni-based catalyst exhibits the highest catalytic activity toward the GOR according to rotating disk electrode voltammetry, reaching a current density of 10 mA cm–2 already at 1.31 V vs RHE, a potential below the formation of Ni3+. Chronoamperometry conducted in a flow-through cell followed by HPLC analysis is used to identify and quantify the GOR products over time, revealing that the applied potential, electrolyte concentration, and duration of the experiment impact strongly the composition of the products’ mixture. Upon optimization, the GOR is directed toward oxalate production. Moreover, oxalate is not further converted and hence accumulates as a major organic product under the chosen conditions in a concentration ratio of 60:1 with acetate as a minor product after 48 h electrolysis in 7 M KOH, which represents a promising route for the synthesis of this highly valued product. © 2022 American Chemical Society

The development of noble-metal-free electrocatalysts is regarded as a key factor for realizing industrial-scale hydrogen production powered by renewable energy sources. Inspired by nature, which uses Fe-and Ni-containing enzymes for efficient hydrogen generation, Fe/Ni-containing chalcogenides, such as oxides and sulfides, received increasing attention as promising electrocatalysts to produce hydrogen. We herein present a novel synthetic procedure for mixed Fe/Ni (oxy)sulfide materials by the controlled (partial) sulfidation of NiFe2O4 (NFO) nanoparticles in H2S-containing atmospheres. The variation in H2S concentration and the temperature allows for a precise control of stoichiometry and phase composition. The obtained sulfidized materials (NFS) catalyze the hydrogen evolution reaction (HER) with increased activity in comparison to NFO, up to −10 and −100 mA cm−2 at an overpotential of approx. 250 and 450 mV, respectively. © 2022 by the authors. Licensee MDPI, Basel, Switzerland.

Soft magnetic materials (SMMs) serve in electrical applications and sustainable energy supply, allowing magnetic flux variation in response to changes in applied magnetic field, at low energy loss1. The electrification of transport, households and manufacturing leads to an increase in energy consumption owing to hysteresis losses2. Therefore, minimizing coercivity, which scales these losses, is crucial3. Yet meeting this target alone is not enough: SMMs in electrical engines must withstand severe mechanical loads; that is, the alloys need high strength and ductility4. This is a fundamental design challenge, as most methods that enhance strength introduce stress fields that can pin magnetic domains, thus increasing coercivity and hysteresis losses5. Here we introduce an approach to overcome this dilemma. We have designed a Fe–Co–Ni–Ta–Al multicomponent alloy (MCA) with ferromagnetic matrix and paramagnetic coherent nanoparticles (about 91 nm in size and around 55% volume fraction). They impede dislocation motion, enhancing strength and ductility. Their small size, low coherency stress and small magnetostatic energy create an interaction volume below the magnetic domain wall width, leading to minimal domain wall pinning, thus maintaining the soft magnetic properties. The alloy has a tensile strength of 1,336 MPa at 54% tensile elongation, extremely low coercivity of 78 A m−1 (less than 1 Oe), moderate saturation magnetization of 100 A m2 kg−1 and high electrical resistivity of 103 μΩ cm. © 2022, The Author(s).

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.

Nickel-based superalloys have a wide range of applications in high temperature and stress domains due to their unique mechanical properties. Under mechanical loading at high temperatures, rafting occurs, which reduces the service life of these materials. Rafting is heavily affected by the loading conditions associated with plastic strain; therefore, understanding plastic strain evolution can help understand these material's service life. This research classifies nickel-based superalloys with respect to creep strain with deep learning techniques, a technique that eliminates the need for manual feature extraction of complex microstructures. Phase-field simulation data that displayed similar results to experiments were used to build a model with pre-trained neural networks with several convolutional neural network architectures and hyper-parameters. The optimized hyper-parameters were transferred to scanning electron microscopy images of nickel-based superalloys to build a new model. This fine-tuning process helped mitigate the effect of a small experimental dataset. The built models achieved a classification accuracy of 97.74% on phase-field data and 100% accuracy on experimental data after fine-tuning. © 2022 The Author(s). Published by IOP Publishing Ltd.

The recent scanning tunneling microscopy (STM) observation of -shaped and -shaped spectra (and their mixture) in superconducting thin films has been interpreted as the presence of two distinct gap symmetries in this nickelate superconductor [Gu, Nat. Commun.11, 6027 (2020)10.1038/s41467-020-19908-1]. Here, using a two-band model of nickelates capturing dominant contributions from Ni- and rare-earth (R)- orbitals, we show that the experimental observation can be simply explained within a pairing scenario characterized by a conventional -wave gap structure with the lowest harmonic on the Ni band and a -wave gap with higher harmonics on the R band. We perform realistic simulations of STM spectra employing first-principles Wannier functions to properly account for the tunneling processes and obtain and mixed spectral line shapes depending on the position of the STM tip within the unit cell. The - and -shaped spectra are contributed by Ni and R bands, respectively, and Wannier functions, in essence, provide position-dependent weighting factors, determining the spectral line shape at a given intra-unit-cell position. We propose a phase-sensitive experiment to distinguish between the proposed -wave gap structure and the time-reversal symmetry-breaking gap which yields very similar intra-unit-cell spectra. © 2021 American Physical Society

CO2 methanation using nickel-based catalysts has attracted large interest as a promising power-to-gas route. Ni nanoparticles supported on nitrogen-doped CNTs with Ni loadings in the range from 10 wt% to 50 wt% were synthesized by impregnation, calcination and reduction and characterized by elemental analysis, X-ray powder diffraction, H2 temperature-programmed reduction, CO pulse chemisorption and transmission electron microscopy. The Ni/NCNT catalysts were highly active in CO2 methanation at atmospheric pressure, reaching over 50% CO2 conversion and over 95% CH4 selectivity at 340 °C and a GHSV of 50,000 mL g−1 h−1 under kinetically controlled conditions. The small Ni particle sizes below 10 nm despite the high Ni loading is ascribed to the efficient anchoring on the N-doped CNTs. The optimum loading of 30 wt%–40 wt% Ni was found to result in the highest Ni surface area, the highest degree of conversion and the highest selectivity to methane. A constant TOF of 0.3 s−1 was obtained indicating similar catalytic properties of the Ni nanoparticles in the range from 10 wt% to 50 wt% Ni loading. Long-term experiments showed that the Ni/NCNT catalyst with 30 wt% Ni was highly stable for 100 h time on stream. © 2020 Science Press

In this study, we report on face-centered cubic structured CoCrFeNi high-entropy alloy thin films with finely dispersed nano-oxide particles which are formed by internal oxidation. Analytical scanning transmission electron microscopy imaging found that the particles are Cr2O3. The oxide particles contribute to the hardening of the film increasing its hardness by 14% compared to that of the film without precipitates, through the Orowan-type strengthening mechanism. Our novel approach paves the way to design medium- and high-entropy alloys with high strength by making use of oxide phases. © 2021

The plastic deformation behavior of single crystals of the quinary, equiatomic Cr−Mn−Fe−Co−Ni high-entropy alloy (HEA) with the face-centered cubic structure has been investigated in tension and compression as a function of crystal orientation and temperature from 10 K to 1373 K. The critical resolved shear stress (CRSS) for {111}<110> slip at room temperature is 42−45 MPa. It does not depend much on crystal orientation (i.e., the Schmid law holds true) and the sense (tension vs. compression) of the applied load. The CRSS for {111}<110> slip increases with the decrease in temperature, without showing any significant inertia effects at cryogenic temperatures below 77 K. Extrapolation from the measured yield stresses down to 10 K yields a CRSS value at 0 K of 168 MPa. At cryogenic temperatures, the measured strain-rate sensitivity of flow stress is consistent with a very small activation volume. The concept of stress equivalence holds true both for the temperature dependence of CRSS and the stress dependence of activation volume, indicating that solid-solution hardening is the major strengthening mechanism. Deformation twinning occurs at 77 K but not at room temperature, resulting in higher tensile elongation to failure at 77 K than at room temperature. Deformation twinning at 77 K occurs at a shear stress of 378 MPa on conjugate (1¯1¯1) planes in the form of Lüders deformation after large plastic strain (about 85%) achieved by the stage I (easy glide) and stage II (linear work-hardening) deformation. © 2020

Employing atomistic simulations, we investigated the void collapse mechanisms in single crystal Ni during hydrostatic compression and explored how the atomistic mechanisms of void collapse are influenced by temperature. Our results suggest that the emission and associated mutual interactions of dislocation loops around the void is the primary mechanism of void collapse, irrespective of the temperature. The rate of void collapse is almost insensitive to the temperature, and the process is not thermally activated until a high temperature (1200-1500 K) is reached. Our simulations reveal that, at elevated temperatures, dislocation motion is assisted by vacancy diffusion and consequently the void is observed to collapse continuously without showing appreciable strain hardening around it. In contrast, at low and ambient temperatures (1 and 300 K), void collapse is delayed after an initial stage of closure due to significant strain hardening around the void. Furthermore, we observe that the dislocation network produced during void collapse remains the sample even after complete void collapse, as was observed in a recent experiment of nickel-base superalloy after hot isostatic pressing. © 2021 by the authors.

The influence of the drop-casted nickel boride catalyst loading on glassy carbon electrodes was investigated in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in alkaline glycerol electrooxidation. The continuously operated radial flow cell consisted of a borehole electrode positioned 50 µm above an internal reflection element enabling operando FTIR spectroscopy. It is identified as a suitable tool for facile and reproducible screening of electrocatalysts under well-defined conditions, additionally providing access to the selectivities in complex reaction networks such as glycerol oxidation. The fast product identification by ATR-IR spectroscopy was validated by the more time-consuming quantitative HPLC analysis of the pumped electrolyte. High degrees of glycerol conversion were achieved under the applied laminar flow conditions using 0.1 M glycerol and 1 M KOH in water and a flow rate of 5 µL min−1. Conversion and selectivity were found to depend on the catalyst loading, which determined the catalyst layer thickness and roughness. The highest loading of 210 µg cm−2 resulted in 73% conversion and a higher formate selectivity of almost 80%, which is ascribed to longer residence times in rougher films favoring readsorption and C–C bond scission. The lowest loading of 13 µg cm−2 was sufficient to reach 63% conversion, a lower formate selectivity of 60%, and, correspondingly, higher selectivities of C2 species such as glycolate amounting to 8%. Thus, only low catalyst loadings resulting in very thin films in the few μm thickness range are suitable for reliable catalyst screening. © 2021 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences

During the operation of turbines in jet engines or in power plants, high thermal and intermittent mechanical loads appear, which can lead to high-temperature fatigue failure if thermal and mechanical loads vary at the same time. Since fatigue testing is a time-consuming process, it is important to develop realistic material models with predictive capabilities that are able to extrapolate the limited experimental results for cyclic plasticity within a wide range of temperatures. To accomplish this, an approach based on a representative volume element (RVE), mimicking the typical γ/γ′ microstructure of a Ni-based single crystal superalloy, is adopted for cyclic loading conditions. With the help of this RVE, the temperature- and deformation-dependent internal stresses in the microstructure can be taken into account in a realistic manner, which proves to be essential in understanding the fatigue behavior of this material. The material behavior in the elastic regime is described by temperature-dependent anisotropic elastic constants. The flow rule for plastic deformation is governed by the thermal activation of various slip systems in the γ matrix, the γ′ precipitate and also by cube slip along the γ/γ′ microstructure. This phenomenological crystal plasticity/creep model takes different mechanisms into account, including thermally activated dislocation slip, the internal stresses due to inhomogeneous strains in different regions of γ matrix channels and in γ′ precipitates, the softening effect due to dislocation climb, the formation of 〈112〉 dislocation ribbons for precipitate shearing, and Kear-Wilsdorf locks. This constitutive law is parameterized based on experimental data for the CMSX-4 single-crystal superalloy by applying an inverse analysis to identify the material parameters based on many low cycle fatigue tests in the intermediate temperature and high stress regime. The identified material parameters could predict cyclic plasticity and low cycle fatigue behavior at different temperatures. The model does not only reliably reproduce the experimental results along different crystallographic loading directions, but it also reveals the relative importance of the different deformation mechanisms for the fatigue behavior under various conditions. © 2021 Elsevier Ltd

Using both novel high-throughput screening via combinatorial thin film deposition and conventional bulk alloy synthesis techniques, a large region of the AlCrFeNiTi composition space has been probed for alloys that could serve as low cost alternatives to nickel-base superalloys for medium-to-high temperature structural applications. Phase formation trends in this highly complex alloying system have been determined using characterisation techniques that span multiple length scales—from bulk X-ray diffraction and differential scanning calorimetry to atomically resolved scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. A large region of stability for both disordered A2 and ordered B2/L21 type phases is observed, with several compositions exhibiting fine-scaled precipitation structures of these two phases. For alloys with ≥20 at.% Al, the precipitation structure was further refined to a nano-scale lamellar arrangement of A2 and B2/L21 phases. Formation of C14 Laves phase, especially for compositions with >10 at.% Ti, has consistently been observed. We include a screening of the mechanical properties based on nanoindentation and macroscopic hardness test data correlated with scanning electron microscope (SEM) observations of the hardness indents. The phase formation trends observed by both combinatorial thin film deposition and bulk alloy synthesis are discussed in detail for samples in the as-deposited and as-cast conditions, respectively. © 2020 Elsevier Ltd

Mesoporous NiFe2O4 for electrocatalytic water splitting was prepared via soft-templating using citric-acid-complexed metal nitrates as precursors. The mesopore evolution during thermal treatment was examined systematically giving insights into the formation process of mesoporous NiFe2O4. Detailed nitrogen physisorption analysis including desorption scanning experiments reveal the presence of highly accessible mesopores generating surface areas of up to 200 m2/g. The ability of the NiFe2O4 powders to perform electrocatalytic oxygen evolution reaction under alkaline conditions was investigated, highlighting the advantages of mesopore insertion. The most active samples reach a current density of 10 mA cm−2 at an overpotential of 410 mV with a small Tafel slope of 50 mV dec−1, indicating an enhanced activity that originated from the increased catalyst surface. © 2020 The Authors. ChemElectroChem published by Wiley-VCH GmbH

Transition metal ferrites, such as CoFe2O4 (CFO) and NiFe2O4 (NFO), have gained increasing attention as potential materials for supercapacitors. Since chemical vapor deposition (CVD) offers advantages like interface quality to the underlying substrates and the possibility for coverage of 3D substrates, two CVD processes are reported for CFO and NFO. Growth rates amount to 150 to 200 nm h−1 and yield uniform, dense, and phase pure spinel ferrite films according to X-ray diffraction (XRD), Raman spectroscopy, Rutherford backscattering spectrometry and nuclear reaction analysis (RBS/NRA) and scanning electron microscopy (SEM). Atom probe tomography (APT) and synchrotron X-ray photoelectron spectroscopy (XPS) give insights into the vertical homogeneity and oxidation states in the CFO films. Cation disorder of CFO is analyzed for the first time from synchrotron-based XPS. NFO is analyzed via lab-based XPS. Depositions on conducting Ni and Ti substrates result in electrodes with pseudocapacitive behavior, as evidenced by cyclovoltammetry (CV) experiments. The interfacial capacitances of the electrodes are up to 185 µF cm−2. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH

In this work, a novel alloy design of a stainless steel with a ferritic-austenitic microstructure is derived for PBF-LB/M (powder bed fusion-laser beam/metal). The alloy was developed based on X2CrNiMo17-12-2 steel, for which an austenite volume content of approx. 54 vol% in the PBF-LB/M state was achieved using a reduced Ni equivalent. Partial substitution of Ni by Mn increases the N solubility of the alloy. By melting and further gas-atomizing this melt in an N2 atmosphere, an N content of 0.27 mass% was set in the produced steel powder. This leads to both high strength and high corrosion resistance of the PBF-LB/M-processed steel. However, microstructural investigations in the PBF-LB/M state confirm a microstructure consisting of ferrite, austenite, and Mo- and Cr-rich nitrides of M2N type. The nitrides were not completely eliminated by a subsequent heat treatment of the PBF-LB/M samples. As a result of the solution annealing, the microstructure approaches the thermodynamic equilibrium so that the austenite volume content increases from 54.2 vol% to 92.7 vol%. The higher Cr and N contents result in a higher corrosion resistance of the investigated steel compared to PBF-LB/M-processed X2CrNiMo17-12-2, regarded as the reference material. In addition, the measured strengths are significantly higher due to the larger amounts of austenite/ferrite interfaces and the N-induced solid-solution strengthening effect compared to X2CrNiMo17-12-2. © 2021 Elsevier B.V.

X-ray-based analytics are routinely applied in many fields, including physics, chemistry, materials science, and engineering. The full potential of such techniques in the life sciences and medicine, however, has not yet been fully exploited. We highlight current and upcoming advances in this direction. We describe different X-ray-based methodologies (including those performed at synchrotron light sources and X-ray free-electron lasers) and their potentials for application to investigate the nano-bio interface. The discussion is predominantly guided by asking how such methods could better help to understand and to improve nanoparticle-based drug delivery, though the concepts also apply to nano-bio interactions in general. We discuss current limitations and how they might be overcome, particularly for future use in vivo. ©

A single Cr-rich σ-phase alloy with a composition of Co17Cr46Fe16.3Mn15.2Ni5.5 (at.%) and a tetragonal lattice structure was produced. The tracer diffusion coefficients of Ni and Fe were measured by secondary electron mass spectroscopy using the highly enriched 64Ni and 58Fe natural isotopes. On the homologous temperature scale, Ni and Fe diffuse in the σ phase faster as compared to the corresponding diffusion rates in the equiatomic and face-centered cubic CoCrFeMnNi alloy. In contrast, on the absolute temperature scale, these elements diffuse roughly at the same rates in both materials. Factors influencing element diffusion and phase stability of the σ phase compared to the equiatomic alloy are discussed. © 2020 Acta Materialia Inc.

Understanding the structure-property relations of non-precious metal heteroatom co-doped carbon electrocatalysts exhibiting high activity as well as long-term durability for both ORR and OER remains challenging but is indispensable for the development of bifunctional ORR/OER electrocatalysts. We propose B-N-co-doped graphitic 2D carbon nanostructures impregnated with controlled amount of transition metals (M-BCN; M=Co, Ni, Fe, Cu) as bifunctional ORR/OER electrocatalysts. Co-BCN outperformed the Ni-, Fe-, Cu-based BCN catalysts exhibiting potential values of 0.87 V and 1.62 V at −1 mA/cm2 and 10 mA/cm2 during ORR and OER, respectively. Importantly, Co-BCN shows bifunctional cyclic stability (Δη; EOER−EORR=0.75 V) of up to 300 cycles in 1 M KOH for a duration of 20 h with total activity loss of only 10.2 % (ORR) and 6.2 % (OER), respectively. A low loading of the metal precursors was used to preserve porosity and to facilitate the formation of metal nanoparticles or M−NxB/C type species embedded in the graphitic carbon layers. The B-N-co-doped graphitic layers also protect the embedded metal nanoparticles explaining the observed long-term stability. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH

Gaining a fundamental understanding of crystal nucleation processes in metal alloys is crucial for the development and design of high-performance materials with targeted properties. Yet, crystallization is a complex non-equilibrium process and, despite having been studied for decades, the microscopic aspects that govern the crystallization mechanism of a material remain elusive to date. Recent evidence shows that the spatial heterogeneity in the supercooled liquid, characterised by extended regions with distinctive mobility and order, may be a key microscopic factor that determines the mechanism of crystal nucleation. These findings have advanced our view of the fundamental nature of crystallization, as most research has assumed that crystal clusters nucleate from random fluctuations in a ‘homogeneous’ liquid. Here, by analysing transition path sampling trajectories, we show that dynamical heterogeneity plays a key role in the mechanism of crystal nucleation in an elemental metal, nickel. Our results demonstrate that crystallization occurs preferentially in regions of low mobility in the supercooled liquid, evidencing the collective dynamical nature of crystal nucleation in Ni. In addition, our results show that low mobility regions form before and spatially overlap with pre-ordered domains that act as precursors to the crystal phase that subsequently emerges. Our results show a clear link between dynamical and structural heterogeneity in the supercooled liquid and its impact on the nucleation mechanism, revealing microscopic descriptors that could pave a novel way to control crystallization processes in metals. © 2022 The Royal Society of Chemistry.

In this work, the nanometer-scale mass flow coupled to dislocation processes near the γ/γ′-interface during high temperature and low stress creep of a model Ni-base single crystal superalloy is investigated. In the early creep stages, the dislocation networks in the γ-phase at γ/γ′-interfaces attract γ-stabilizing elements like Cr, Co and in particular Re, resulting in compositional gradients close to the interface. At larger strains, where dislocations frequently cut into the γ′-phase, this local interfacial enrichment in these elements is no longer observed. The cutting dislocations take part of the segregated atoms away, whilst the remaining atoms are released and diffuse back into the γ-channels. © 2020

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).

In this work, an automated image analysis procedure for the quantification of microstructure evolution during creep is proposed for evaluating scanning electron microscopy micrographs of a single crystal Ni-based superalloy before and after creep at 950 °C and 350 MPa. scanning electron microscopy-micrographs of γ/γ′ microstructures are transformed into binary images. Image analysis, which involves pixel by pixel classification and feature extraction, is then combined with a supervised machine learning algorithm to improve the binarization and the quality of the results. The binarization of the gray scale images is not always straight forward, especially when the difference in gray levels between the γ-channels and the γ′-phase is small. To optimize feature extraction, we utilized a series of bilateral filters as well as a machine learning algorithm, known as the gradient boosting method, that was used for training and classifying the micrograph pixels. After testing the two methods, the gradient boosting method was identified as the most effective. Subsequently, a Python routine was written and implemented for the automated quantification of the γ′ area fraction and the γ channel width. Our machine learning method is documented and the results of the automatic procedure are discussed based on results which we previously reported in the literature. © 2021 The Author(s). Published by IOP Publishing Ltd.

Metal-rich transition metal sulfides recently gained increasing attention as electrocatalysts for the hydrogen evolution reaction (HER), as they are capable to overcome major challenges faced by sulfide-rich metal catalysts such as limited conductivity and the necessity of nanostructuring. Herein, we present the synthesis, characterization and electrocatalytic investigation of ternary metal-rich sulfide composites FexCo9–xS8 as well as NiyCo9–yS8 (x = y = 0–4.5), which possess pentlandite-type structures. In this study, we show a stepwise alteration of the binary cobalt pentlandite Co9S8 and report on the replacement of cobalt with up to 4.5 equivalents of either iron or nickel. These altered pentlandite composites facilitate the proton reduction in acidic media at different temperatures. We furthermore show that the stoichiometric variation has a decisive influence on the electrochemical activation/deactivation behavior of the catalysts under reductive electrocatalytic conditions. Here, Co-deficient composites display an improved HER performance in contrast to Co9S8. Notably, Ni/Co compounds generally tend to show higher catalytic activities towards HER than their respective Fe/Co compounds. © 2021 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences

The development of accurate kinetic databases by parametrizing the composition and temperature dependence of elemental atomic mobilities, is essential for correct multicomponent calculations and simulations. In this work the automated assessment procedure for the establishment of CALPHAD-type kinetic databases is proposed, including the storage of raw data and assessment results, automatic weighting of data, parameter selection and automated reassessments. This allows the establishment of reproducible up-to-date databases. The proposed software, written in python, is applied to the assessment of a kinetic database for the fcc Co-Cr-Fe-Mn-Ni high entropy alloy using only tracer diffusion data for a sharp separation of thermodynamic and kinetic data. The established database is valid for the whole composition range of the five-component high entropy alloy. © 2021 The Author(s). Published by IOP Publishing Ltd Printed in the UK

The effectiveness of the mechanism of precipitation strengthening in metallic alloys de-pends on the shapes of the precipitates. Two different material systems are considered: tetragonal γ′′ precipitates in Ni-based alloys and tetragonal θ′ precipitates in Al-Cu-alloys. The shape formation and evolution of the tetragonally misfitting precipitates was investigated by means of experiments and phase-field simulations. We employed the method of invariant moments for the consistent shape quantification of precipitates obtained from the simulation as well as those obtained from the experiment. Two well-defined shape-quantities are proposed: (i) a generalized measure for the particles aspect ratio and (ii) the normalized λ2, as a measure for shape deviations from an ideal ellipse of the given aspect ratio. Considering the size dependence of the aspect ratio of γ′′ precipitates, we find good agreement between the simulation results and the experiment. Further, the precipitates’ in-plane shape is defined as the central 2D cut through the 3D particle in a plane normal to the tetragonal c-axes of the precipitate. The experimentally observed in-plane shapes of γ′′-precipitates can be quantitatively reproduced by the phase-field model. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Ni-based single crystal superalloys contain microstructural regions that are separated by low-angle grain boundaries. This gives rise to the phenomenon of mosaicity. In the literature, this type of defect has been associated with the deformation of dendrites during Bridgman solidification. The present study introduces a novel serial sectioning method that allows to rationalize mosaicity on the basis of spatial dendrite growth. Optical wide-field micrographs were taken from a series of cross sections and evaluated using quantitative image analysis. This allowed to explore the growth directions of close to 2500 dendrites in a large specimen volume of approximately 450 mm3. The application of tomography in combination with the rotation vector base-line electron back-scatter diffraction method allowed to analyze how small angular differences evolve in the early stages of solidification. It was found that the microstructure consists of dendrites with individual growth directions that deviate up to ≈4° from the average growth direction of all dendrites. Generally, individual dendrite growth directions coincide with crystallographic <001> directions. The quantitative evaluation of the rich data sets obtained with the present method aims at contributing to a better understanding of elementary processes that govern competitive dendrite growth and crystal mosa-icity. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Abstract: Surface degradation phenomena of two model equiatomic alloys from the CrMnFeCoNi alloy system were investigated in 2% O2 and 10% H2O (pO2 = 0.02 and 10−7 atm, respectively) at 800 °C for times up to 96 h. The crystallographic structures, morphologies, and chemical compositions of the corrosion layers developing on CrMnFeCoNi and CrCoNi were comparatively analyzed by mass gain analysis, X-ray diffraction, and scanning electron microscopy combined with energy-dispersive X-ray spectroscopy and electron backscatter diffraction. The oxidation resistance of CrMnFeCoNi is relatively poor due to the fast growth of porous Mn-oxide(s). CrCoNi forms an external chromia layer that is dense and continuous in a dry 2% O2 atmosphere. This layer buckles and spalls off after exposure to 10% H2O atmosphere. Beneath the chromia layer, a Cr-depleted zone forms in the CrCoNi alloy in both environments. As the oxide scale spalls off in the H2O-containing atmosphere, a secondary chromia layer was observed and correspondingly enlarges the Cr-depleted zone. In contrast, as the chromia layer remains without significant spallation when CrCoNi is exposed to a dry oxidizing atmosphere, the region depleted in Cr is narrower. Graphic Abstract: [Figure not available: see fulltext.]. © 2020, The Author(s).

The development of efficient and cost-effective electrocatalytic materials is an important part in scaling up sustainable electrochemical energy devices such as electrolyzers and fuel cells. In particular, the sluggish kinetics of the oxygen evolution reaction (OER) during water splitting renders the need of a catalyst indispensable. However, the development of catalysts is often based on laboratorial trial-and-error approaches and complex synthetic routes. Herein, the facile and systematic synthesis of pentlandite-like FexNi9-xS8 (x=0–9) nanosized particles from its elements with distinct Fe: Ni ratios was achieved using a mechanochemical method. The OER performance is optimized through tailoring the surface properties via altering the catalyst composition. The catalytic activity increases with higher nickel content in the structure, accomplishing an overpotential of 354 and 420 mV for ‘Ni9S8’ to drive 10 and 100 mA cm−2, respectively, with high stability. The in-situ formed nickel oxide/hydroxide species concurrent with sulphur depletion from the pentlandite structure upon OER are more active than NiS, inferring the crucial role of the pentlandite structure in activity. The herein reported simple synthetic approach could bring significant progress in the catalyst material development via rationally screening pentlandites with desired properties for modern energy systems. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH.

Hydrogen production is a key driver for sustainable and clean fuels used to generate electricity, which can be achieved through electrochemical splitting of water in alkaline solutions. However, the hydrogen evolution reaction (HER) is kinetically sluggish in alkaline media. Therefore, it has become imperative to develop inexpensive and highly efficient electrocatalysts that can replace the existing expensive and scarce noble-metal-based catalysts. Herein, we report on the rational design of nonprecious heterostructured electrocatalysts comprising a highly conductive face-centered cubic nickel metal, a nickel sulfide (NiS) phase, and a reduced graphene oxide (rGO) doped with phosphorous (P), sulfur (S), and nitrogen (N) in one ordered heteromaterial named Ni/NiS/P,N,S-rGO. The Ni/NiS/P,N,S-rGO electrode shows the best performance toward HER in 1.0 M KOH media among all materials tested with an overpotential of 155 mV at 10.0 mA cm-2 and a Tafel slope of 135 mV dec-1. The performance is comparable to the herein used Pt/C-20% benchmark catalyst examined under the same experimental conditions. The chronoamperometry and chronopotentiometry measurements have reflected the high durability of the Ni/NiS/P,N,S-rGO electrode for technological applications. At the same time, the current catalyst showed a high robustness and structure retention after long-term HER performance, which is reflected by SEM, XRD, and XPS measurements. ©

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.

In this work, the subcritical crack growth in Fe-, Ni- and Co-base hard alloys was investigated. Specimens were cyclically loaded in the pressure threshold range until a ring crack resulted as a failure criterion. Crack propagation along with the individual microstructural constituents and the associated resistance of the individual materials to crack propagation was investigated by scanning electron microscopy and by the methods adapted to it. For the Ni-base alloys, the formation of a closed ring fracture occurred after the lowest load cycle number, followed by the Co- and Fe-base alloys. Almost no crack deflection by the hard phases was detected in the Ni-base alloys. The higher number of loading cycles to produce a closed crack ring in the Fe-base alloys is attributed to the pronounced crack deflection by the hard phases and to the higher matrix strength. Besides, phase transformations were registered in front of the crack tip of the Co- and the partially austenitic Fe-base alloy. This phase transformation counteracts crack formation in the case of the Fe-base matrix but promotes crack propagation in the Co-base alloy. © 2020 The Authors. Fatigue & Fracture of Engineering Materials & Structures published by John Wiley & Sons Ltd

High-entropy alloys (HEAs) and compositionally complex alloys (CCAs) represent new classes of materials containing five or more alloying elements (concentration of each element ranging from 5 to 35 at. %). In the present study, HEAs are defined as single-phase solid solutions; CCAs contain at least two phases. The alloy concept of HEAs/CCAs is fundamentally different from most conventional alloys and promises interesting properties for industrial applications (e.g., to overcome the strength-ductility trade-off). To date, little attention has been paid to the weldability of HEAs/CCAs encompassing effects on the welding metallurgy. It remains open whether welding of HEAs/CCAs may lead to the formation of brittle intermetallics and promote elemental segregation at crystalline defects. The effect on the weld joint properties (strength, corrosion resistance) must be investigated. The weld metal and heat-affected zone in conventional alloys are characterized by non-equilibrium microstructural evolutions that most probably occur in HEAs/CCAs. The corresponding weldability has not yet been studied in detail in the literature, and the existing information is not documented in a comprehensive way. Therefore, this study summarizes the most important results on the welding of HEAs/CCAs and their weld joint properties, classified by HEA/CCA type (focused on CoCrFeMnNi and AlxCoCrCuyFeNi system) and welding process. © 2021, The Author(s).

By photodeposition of CrOxon SrTiO3-based semiconductors doped with aliovalent Mg(II) and functionalized with Ni/NiOxcatalytic nanoparticles (economically significantly more viable than commonly used Rh catalysts), an increase in apparent quantum yield (AQYs) from ∼10 to 26% in overall water splitting was obtained. More importantly, deposition of CrOxalso significantly enhances the stability of Ni/NiO nanoparticles in the production of hydrogen, allowing sustained operation, even in intermittent cycles of illumination.In situelemental analysis of the water constituents during or after photocatalysis by inductively coupled plasma mass spectrometry/optical emission spectrometry shows that after CrOxdeposition, dissolution of Ni ions from Ni/NiOx-Mg:SrTiO3is significantly suppressed, in agreement with the stabilizing effect observed, when both Mg dopant and CrOxare present. State-of-the-art electron microscopy and energy-dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS) analyses demonstrate that upon preparation, CrOxis photodeposited in the vicinity of several, but not all, Ni/NiOxparticles. This implies the formation of a Ni-Cr mixed metal oxide, which is highly effective in water reduction. Inhomogeneities in the interfacial contact, evident from differences in contact angles between Ni/NiOxparticles and the Mg:SrTiO3semiconductor, likely affect the probability of reduction of Cr(VI) species during synthesis by photodeposition, explaining the observed inhomogeneity in the spatial CrOxdistribution. Furthermore, by comparison with undoped SrTiO3, Mg-doping appears essential to provide such favorable interfacial contact and to establish the beneficial effect of CrOx. This study suggests that the performance of semiconductors can be significantly improved if inhomogeneities in interfacial contact between semiconductors and highly effective catalytic nanoparticles can be resolved by (surface) doping and improved synthesis protocols. © 2021 The Authors. Published by American Chemical Society

Abstract: The present work shows that thermal expansion experiments can be used to measure the γʼ-solvus temperatures of four Ni-base single-crystal superalloys (SX), one with Re and three Re-free variants. In the case of CMSX-4, experimental results are in good agreement with numerical thermodynamic results obtained using ThermoCalc. For three experimental Re-free alloys, the experimental and calculated results are close. Transmission electron microscopy shows that the chemical compositions of the γ- and the γʼ-phases can be reasonably well predicted. We also use resonant ultrasound spectroscopy (RUS) to show how elastic coefficients depend on chemical composition and temperature. The results are discussed in the light of previous results reported in the literature. Areas in need of further work are highlighted. Graphical abstract: [Figure not available: see fulltext.] © 2021, The Author(s).

High entropy alloys (HEAs) provide superior mechanical and functional properties. However, these advantages may disappear when a metastable single-phase solid solution decomposes at low temperatures upon long-term annealing. Therefore, understanding the underlying phase separation mechanisms is important for the design of new HEAs with controlled properties. In the current work, the thermal stability of a nanocrystalline CrMnFeCoNi HEA was investigated at different annealing conditions using a combinatorial processing platform, involving fast and parallel synthesis of nanocrystalline thin films, short annealing time for a rapid phase evolution, and direct characterization by atom probe tomography. The microstructural features of the decomposed CrMnFeCoNi alloy as well as its decomposition process were analyzed in terms of elemental distributions at the near-atomic scale. The results show that the segregation of Ni and Mn to grain boundaries in the initial single-phase alloy is a prerequisite and is observed to be the only occurring physical process at the early stage of phase decomposition. When the concentrations of Ni and Mn reach a certain value, phase decomposition starts and a MnNi-rich phase forms at grain boundaries. Next, two Cr-rich phases form at the interface between the MnNi-rich phase and the matrix. Meanwhile, a FeCo-rich phase forms in the grain interior. Based on these observations, the underlying mechanisms involving nucleation, diffusivity as well as thermodynamic considerations were discussed. © 2021 Author(s).

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).

Water electrolysis is a promising technology for sustainable hydrogen production; however, its commercialisation is limited by sluggish kinetics of the oxygen evolution reaction (OER). A potential alternative to the OER is hence required and is seen in the electrocatalytic glycerol oxidation reaction (GOR) as it offers concomitant value-added product generation from a cheap and abundant feedstock. Here, we show a facile solid-state synthesis method to obtain Ni-boride, a non-noble metal-based catalyst subsequently used in an in-depth study of the GOR product distribution as a function of key electrolysis parameters. Highly crystalline, mixed-phase Ni borides were obtained, and their synthesis was successfully optimised regarding GOR activity. Long-term chronoamperometry was conducted in a circular flow-through cell and samples were analysed by HPLC. It is shown that the formation of lactic acid, one of the most valuable GOR products, can be enhanced by optimising the electrolyte composition and the applied potential. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH

A dislocation network which formed during selective laser melting (SLM) of a Ni-base superalloy was analyzed using scanning transmission electron microscopy (STEM). This network traverses an ordered Gamma'-phase domain, in between two adjacent Gamma-solid solution regions. The Gamma’-phase region has formed when two Gamma’-phase particles have started to coalesce, trapping the dislocation network in this ordered region so that it formed two dislocation families with pairs of anti-phase boundary (APB) coupled super partial dislocations. The network features are presented and unusual features (twist character and low APB energies), not previously reported, are discussed. © 2020

NaNbO3 enriched with oxygen vacancies by Ni doping was successfully synthesized via a polymerized complex method and applied as a photocatalyst in the oxidation of cinnamyl alcohol (CA) to cinnamaldehyde in air. Reaction rates as high as 45 μmol h-1 were achieved under visible light with a high apparent quantum efficiency of 67.2% and excellent chemoselectivity larger than 99%. UV-vis, electron paramagnetic resonance, and attenuated total reflectance infrared spectroscopy results indicate that the CA molecules preferentially adsorb at the oxygen vacancies, thus enabling electron transfer between coordinatively bound CA and NaNbO3 under visible light, inducing CA oxidation. The photocatalytic aerobic oxidation of CA is assumed to proceed via the one-photon pathway with H2O2 as the coupled product. The photodeposited Pt nanoparticles on the surface not only enhanced the oxidation rate but also improved the selectivity to cinnamaldehyde substantially because of the fast decomposition of formed H2O2, in this way avoiding its consecutive oxidation by H2O2. The oxygen vacancies on the surface generated by Ni doping are identified to play a decisive role in the chemisorption of cinnamyl alcohol and the interface charge transfer. © 2021 American Chemical Society. All rights reserved.

The service performance of the turbine blade root of an aero-engine depends on the microstructures in its superficial layer. This work investigated the surface deformation structures of turbine blade root of single crystal nickel-based superalloy produced under different creep feed grinding conditions. Gradient microstructures in the superficial layer were clarified and composed of a severely deformed layer (DFL) with nano-sized grains (48-67 nm) at the topmost surface, a DFL with submicron-sized grains (66-158 nm) and micron-sized laminated structures at the subsurface, and a dislocation accumulated layer extending to the bulk material. The formation of such gradient microstructures was found to be related to the graded variations in the plastic strain and strain rate induced in the creep feed grinding process, which were as high as 6.67 and 8.17 × 107 s-1, respectively. In the current study, the evolution of surface gradient microstructures was essentially a transition process from a coarse single crystal to nano-sized grains and, simultaneously, from one orientation of a single crystal to random orientations of polycrystals, during which the dislocation slips dominated the creep feed grinding induced microstructure deformation of single crystal nickel-based superalloy. © 2021 IOP Publishing Ltd.

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.

Advanced methods for the repair of single-crystalline (SX) Ni-based superalloys are of special interest for the gas turbine industry. Polycrystalline repair approaches show promising results, while the repair of SX materials is still challenging. Directional annealing experiments resulted in large columnar grains by imposing thermal gradients at the abnormal grain growth temperature of a specific Ni-based superalloy. A numerical model of the Bridgman process is applied to provide an insight into the temperature evolution during zone annealing of the Vacuum-Plasma-Spray (VPS) repair coatings with the aim of promoting grain growth from the SX substrate. The results presented here suggest that this is a promising approach to repair or manufacture SX turbine blades. © 2020 Elsevier B.V.

It is widely accepted that the different types of crystalline imperfections, such as vacancies or dislocations, greatly influence a material's physical and mechanical properties. However, imaging individual vacancies in solids and revealing their atomic neighborhood remains one of the frontiers of microscopy and microanalysis. Here, we study a creep-deformed binary Ni-2 at.% Ta alloy. Atom probe tomography reveals a random distribution of Ta. Field ion microscopy, with contrast interpretation supported by density-functional theory and time-of-flight mass spectrometry, evidences a positive correlation of Ta with vacancies, supporting positive solute-vacancy interactions previously predicted by atomistic simulations. © 2021

We have investigated the partitioning of solutes at crystal defects in intergranular Cr-rich M2B borides after creep at 850°C/185MPa and annealing at 850°C for approximately 3000 h in a polycrystalline nickel-based superalloy. Borides were found to coarsen in both cases, with the borides after creep being the thickest (800–1100 nm), compared to borides annealed in the absence of an external applied load (400–600 nm). Transmission electron microscopy revealed that the coarsened borides have either a tetragonal I4/mcm structure, or an orthorhombic Fddd, with those two structures coexisting in a single particle. The presence of a very high density of planar faults was systematically observed within the coarsened borides. The faults were correlated with chemical fluctuations of B and Cr, revealed by atom probe tomography. In addition, partitioning of Ni and Co was observed at dislocations within the borides after creep, providing insights into the deformation of borides. © 2021, The Minerals, Metals & Materials Society.

The electrochemical CO2 reduction (CO2R) is a promising approach to decrease the amount of CO2 in the atmosphere by producing commodity chemicals or fuels using renewable energies. Herein, the development of non-noble metal electrocatalysts is regarded as a key point for achieving the transition of CO2R to industrial scales. Transition metal chalcogenides of the pentlandite structure (M9X8) have emerged as promising electrocatalysts to produce syngas. In this line, we present the electrochemical CO2R of FexNi9-xS8 (x=3–6) with variable Fe : Ni ratios. All materials can reduce H2O/CO2 mixtures to CO or H2 respectively with varying efficiency depending on the Fe : Ni ratio and the water content. While CO2R in proton-rich organic electrolytes was mainly accompanied by hydrogen evolution, the CO2R activity climaxed with F.E. of 3.6 % for CO and 0.3 % for methane using Fe3Ni6S8. Using electrolytes with low water content, CO production with F.E. close to 90 % was demonstrated. Counterintuitively, the variation of the Fe : Ni ratio led only to small alterations in the CO2R activity. Quantum mechanical studies were performed to get further information on the observed trends and provide further insight into structure/activity relationships for the Fe/Ni pentlandite system and its CO2R activity opening the path towards the development of more active and robust CO2R electrocatalysts. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH

A new wrought CrCoNi-based medium-entropy superalloy (MESA) was designed by changing the composition of a commercial superalloy of type C-263, which is used for stationary components in gas turbines. ∼5 at.% Cr and 0.85 at.% Ti + Al were added at the expense of Ni while the Ti/Al ratio was decreased. Owing to these modifications, the brittle η phase, which is stable in C-263 below 900 °C is no longer observed in C-264. Besides, the solvus temperature and volume fraction of the γ′ phase in the peak-aged state are larger in C-264 (∼935 °C, 13.5%) compared to C-263 (∼890 °C, 12.8%), resulting in superior tensile and creep properties. The stress and temperature dependencies of the creep rates were described by power-law and Arrhenius relationships. The stress exponents were between 4 and 5, while the apparent activation energies were 550 and 400 kJ/mol for C-264 and C-263, respectively. During creep at 880 °C in air, internal nitridation in both MESAs resulted in the formation of TiN precipitates, with C-264 being slightly more affected due to its higher nitrogen solubility. Due to its superior creep resistance, good malleability and machinability, the C-264 MESA is currently commercially available from VDM Metals International. © 2021 The Authors

The γ′ volume fraction is a key parameter in precipitation-strengthened Co- and Ni-base superalloys and mainly determines the alloys’ properties. However, systematic studies with varying γ′ volume fractions are rare and the influence on thermal expansion has not been studied in detail. Therefore, a series of six Ta-containing Co-based alloys was designed with compositions on a γ–γ′ tie-line, where the γ′ volume fraction changes systematically. During solidification, Laves (C14-type) and µ (D85-type) phases formed in alloys with high levels of W and Ta. Single-phase γ or two-phase γ/γ′ microstructures were obtained in four experimental alloys after heat treatment as designed, whereas secondary precipitates, such as χ (D019-type), Laves, and μ, existed in alloys containing high levels of γ′-forming elements. However, long-term heat treatments for 1000 hours revealed the formation of the χ phase also in the former χ-free alloys. The investigation of the thermal expansion behavior revealed a significant anomaly related to the dissolution of γ′, which can be used to determine the γ′ solvus temperature with high accuracy. Compared to thermodynamic calculations, differential scanning calorimetry (DSC) and thermal expansion analysis revealed a larger increase of the γ′ solvus temperatures and a lesser decline of the solidus temperatures when the alloy composition approached the composition of the pure γ′ phase. © 2021, The Author(s).

Gas turbine components are often operated in harsh conditions, which can lead to severe damage. As it is highly desirable from both an economical and an ecological point of view to restore these worn areas instead of manufacturing new components, repair technologies are of huge interest for companies supplying maintenance and overhaul of gas turbines. In this article, two thermal techniques are described that can be used for this application: cold gas spraying (CGS) and vacuum plasma spraying (VPS). The CGS process allows the deposition of metallic coatings with excellent mechanical properties; several examples including γ-TiAl, Inconel (IN) 718, and IN 738 are given. Essential for the deposition of high-performance coatings in CGS is to exceed the so-called critical velocity. This is discussed also with experimental findings. As a final topic, experiments that use VPS for the repair of single-crystal alloys are described. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The electrochemical reduction of CO2 is an attractive strategy towards the mitigation of environmental pollution and production of bulk chemicals as well as fuels by renewables. The bimetallic sulfide Fe4.5Ni4.5S8 (pentlandite) was recently reported as a cheap and robust catalyst for electrochemical water splitting, as well as for CO2 reduction with a solvent-dependent product selectivity. Inspired by numerous reports on monometallic sulfoselenides and selenides revealing higher catalytic activity for the CO2 reduction reaction (CO2RR) than their sulfide counterparts, the authors investigated the influence of stepwise S/Se exchange in seleno-pentlandites Fe4.5Ni4.5S8-YSeY (Y=1–5) and their ability to act as CO2 reducing catalysts. It is demonstrated that the incorporation of higher equivalents of selenium favors the CO2RR with Fe4.5Ni4.5S4Se4 revealing the highest activity for CO formation. Under galvanostatic conditions in acetonitrile, Fe4.5Ni4.5S4Se4 generates CO with a Faradaic Efficiency close to 100 % at applied current densities of −50 mA cm−2 and −100 mA cm−2. This work offers insight into the tunability of the pentlandite based electrocatalysts for the CO2 reduction reaction. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Grain boundary (GB) segregation has a substantial effect on the microstructure evolution and properties of polycrystalline alloys. The mechanism of nanoscale segregation at the various GBs in multicomponent alloys is of great challenge to reveal and remains elusive so far. To address this issue, we studied the GB segregation in a representative equiatomic FeMnNiCoCr high-entropy alloy (HEA) aged at 450 °C. By combining transmission Kikuchi diffraction, atom probe tomography analysis and a density-based thermodynamics modeling, we uncover the nanoscale segregation behavior at a series of well-characterized GBs of different characters. No segregation occurs at coherent twin boundaries; only slight nanoscale segregation of Ni takes place at the low-angle GBs and vicinal ς29b coincidence site lattice GBs. Ni and Mn show cosegregation of high levels at the general high-angle GBs with a strong depletion in Fe, Cr, and Co. Our density-based thermodynamic model reveals that the highly negative energy of mixing Ni and Mn is the main driving force for nanoscale cosegregation to the GBs. This is further assisted by the opposite segregation of Ni and Cr atoms with a positive enthalpy of mixing. It is also found that GBs of higher interfacial energy, possessing lower atomic densities (higher disorder and free volume), show higher segregation levels. By clarifying the origins of GB segregations in the FeMnNiCoCr HEA, the current work provides fundamental ideas on nanoscale segregation at crystal defects in multicomponent alloys. © 2020 authors.

Strong and ductile materials that have high resistance to corrosion and hydrogen embrittlement are rare and yet essential for realizing safety-critical energy infrastructures, hydrogen-based industries, and transportation solutions. Here we report how we reconcile these constraints in the form of a strong and ductile CoNiV medium-entropy alloy with face-centered cubic structure. It shows high resistance to hydrogen embrittlement at ambient temperature at a strain rate of 10−4 s−1, due to its low hydrogen diffusivity and the deformation twinning that impedes crack propagation. Moreover, a dense oxide film formed on the alloy’s surface reduces the hydrogen uptake rate, and provides high corrosion resistance in dilute sulfuric acid with a corrosion current density below 7 μA cm−2. The combination of load carrying capacity and resistance to harsh environmental conditions may qualify this multi-component alloy as a potential candidate material for sustainable and safe infrastructures and devices. © 2020, The Author(s).

The present work contributes to a better understanding of the basic assumptions and principles behind the design of Ni-based single crystal superalloys (SXs). For this purpose, we cast and heat-treat four Ni-based single crystal superalloys (SXs) and compare their creep performances: ERBO/1 (with Re) and three ERBO/15 variants (no Re but increased levels of Ti, Mo and W). We show that Re can be replaced by other elements without losing creep strength. To come to this conclusion one has to consider both, alloy composition and microstructure. We analyze the mechanical, microstructural and chemical results (creep rates, γʼ-volume fractions, average γʼ-particle sizes, average γ-channel widths and the chemistry of γ- and γʼ-phases) obtained for ERBO/15 and its two leaner variants (less Mo: ERBO/15-Mo and less W: ERBO/15-W). ERBO/15-Mo and ERBO/15-W show higher creep rates than ERBO/15, because they exhibit lower Mo and W concentrations in the γ-channels. This results in higher diffusion rates, accelerated rafting and faster dislocation climb at γ/γʼ-interfaces. © 2020 The Authors

The evolution of dislocation density with creep strain in single-crystal superalloys is studied quantitatively using high-resolution electron backscatter diffraction (HR-EBSD) and electron channelling contrast imaging under controlled diffraction conditions (cECCI). Data regarding dislocation density/structure is measured for deformation at 900 °C and 450 MPa up to ≈ 1% plastic strain. Effects of chemical composition are elucidated via three purpose-designed superalloys of differing rhenium and ruthenium contents. The evidence indicates that dislocation avalanching is already prevalent at plastic strains of ≈ 0.1%; thereafter, an exponential decay in the dislocation multiplication rate is indicative of self-hardening due to dislocation constriction within the matrix channels, as confirmed by the imaging. The results are rationalised using discrete dislocation dynamics modelling: a universal dislocation evolution law emerges, which will be useful for alloy design efforts. © 2019

Several H−H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2. Understanding HER processes, especially controllable switching between homolytic and heterolytic H−H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis. © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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.

Intensive research is being conducted into highly efficient and cheap nanoscale materials for the electrocatalytic oxidation of water. In this context, we built heterostructures of multilayered CoNi-cyanide bridged coordination (CoNi-CP) nanosheets and graphene oxide (GO) sheets (CoNi-CP/GO) as a source for heterostructured functional electrodes. The layered CoNi-CP/GO hybrid components heated in nitrogen gas (N2) at 450 °C yield CoNi-based carbide (CoNi-C) through thermal decomposition of CoNi-CP, while GO is converted into reduced GO (rGO) to finally form a CoNi-C/rGO-450 composite. The CoNi-C/rGO-450 composite shows a reasonable efficiency for oxygen evolution reaction (OER) through water oxidations in alkaline solution. Meanwhile, regulated annealing of CoNi-CP/GO in N2 with thiourea at 450 and 550 °C produces CoNi-based sulfide (CoNi-S) rather than CoNi-C between rGO sheets co-doped by nitrogen (N) and sulfur (S) heteroatoms (NS-rGO) to form CoNi-S/NS-rGO-450 and CoNi-S/NS-rGO-550 composites, respectively. The CoNi-S/NS-rGO-550 shows the best efficiency for electrocatalytic OER among all electrodes with an overpotential of 290 mV at 10 mA cm-2 and a Tafel slope of 79.5 mV dec-1. By applying the iR compensation to remove resistance of the solution (2.1 ω), the performance is further improved to achieve a current density of 10 mA cm-2 at an overpotential of 274 mV with a Tafel slope of 70.5 mV dec-1. This result is expected to be a promising electrocatalyst compared to the currently used electrocatalysts and a step for fuel cell applications in the future. © 2020 American Chemical Society.

Based on our recently-developed combinatorial processing platforms for accelerated investigations of phase evolution in multinary alloys, a novel correlative atom probe tomography and transmission electron microscopy approach is proposed to study phase stability in a nanocrystalline CrMnFeCoNi alloy. We observed that the material can decompose at 250 °C for 5 h or 300 °C for 1 h, having the same decomposed products as in its coarse-grained counterpart after annealing at 500 °C for 500 days. A low apparent activation energy for the diffusion of Ni in the nanocrystalline alloy is derived and explains the fast kinetics of phase decomposition in nanocrystalline alloys. © 2020 Acta Materialia Inc.

The equiatomic CrCoNi alloy is regarded as a model single-phase face-centered cubic medium-entropy alloy. A CrCoNi single crystal was grown by a Bridgman technique using a Ni-base superalloy seed. The elastic stiffnesses and thermal expansion coefficient were determined between 100 K and 673 K employing resonant ultrasound spectroscopy and dilatometry, respectively. All data were found to be in excellent agreement with those reported for polycrystalline CrCoNi. A comparison of the normalized Cauchy pressure of CrCoNi with those of other alloys indicates that interatomic bonds become more directional with increasing Cr-concentration while Co and Ni promote a metallic character. © 2019 Acta Materialia Inc.

In the present study, X-ray diffraction was applied to measure stacking fault energy of Cr–Ni austenitic steels containing different amounts of alloying elements. The results in austenitic steels show that the Ni content and Cr/Ni ratio have a strong effect on SFE. Cu, Si and N increase SFE, being the effect of nitrogen more pronounced; Mo has the opposite effect. In situ XRD experiments up to 300 °C were employed to determine experimentally the SFE and its temperature dependence in Ni and AISI 304. The microstructural parameters required to determine SFE, obtained by Rietveld refinement, made possible to determine experimentally an increase in the SFE with the temperature, related to a decrease in the accumulated deformation, a lower tendency to form stacking faults and a thermal expansion as the temperature increases. The accuracy was determined based on SFE measurements of Au, Cu and Ni pure metals, where the error of the applied method was carefully evaluated. © 2020, Springer Science+Business Media, LLC, part of Springer Nature.

NiyP emerged as a highly active precatalyst for the alkaline oxygen evolution reaction where structural changes play a crucial role for its catalytic performance. We probed the chemical stability of NiyP in 1 M KOH at 80 °C and examined how exposure up to 168 h affects its structure and catalytic performance. We observed selective P-leaching and formation of NiyP/NiOx core-shell heterostructures, where shell thickness increases with ageing time, which is detrimental for the activity. By tuning the particle size, we demonstrate that prevention of complete catalyst oxidation is essential to preserve the outstanding electrochemical performance of NiyP in alkaline media. © 2020 American Chemical Society.

Ni-base single-crystal superalloys exhibit a dynamic evolution of their microstructure during operation at elevated temperatures. The rafting of γ′ precipitates changes the mechanical behavior in a way that was understood insufficiently. In this work, we combine a phase-field method with a discrete dislocation dynamics model to clarify the influence of different rafted microstructures with the same initial dislocation density and configuration on creep behavior. The unrafted and rafted microstructures of Ni-base single crystal superalloys are simulated by a phase-field crystal plasticity method. By introducing these microstructures into a 3D discrete dislocation dynamics (DDD) model, the creep behavior under uniaxial loads of 350 and 250 MPa along [100] direction at 950 °C is studied. Due to the negative lattice mismatch of Ni-base superalloys, the N-type rafting with the formation of plate-like γ′ precipitates occurs under uniaxial tensile loads along {100} direction at high temperatures, while the P-type rafting with the formation of rod-like γ′ precipitates occurs under compressive loads. Taking the cuboidal, N-type rafted and P-type rafted microstructures as the initial and fixed microstructures for the same loading conditions, it is found from DDD simulations that the rafted microstructures result in smaller creep deformation than the cuboidal microstructure. The reason for this is that the coalescence of γ′ precipitates during the rafting diminishes the width of some γ channels, so as to increase the local Orowan stresses which retard the dislocation glide. For tensile loads, the N-type rafted microstructure has the best creep resistance. For a low compressive load, the P-type rafting shows a better creep resistance than N-type rafting. © 2019 IOP Publishing Ltd.

Phase stability of a nanocrystalline CrCoNi alloy is investigated using the combinatorial processing platform approach, which enables synthesis, processing and direct atomic-scale characterizations of alloys by atom probe tomography and transmission electron microscopy. Phase decomposition with formation of CoNi-rich phase occurs faster in the smaller (10 nm) grain-sized region than the larger one (20 nm), both being present in the same sample. Chemical analyses indicate that diffusion of Co and Cr plays an important role in phase decomposition. Comparison of phase stability between CrMnFeCoNi and CrCoNi implies that elemental segregation may promote phase decomposition by providing an additional chemical driving force for it. © 2020 Acta Materialia Inc.

In the present work, we investigate the stress and temperature dependence of low-temperature (750 ± 20 °C) and high-stress (300 ± 20 MPa) shear creep of a Ni-base single crystal superalloy. From continuous isothermal experiments and stress and temperature change tests the stress exponent n and the apparent activation energy Qapp of the phenomenological Sherby-Dorn equation were determined for the two macroscopic crystallographic shear systems (MCSS) [011¯](111) and [112¯](111). The activation parameters of creep, the stress exponents and the apparent activation energies were identified as 16 and 620 kJ/mol (MCSS: [011¯](111)) and 14 and 460 kJ/mol (MCSS: [112¯](111)). We show that during shear creep testing these phenomenological parameters do not change between the early (0.5–1% strain) and later stages of creep (4.5–5% strain), in contrast to what was observed for uniaxial tensile testing. The results are discussed in the light of what is known about stress and temperature dependencies of deformation rates in the creep literature and in view of the recent work by Bürger et al., 2020, who combined shear creep testing with analytical transmission electron microscopy to identify the elementary deformation mechanism, which governs low temperature and high stress creep. © 2020 The Authors

Complex solid solution electrocatalysts (often called high-entropy alloys) present a new catalyst class with highly promising features due to the interplay of multi-element active sites. One hurdle is the limited knowledge about structure-activity correlations needed for targeted catalyst design. We prepared Cr-Mn-Fe-Co-Ni nanoparticles by magnetron sputtering a high entropy Cantor alloy target simultaneously into an ionic liquid library. The synthesized nanoparticles have a narrow size distribution but different sizes (from 1.3 ± 0.1 nm up to 2.6 ± 0.3 nm), different crystallinity (amorphous, face-centered cubic or body-centered cubic) and composition (i.e. high Mn versus low Mn content). The Cr-Mn-Fe-Co-Ni complex solid solution nanoparticles possess an unprecedented intrinsic electrocatalytic activity for the oxygen reduction reaction in alkaline media, some of them even surpassing that of Pt. The highest intrinsic activity was obtained for body-centered cubic nanoparticles with a low Mn and Fe content which were synthesized using the ionic liquid 1-etyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Emimi][(Tf)2N]. This journal is © The Royal Society of Chemistry.

Carbon is a frequently used electrode material and an important additive in catalyst films. Its corrosion is often reported during electrocatalysis at high anodic potentials, especially in acidic electrolyte. Investigation of the carbon corrosion in alkaline environment is difficult due to the CO2/CO32− equilibrium. We report the on-line determination of electrolysis products generated on NixB/C hybrid electrocatalysts in alkaline electrolyte at anodic potentials using differential electrochemical mass spectrometry (DEMS). NixB/C catalyst films were obtained from mixtures containing different ratios of NiXB and benzoxazine monomers followed by polymerization and pyrolysis. The impact of the composition of the electrocatalyst on the dominant electrolysis process allows to distinguish between the oxygen evolution reaction and carbon corrosion using DEMS results as well as the catalyst surface composition evaluated from X-ray photoelectron spectra. At the imposed highly oxidative conditions, an increasing amount of NixB in the electrocatalyst leads to a suppression of carbon corrosion. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

The role of coherency loss on rafting of superalloys under high temperature low stress creep conditions is investigated by phase-field crystal plasticity simulations. It is demonstrated that coalescence, critically depending on the state of coherency between precipitate and matrix is crucial to understand the rafting behavior of superalloys. An explicit mechanisms is developed predicting coherency loss based on the plastic activity in the matrix. The simulations are verified using experimental creep test results. © 2019 Elsevier B.V.

Laser additive manufacturing is attractive for the production of complex, three-dimensional parts from metallic powder using a computer-aided design model1–3. The approach enables the digital control of the processing parameters and thus the resulting alloy’s microstructure, for example, by using high cooling rates and cyclic re-heating4–10. We recently showed that this cyclic re-heating, the so-called intrinsic heat treatment, can trigger nickel-aluminium precipitation in an iron–nickel–aluminium alloy in situ during laser additive manufacturing9. Here we report a Fe19Ni5Ti (weight per cent) steel tailor-designed for laser additive manufacturing. This steel is hardened in situ by nickel-titanium nanoprecipitation, and martensite is also formed in situ, starting at a readily accessible temperature of 200 degrees Celsius. Local control of both the nanoprecipitation and the martensitic transformation during the fabrication leads to complex microstructure hierarchies across multiple length scales, from approximately 100-micrometre-thick layers down to nanoscale precipitates. Inspired by ancient Damascus steels11–14—which have hard and soft layers, originally introduced via the folding and forging techniques of skilled blacksmiths—we produced a material consisting of alternating soft and hard layers. Our material has a tensile strength of 1,300 megapascals and 10 per cent elongation, showing superior mechanical properties to those of ancient Damascus steel12. The principles of in situ precipitation strengthening and local microstructure control used here can be applied to a wide range of precipitation-hardened alloys and different additive manufacturing processes. © 2020, The Author(s), under exclusive licence to Springer Nature Limited.

Mo-doped BiVO4 has emerged as a promising material for photoelectrodes for photoelectrochemical water splitting, however, still shows a limited efficiency for light-driven water oxidation. We present the influence of an oxygen-evolution catalyst composed of Ni, Fe, and Cr oxides on the activity of Mo:BiVO4 photoanodes. The photoanodes are prepared by spray-coating, enabling compositional and thickness gradients of the incorporated catalyst. Two different configurations are evaluated, namely with the catalyst embedded into the Mo:BiVO4 film or deposited on top of it. Both configurations provide a significantly different impact on the photoelectrocatalytic efficiency. Structural characterisation of the materials by means of SEM, TEM and XRD as well as the photoelectrocatalytic activity investigated by means of an optical scanning droplet cell and in situ detection of oxygen using scanning photoelectrochemical microscopy are presented. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Industrial scale single crystal (SX) Ni-base superalloys contain numerous low angle grain boundaries inherited from the solidification process. Here, we demonstrate that low angle grain boundaries in a fully heat-treated SX model Ni-base superalloy are strongly segregated with up to 12 at% Re. Some Re-rich dislocations forming this grain boundary are found located inside γ, others close to a γ/γ′ interface. Although these segregated Re atoms lose their solid-solution strengthening effect, they may enhance the creep resistance by pinning the low angle grain boundaries and slowing down dislocation reactions. © 2020 Acta Materialia Inc.

Nickel-based nanostructured materials have gained widespread attention, particularly for energy-related applications. Employing chemical vapor deposition (CVD) for NiO necessitates suitable nickel precursors that are volatile and stable. Herein, we report the synthesis and characterization of a series of new nickel β-ketoiminato complexes with different aliphatic and etheric side chain substitutions, namely, bis(4-(isopropylamino)-pent-3-en-2-onato)nickel(II) ([Ni(ipki)2], 1), bis(4-(2-methoxyethylamino)pent-3-en-2-onato)nickel(II) ([Ni(meki)2], 2), bis(4-(2-ethoxyethylamino)pent-3-en-2-onato)nickel(II) ([Ni(eeki)2], 3), bis(4-(3-methoxy-propylamino)-pent-3-en-2-onato)nickel(II) ([Ni(mpki)2], 4), and bis(4-(3-ethoxypropylamino)pent-3-en-2-onato)nickel(II) ([Ni(epki)2], 5). These compounds have been thoroughly characterized with regard to their purity and identity by means of nuclear magnetic resonance spectroscopy (NMR) and electron impact mass spectrometry (EI-MS). Contrary to other transition metal β-ketoiminates, the imino side chain strongly influences the structural geometry of the complexes, which was ascertained via single-crystal X-ray diffraction (XRD). As a result, the magnetic momenta of the molecules also differ significantly as evidenced by the magnetic susceptibility measurements employing Evan's NMR method in solution. Thermal analysis revealed the suitability of these compounds as new class of precursors for CVD of Ni containing materials. As a representative precursor, compound 2 was evaluated for the CVD of NiO thin films on Si(100) and conductive glass substrates. The as-deposited nanostructured layers were stoichiometric and phase pure NiO as confirmed by XRD, Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA). X-ray photoelectron spectroscopy (XPS) indicated the formation of slightly oxygen-rich surfaces. The assessment of NiO films in electrocatalysis revealed promising activity for the oxygen evolution reactions (OER). The current densities of 10 mA cm-2 achieved at overpotentials ranging between 0.48 and 0.52 V highlight the suitability of the new Ni complexes in CVD processes for the fabrication of thin film electrocatalysts. Copyright © 2020 American Chemical Society.

45° rafting of Ni-based superalloys has been investigated with the help of creep test simulations applying a strain gradient crystal plasticity model coupled to the multi-phase field method. This mode of rafting lies in between P- A nd N-type rafting modes. The model parameters are calibrated against experimental data for N-type rafting under high temperature and low stress creep condition. By increasing the stress level, the mixed-mode rafting of precipitates with a clear tendency toward formation of 45° rafts is observed. We show that the key factor for the occurrence of this type of rafting is the generation of highly localized creep strain of more than 10% due to non-homogeneous creep deformation in the form of slip bands. We have successfully captured the evolution of microstructure under high stress leading to production of localized shear bands. © 2020 Elsevier Ltd.

Aiming to devise suitable materials for sliding wear protection at high temperature, aluminium oxide-dispersion strengthened (ODS) CoNiCrAlY coatings were manufactured by vacuum plasma spraying (VPS). Feedstock materials were ball-milled powders with 2, 10 and 30 wt% Al2O3 content. The ball-on-disc sliding wear behaviour of the coatings was tested at 750 °C against an Al2O3 counterpart, and compared to a pure CoNiCrAlY coating (obtained from a commercial feedstock not subjected to ball milling) and to an uncoated Ni-base superalloy. Sliding wear rates decrease from the uncoated superalloy (≈3 × 10−5 mm3/(N·m)) to the pure CoNiCrAlY coating (≈2 × 10−5 mm3/(N·m)) and to the ODS ones, with the notable exception of the 10 wt% Al2O3-containing sample. Analyses of worn samples indicate that pure CoNiCrAlY is subject to severe adhesive wear, mitigated by the formation of a thick (>1 μm) “glaze” layer via compaction and (probable) sintering of tribo-oxidized debris particles. Addition of Al2O3 particles to the CoNiCrAlY matrix can either enhance or worsen the “glaze” stability. Specifically, a coating strengthened with 30 wt% Al2O3 provides an especially good mechanical support to the “glaze”. This produces beneficial effects resulting in a particularly low wear rate of ≈3 × 10−6 mm3/(N·m). © 2019 Elsevier B.V.

Contemporary powder-based polycrystalline nickel-base superalloys inherit microstructures and properties that are heavily determined by their thermo-mechanical treatments during processing. Here, the influence of a thermal exposure to an alloy powder is studied to elucidate the controlling formation mechanisms of the strengthening precipitates using a combination of atom probe tomography and in-situ neutron diffraction. The initial powder comprised a single-phase supersaturated γ only; from this, the evolution of γ′ volume fraction and lattice misfit was assessed. The initial powder notably possessed elemental segregation of Cr and Co and elemental repulsion between Ni, Al and Ti with Cr; here proposed to be a precursor for subsequent γ to γ′ phase transformations. Subsolvus heat treatments yielded a unimodal γ′ distribution, formed during heating, with evidence supporting its formation to be via spinodal decomposition. A supersolvus heat treatment led to the formation of this same γ′ population during heating, but dissolves as the temperature increases further. The γ′ then reprecipitates as a multimodal population during cooling, here forming by classical nucleation and growth. Atom probe characterisation provided intriguing precipitate characteristics, including clear differences in chemistry and microstructure, depending on whether the γ′ formed during heating or cooling. © 2020 Acta Materialia Inc.

CrCoNi-based high-entropy alloys have demonstrated outstanding mechanical properties, particularly at cryogenic temperatures. Here we investigate the fatigue-crack propagation properties of the equiatomic, single-phase, face-centered cubic, medium-entropy alloy (MEA), CrCoNi, that displays exceptional strength, ductility and toughness, all of which are enhanced at cryogenic temperatures. Fatigue-crack growth is examined, at a load ratio of 0.1 over a wide range of growth rates, from ~10−11 to >10−7 m/cycle, at room (293 K) and cryogenic (198 K, 77 K) temperatures for two grain sizes (~7 and 68 µm), with emphasis on near-threshold behavior. We find that the ΔKth fatigue thresholds are increased with decreasing temperature and increasing grain size: from 5.7 MPa√m at 293 K to 8 MPa√m at 77 K in the fine-grained alloy, and from 9.4 MPa√m at 293 K to 13.7 MPa√m at 77 K in the coarse-grained alloy. Mechanistically, transgranular cracking at 293 K transitions to a mixture of intergranular and transgranular at cryogenic temperatures, where the increased propensity of nano-twins appears to inhibit growth rates by deflecting the crack path. However, the main factor affecting near-threshold behavior is roughness-induced crack closure from interference between the crack flanks, which is enhanced by the rougher fracture surfaces at low temperatures, particularly in the coarser-grained microstructure. Fatigue-crack propagation behavior in CrCoNi is comparable to nickel-based superalloys but is superior to that of the high-entropy CrMnFeCoNi (Cantor) alloy and many high-strength steels, making the CrCoNi alloy an excellent candidate material for safety-critical applications, particularly involving low temperatures. © 2020

Machine learning of the quantitative relationship between local environment descriptors and the potential energy surface of a system of atoms has emerged as a new frontier in the development of interatomic potentials (IAPs). Here, we present a comprehensive evaluation of machine learning IAPs (ML-IAPs) based on four local environment descriptors - atom-centered symmetry functions (ACSF), smooth overlap of atomic positions (SOAP), the spectral neighbor analysis potential (SNAP) bispectrum components, and moment tensors - using a diverse data set generated using high-throughput density functional theory (DFT) calculations. The data set comprising bcc (Li, Mo) and fcc (Cu, Ni) metals and diamond group IV semiconductors (Si, Ge) is chosen to span a range of crystal structures and bonding. All descriptors studied show excellent performance in predicting energies and forces far surpassing that of classical IAPs, as well as predicting properties such as elastic constants and phonon dispersion curves. We observe a general trade-off between accuracy and the degrees of freedom of each model and, consequently, computational cost. We will discuss these trade-offs in the context of model selection for molecular dynamics and other applications. © 2020 American Chemical Society.

Diffusion in multi-component alloys is attracting renewed attention because of the worldwide interest in high- and medium-entropy alloys (HEAs/MEAs). In the present work, we used diffusion multiples made from MEAs of the quaternary Cr–Fe–Co–Ni system arranged as six distinct pseudo-binary diffusion couples (Cr29Fe13Co29Ni29–Cr29Fe29Co29Ni13, Cr29Fe29Co13Ni29–Cr29Fe29Co29Ni13, and so on, where the interdiffusing elements are italicized for clarity). In the two halves of each couple, the starting concentrations of the interdiffusing elements (Fe,Ni and Co,Ni in the above examples) were different while those of the background elements (Cr,Co and Cr,Fe in the above examples) were the same. The diffusion multiples were annealed at temperatures between 1153 and 1355 K at times from 100 to 900 h, after which the concentrations of the different elements were measured as a function of distance across each couple. Interdiffusion coefficients were derived from such concentration profiles using the standard Sauer-Freise method and compared with literature data as well as with published tracer diffusion coefficients. Although the background elements were homogeneously distributed initially, some of them developed distinct sine-wave shaped concentration gradients near the interfaces after annealing, implying that uphill diffusion of these elements had occurred. We show using a kinetic model for substitutional diffusion via vacancy hopping that such uphill diffusion can occur even in the absence of thermodynamic interactions, i.e. in ideal solid solutions in which the thermodynamic factor Φ of each element is equal to one (Φi=1+∂lnfi/∂lnci where fi and ci are the activity coefficient and mole fraction of element i, respectively). The model accounts for all elemental fluxes and also rationalizes the diffusion profiles of the major interdiffusing elements. © 2020

A universal nano-capillary based method for sample deposition on the silicon nitride membrane of liquid-cell transmission electron microscopy (LCTEM) chips is demonstrated. It is applicable to all substances which can be dispersed in a solvent and are suitable for drop casting, including catalysts, biological samples, and polymers. Most importantly, this method overcomes limitations concerning sample immobilization due to the fragility of the ultra-thin silicon nitride membrane required for electron transmission. Thus, a straightforward way is presented to widen the research area of LCTEM to encompass any sample which can be externally deposited beforehand. Using this method, NixB nanoparticles are deposited on the μm-scale working electrode of the LCTEM chip and in situ observation of single catalyst particles during ethanol oxidation is for the first time successfully monitored by means of TEM movies. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Controlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic-core hexagonal-branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF), as an example for biomass conversion. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA

Discovering precious metal-free electrocatalysts exhibiting high activity and stability toward both the oxygen reduction (ORR) and the oxygen evolution (OER) reactions remains one of the main challenges for the development of reversible oxygen electrodes in rechargeable metal–air batteries and reversible electrolyzer/fuel cell systems. Herein, a highly active OER catalyst, Fe0.3Ni0.7OX supported on oxygen-functionalized multi-walled carbon nanotubes, is substantially activated into a bifunctional ORR/OER catalyst by means of additional incorporation of MnOX. The carbon nanotube-supported trimetallic (Mn-Ni-Fe) oxide catalyst achieves remarkably low ORR and OER overpotentials with a low reversible ORR/OER overvoltage of only 0.73 V, as well as selective reduction of O2 predominantly to OH−. It is shown by means of rotating disk electrode and rotating ring disk electrode voltammetry that the combination of earth-abundant transition metal oxides leads to strong synergistic interactions modulating catalytic activity. The applicability of the prepared catalyst for reversible ORR/OER electrocatalysis is evaluated by means of a four-electrode configuration cell assembly comprising an integrated two-layer bifunctional ORR/OER electrode system with the individual layers dedicated for the ORR and the OER to prevent deactivation of the ORR activity as commonly observed in single-layer bifunctional ORR/OER electrodes after OER polarization. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Among the numerous homogeneous electrochemical CO2 reduction catalysts, [Ni(cyclam)]2+ is known as one of the most potent catalysts. Likewise, [Ni(isocyclam)]2+ was reported to enable electrochemical CO2 conversion but has received significantly less attention. However, for both catalysts, a purposeful substitution of a single nitrogen donor group by chalcogen atoms was never reported. In this work, we report a series of isocyclam-based Ni complexes with {ON3}, {SN3}, {SeN3}, and {N4} moieties and investigated the influence of nitrogen/chalcogen substitution on electrochemical CO2 reduction. While [Ni(isocyclam)]2+ showed the highest selectivity toward CO2 reduction within this series with a Faradaic efficiency of 86% for the generation of CO at an overpotential of-1.20 V and acts as a homogeneous catalyst, the O-and S-containing Ni complexes revealed comparable catalytic activities at ca. 0.3 V milder overpotential but tend to form deposits on the electrode, acting as precursors for a heterogeneous catalysis. Moreover, the heterogeneous species generated from the O-and S-containing complexes enable a catalytic hydride transfer to acetonitrile, resulting in the generation of acetaldehyde. The incorporation of selenium, however, resulted in loss of CO2 reduction activity, mainly leading to hydrogen generation that is also catalyzed by a heterogeneous electrodeposit. Copyright © 2020 American Chemical Society.

A new medium-entropy superalloy was produced based on the compositions of equiatomic CrCoNi and Ni-base superalloy Inconel 740H. Initial alloy design was performed using Thermo-Calc. The aging response and microstructural stability were assessed following heat treatment at temperatures between 600 and 900 °C and durations up to 100 h. Aging from a fully recrystallized state resulted in negligible grain growth and produced γ’ and σ phases. The same phases were present after aging from a cold-rolled state, but partially recrystallized microstructures resulted in multi-modal size distributions and heterogeneous spatial arrangements. Room temperature hardness measurements were used to correlate aging conditions with quantitative precipitate measurements and mechanical properties. © 2019 Elsevier B.V.

The present work contributes to a better understanding of the effect of stress multiaxiality on the creep behavior of single crystal Ni-base superalloys. For this purpose we studied the creep deformation and rupture behavior of double notched miniature creep tensile specimens loaded in three crystallographic directions [100], [110] and [111] (creep conditions: 950 °C and 400 MPa net section stress). Crystal plasticity finite element method (CPFEM) was used to analyze the creep stress and strain distributions during creep. Double notched specimens have the advantage that when one notch fails, the other is still intact and allows to study a material state which is close to rupture. No notch root cracking was observed, while microstructural damage (pores and micro cracks) were frequently observed in the center of the notch root region. This is in agreement with the FEM results (high axial stress and high hydrostatic stress in the center of the notched specimen). Twinning was observed in the notch regions of [110] and [111] specimens, and <112> {111} twins were detected and analyzed using orientation imaging scanning electron microscopy. The present work shows that high lattice rotations can be detected in SXs after creep fracture, but they are associated with the high strains accumulated in the final rupture event. © 2020 The Authors

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.

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.

Under the typical hot isostatic pressing (HIP) processing conditions, plastic deformation by dislocation slip is considered the primary mechanism for pore shrinkage, according to experimental observations and deformation mechanism maps. In the present work, a crystal plasticity model has been used to investigate the influence of applied pressure and holding time on porosity reduction in a nickel-base single crystal superalloy. The influence of trapped gas on pore shrinkage is modeled by coupling mechanical deformation with pore–gas interaction. In qualitative agreement with experimental investigations, we observe that increasing the applied pressure or the holding time can effectively reduce porosity. Furthermore, the effect of pore shape on the shrinkage is observed to depend on a combination of elastic anisotropy and the complex distribution of stresses around the pore. Simulation results also reveal that, for pores of the same shape, smaller pores (radius < 0.1 µm) have a higher shrinkage rate in comparison to larger pores (radius ≥ 0.1 µm), which is attributed to the increasing pore surface energies with decreasing pore sizes. It is also found that, for smaller initial gas-filled pores (radius < 0.1 µm), HIP can result in very high gas pressures (on the order of GPa). Such high pressures either act as a driving force for argon to diffuse into the surrounding metal during HIP itself, or it can result in pore re-opening during subsequent annealing or mechanical loading. These results demonstrate that the micromechanical model can quantitatively evaluate the individual influences of HIP processing conditions and pore characteristics on pore annihilation, which can help optimize the HIP process parameters in the future. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

In the present work, three Ni-based single-crystal superalloys (SXs) were investigated, a Re-containing alloy ERBO/1 (CMSX-4 type) and two Re-free SXs referred to as ERBO/15 and ERBO/15-W, which differ in W content. The microstructural evolution of the three alloys during heat treatment and their creep behavior is investigated. When one applies one heat treatment to all three alloys, one obtains different γ/γ′-microstructures. Subjecting these three alloys to creep in the high-temperature low-stress creep regime, ERBO/15 outperforms ERBO/1. In order to separate the effects of alloy chemistry and microstructure, the kinetics of the microstructural evolution of the three alloys was measured. The results were used to establish similar microstructures in all three alloys. Comparing ERBO/15 with ERBO/15-W, it was found that in ERBO/15-W particles grow faster during the first precipitation heat treatment and that ERBO/15-W creeps significantly faster. At constant microstructures, ERBO/15 and ERBO/1 show similar creep behavior. In the high-temperature and low-stress creep regime, ERBO/15 shows lower minimum creep rates but ERBO/1 features a slower increase of creep rate in the tertiary creep regime. It was also found that in the high-temperature low-stress creep regime, ERBO/1 shows a double minimum creep behavior when particles are small. © 2020, The Minerals, Metals & Materials Society.

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.

The role and effect of γ′ precipitate size on the mechanical properties of Ni-base single crystal superalloy is investigated. The underlying mechanisms are analyzed on the one hand with the help of experiments including hardness and creep tests, and on the other hand with the help of two different simulation approaches by taking the typical γ/γ′ microstructure into account. Simulations, based on the crystal plasticity finite element method (CPFEM) are carried out for the hardness tests, whereas simulations, based on the crystal plasticity coupled phase-field method (CPPFM) are carried out for the creep tests. The hardness test simulation results show that the hardness of material varies inversely with the size of γ′ precipitates for a given γ′ phase volume fraction and it varies directly with the volume fraction of γ′ precipitates for a given precipitate size. These results are qualitatively consistent with the experimental observations. The creep simulation results show that the refinement of γ′ precipitates with a certain volume fraction of precipitates leads to an improvement of creep resistance by delaying the plastic activity in the material. © 2020 Acta Materialia Inc.

Ultrafast construction of oxygen-containing scaffold over graphite for trapping Ni2+ into single atom catalysts (SACs) was developed and presented by a one-step electrochemical activation technique. The present method for Ni SACs starts with graphite foil and is capable of achieving ultrafast preparation (1.5 min) and mass production. The defective oxygen featuring the strong electronegativity enables primarily attracting Ni2+ ions and stabilizing Ni atoms via Ni-O6 coordination instead of conventional metal-C or metal-N. In addition, the oxygen defects for trapping are tunable through altering the applied voltage or electrolyte, further altering the loading of Ni atoms, indicative of enhanced oxygen evolution activity. This simple and ultrafast electrochemical synthesis is promising for the mass and controllable production of oxygen-coordinated Ni SACs, which exhibit good performance for oxygen evolution reaction. © 2020 American Chemical Society.

Single crystal Ni-based superalloys have long been an essential material for gas turbines in aero engines and power plants due to their outstanding high temperature creep, fatigue and oxidation resistance. A turning point was the addition of only 3 wt.% Re in the second generation of single crystal Ni-based superalloys which almost doubled the creep lifetime. Despite the significance of this improvement, the mechanisms underlying the so-called “Re effect” have remained controversial. Here, we provide direct evidence of Re enrichment to crystalline defects formed during creep deformation, using combined transmission electron microscopy, atom probe tomography and phase field modelling. We reveal that Re enriches to partial dislocations and imposes a drag effect on dislocation movement, thus reducing the creep strain rate and thereby improving creep properties. These insights can guide design of better superalloys, a quest which is key to reducing CO2 emissions in air-traffic. © 2020, The Author(s).

Breakthroughs toward effective water-splitting electrocatalysts for mass hydrogen production will necessitate material design strategies based on unexplored material chemistries. Herein, Ni-metalloid (B, Si, P, As, Te) alloys are reported as an emergent class of highly promising electrocatalysts for the oxygen evolution reaction (OER) and insight is offered into the origin of activity enhancement on the premise of the surface electronic structure, the OER activation energy, influence of the guest metalloid elements on the lattice structure of the host metal (Ni), and surface-oxidized metalloid oxoanions. The metalloids modify the lattice structure of Ni, causing changes in the nearest Ni–Ni interatomic distance (dNi–Ni). The activation energy Ea scales with dNi–Ni indicating an apparent dependence of the OER activity on lattice properties. During the OER, surface Ni atoms are oxidized to nickel oxyhydroxide, which is the active state of the catalyst, meanwhile, the surface metalloids are oxidized to the corresponding oxoanions that affect the interfacial electrode/electrolyte properties and hence the adsorption/desorption interaction energies of the reacting species. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

In the present work we present the Rotation Vector Base Line Electron Back Scatter Diffraction (RVB-EBSD) method, a new correlative orientation imaging method for scanning electron microscopy (OIM/SEM). The RVB-EBSD method was developed to study crystal mosaicity in as-cast Ni-base superalloy single crystals (SX). The technique allows to quantify small crystallographic deviation angles between individual dendrites and to interpret associated accommodation processes in terms of geometrically necessary dislocations (GNDs). The RVB-EBSD method was inspired by previous seminal approaches which use cross correlation EBSD procedures. It applies Gaussian band pass filtering to improve the quality of more than 500 000 experimental patterns. A rotation vector approximation and a correction procedure, which relies on a base line function, are used. The method moreover features a novel way of intuitive color coding which allows to easily appreciate essential features of crystal mosaicity. The present work describes the key elements of the method and shows examples which demonstrate its potential. © 2019 Elsevier B.V.

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.

The direct growth of Pt islands on lattice mismatched Ni nanoparticles is a major synthetic challenge and a promising strategy to create highly strained Pt atoms for electrocatalysis. By using very mild reaction conditions, Pt islands with tunable strain were formed directly on Ni branched particles. The highly strained 1.9 nm Pt-island on branched Ni nanoparticles exhibited high specific activity and the highest mass activity for hydrogen evolution (HER) in a pH 13 electrolyte. These results show the ability to synthetically tune the size of the Pt islands to control the strain to give higher HER activity. Copyright © 2019 American Chemical Society.

We present a ballistic rectification effect in an orthogonal four-terminal cross junction where the symmetry is broken by local magnetic fields. The input current is injected between opposing branches and the current-free branches serve as potential probes. The local magnetic field is induced by two permalloy (Py) stripes with a magnetic single-domain structure, where one end of each stripe is positioned close to the junction center. The Py stripes are oriented such that an external in-plane magnetic field can magnetize them into two different main configurations having either equally or oppositely magnetized ends. Equal magnetic ends are expected to result in a Hall-effect device, while for opposite magnetic ends, the stray field should deflect the electrons into the same output lead for both current polarities, leading to a rectifying behavior. Here, we present the proof of concept for stray-field controlled transfer characteristics. First, we show by magnetic force microscopy that both configurations are stable and the Py stripes exhibit a remanent magnetic single-domain structure. Second, we demonstrate the influence of the remanent magnetization on the low-temperature dc characteristics which are superimposed by a parasitic background. Third, we present the extracted Hall and the rectified voltage which are, respectively, linearly and parabolically dependent on the input current up to ±55 μA. © 2019 Author(s).

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.

The effect of finely dispersed particles on the functional properties and morphology of thermally induced martensite in Co-Ni-Ga shape memory alloys has been already reported in literature, however, still important aspects are not fully understood. The current study focuses on the stress-induced martensitic transformation of solution-annealed, i.e. precipitate-free, and aged 〈001〉-oriented single crystals. In situ optical microscopy and neutron diffraction experiments show a significant influence of γ′-particles on the martensite variant selection and its morphology under pseudoelastic deformation. In addition, the results reveal detwinning upon loading in the presence of nanometric particles, which is experimentally proven for the first time. © 2019 Elsevier Ltd

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

Gas evolving electrochemical reactions induce bubble formation and growth at surfaces of electrodes. To study one such situation, hydrogen evolution on nickel electrodes, short time chronoamperometric experiments were performed in combination with in-situ microscopy. The entire electrode of 3.14 mm2 was imaged with confocal microscopy and the current response of the electrode then correlated to the observed bubble growth features. Somehow counterintuitively, first a 2–3% increase in current was observed consistently when a bubble grows close to the electrode on the edge of the electrode holder, made of a polymer. This is argued to be due to the removal of surface attached gas from the electrode. Next, we observe a consecutive regime of decreasing current, in which large bubbles accumulate on the surface. Interestingly, when these surface attached bubbles coalesce, a steep change in current is observed, which is accompanied by a burst of small bubbles nucleating on the surface previously occupied by the large bubble. These phenomena are qualitatively discussed on the basis of existing literature, and implications for improvements for electrodes on which gases are produced, are outlined. © The Author(s) 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.

Hydrogen environment embrittlement (HEE) of low-nickel austenitic stainless steels (AISI 300 series) with different chemical compositions was studied focusing on the impact of the steels surface oxides, grain sizes and dislocation arrangements. The susceptibility of the steels to HEE is judged with respect to the relative reduction of area (RRA), where the HEE susceptibility is lower for larger RRA values. For many AISI 300 steels a linear trend is observed correlating RRA and the probability of strain induced martensite formation in tensile tests. Some steels, however, depart from the general trend, revealing greater HEE resistances. A careful examination of possible factors influencing HEE of the investigated steels reveals that high RRA values are linked to a specific type of oxide layer, namely the “high constant level oxide”, as categorized by TOF-SIMS evaluation. Thus, this type of oxide layer may be able to lower the steels HEE susceptibility. Other types of surface oxides, grain sizes and dislocation arrangements in the matrix of the particular AISI 300 steels appear to be of secondary importance. © 2019 Acta Materialia Inc.

Large magnetocrystalline anisotropy (MCA) is of high technical relevance, in particular for magnetic actuators, permanent magnets, and memory devices with high density. Large MCAs have been reported for the low temperature L10 phase of Ni2MnGa. Both, Mn and Pt substitution can stabilize this phase at and above room temperature. Despite the larger spin-orbit coupling in the heavy 5d-element Pt, it has been reported that Pt substitution may result in degeneration of the MCA. In this paper, we study the MCA for a combination of epitaxial strain and Mn and Pt substitution based on density functional theory methods. We show that one can stabilize both large uniaxial and easy-plane anisotropies depending on the value of strain. In particular, small changes of the applied strain may allow to switch between low- and high-anisotropy states or even switch the direction of the easy-axis magnetization direction. © 1965-2012 IEEE.

The high temperature low cycle fatigue behavior of specimens manufactured from a single crystalline nickel base superalloy processed by selective electron beam melting (SEBM) has been investigated with respect to the effect of different heat treatments. The fatigue lifetime of heat treated material was significantly higher than that of as-built material. Applying hot isostatic pressing (HIP) with an integrated heat treatment resulted in even longer fatigue life. Lifetime limiting crack initiation occurred at interfaces of melting layers, at micro-porosity generated during solidification or, in HIP treated samples, at precipitates which formed at the location of collapsed pores. © 2019 Elsevier Ltd

Turbine blades in aviation engines and land based gas-turbines are exposed to extreme environments. They suffer damage accumulation associated with creep, oxidation and fatigue loading. Therefore, advanced repair methods are of special interest for the gas-turbine industry. In this study, CMSX-4 powder is sprayed by Vacuum Plasma Spray (VPS) on single-crystalline substrates with similar compositions. The influence of the substrate temperature is investigated altering the temperature of the heating stage between 850 °C to 1000 °C. Different spray parameters were explored to identify their influence on the microstructure. Hot isostatic pressing (HIP) featuring fast quenching rates was used to minimize porosity and to allow for well-defined heat-treatments of the coatings. The microstructure was analysed by orientation imaging scanning electron microscopy (SEM), using electron backscatter diffraction (EBSD). The effects of different processing parameters were analysed regarding their influence on porosity and grain size. The results show that optimized HIP heat-treatments can lead to dense coatings with optimum γ/γ′ microstructure. The interface between the coating and the substrate is oxide free and shows good mechanical integrity. The formation of fine crystalline regions as a result of fast cooling was observed at the single-crystal surface, which resulted in grain growth during heat-treatment in orientations determined by the crystallography of the substrate. © 2019

The formation, characterization, and dye sensitized solar cell application of nickel(II), zinc(II) and cadmium(II) ferrocenyl dithiophosphonate complexes were investigated. The multidentate monoanionic ligand [S2PFc(OH)]− (L1) was synthesized. The reaction between metal salt precursors and L1 produced Ni(II) complexes of the type [Ni{S2P(Fc)(OH)}2] (1) (molar ratio 1:2), and a tetranickel(II) complex of the type [Ni2{S2OP(Fc)}2]2 (2) (molar ratio (1:1). It also produced a Zn(II) complex [Zn{S2P(Fc)(OH)}2]2 (3), and a Cd(II) complex [Cd{S2P(Fc)(OH)}2]2 (4). Complexes 1–4 were characterized by 1H and 31P NMR, FTIR and elemental analysis, and complexes 1 and 2 were additionally analyzed by X-ray crystallography. The first examples of dye-sensitized solar cells (DSSCs) co-sensitized with ferrocenyl dithiophosphonate complexes 1–4 are reported. Co-sensitization with the ruthenium dye N719, produced the dye materials (3)-N719 (η=8.30%) and (4)-N719 (η=7.78%), and they were found to have a better overall conversion efficiency than the pure Ru N719 dye standard (η=7.14%) under the same experimental conditions. The DSSCs were characterized using UV/vis, cyclic voltammetry, electrochemical impedance spectroscopy (EIS), photovoltaic- (I−V curves), and performing incident photon-to-current efficiency (IPCE) measurements. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The replacement of the opposing nitrogen atoms in 1,4,8,11-tetraazacyclotetradecane (cyclam) with two sulfur atoms in 1,8-dithia-4,11-diazacyclotetradecane (dithiacyclam) enables the electrochemical reduction of protons and CO2via the corresponding nickel(ii) complex at more positive potentials. In addition, a 10-fold enhancement in the proton reduction rate of [Ni(dithiacyclam)]2+ relative to [Ni(cylcam)]2+ was observed. The study provides vital insight into Nature's choice of employing predominantly sulfur based ligand platforms in achieving biological proton and CO2 reductions. © 2019 The Royal Society of Chemistry.

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

The electrocatalytic reduction of carbon dioxide (CO 2 RR) to valuable bulk chemicals is set to become a vital factor in the prevention of environmental pollution and the selective storage of sustainable energy. Inspired by structural analogues to the active site of the enzyme CODH Ni , we envisioned that bulk Fe/Ni sulfides would enable the efficient reduction of CO 2 . By careful adjustment of the process conditions, we demonstrate that pentlandite (Fe 4.5 Ni 4.5 S 8 ) electrodes, in addition to HER, also support the CO 2 RR reaching a peak faradaic efficiency of 87% and 13% for the formation of CO and methane, respectively at 3 mA cm -2 . The choice of solvent, the presence of water/protons and CO 2 solubility are identified as key-properties to adjust the balance between HER and CO 2 RR in favour of the latter. Such experiments can thus serve as model reactions to elucidate a potential catalyst within gas diffusion electrodes. © 2019 The Royal Society of Chemistry.

In the present work, we study the effect of HIP rejuvenation treatments on the creep behavior and residual life of a pre-crept single crystal Ni-base superalloy of type CMSX-4. The present work combines miniature creep experiments of precisely oriented [001]tensile creep specimens with HIP treatments and quantitative analysis of scanning and transmission electron micrographs. A HIP-rejuvenation treatment after 5.0% creep pre-strain significantly improves creep strength. However, the microstructural damage induced by the creep pre-deformation could not be fully removed. In a series of sequential creep/HIP/creep-experiments, increasing levels of pre-deformation result in increasing levels of creep rates even after identical HIP-rejuvenation treatments. The memory effect, which causes this phenomenon, is related to an accumulation of permanent microstructural damage, which is not associated with rafting or cavitation. The mechanical results obtained in the present work are interpreted based on microstructural results on the γ/γʼ-microstructure (γ-channel widths and γʼ-size), on the pore population (number density of pores, pore size distributions and pore area fractions)and dislocation substructures which have formed during creep. The results are discussed in the light of previous results reported in the literature. © 2019 The Authors

Partitioning of C during tempering of quenched Fe-9.6Ni-0.5C-0.6Mn-0.6Mo-0.7Cr-0.1V (at.%) steel is determined by atom probe tomography and the resulting microstructure is described. The precipitated austenite size, together with its C and Ni content control its thermal stability and these can vary differently with tempering time and temperature. Thus, both austenite and strong carbide formers compete for the available C early in the process. Due to widely different transport kinetics, C likely plays a dominant role early but is either fully consumed or its role diminishes by dilution, and Ni partitioning eventually takes over as the austenite stability-controlling species. © 2019 Elsevier Ltd

Dislocation-precipitate interaction and solute segregation play important roles in controlling the mechanical behavior of Ni-based superalloys at high temperature. In particular, the increased mobility of solutes at high temperature leads to increased dislocation-solute interaction. For example, atom probe tomography (APT) results [1] for single crystal MC2 superalloy indicate significant segregation of solute elements such as Co and Cr to dislocations and stacking faults in γ′ precipitates. To gain further insight into solute segregation, dislocation-solute interaction, and its effect on the mechanical behavior in such Ni-superalloys, finite-deformation phase field chemomechanics [2] is applied in this work to develop a model for dislocation-solute-precipitate interaction in the two-phase γ-γ′ Ni-based superalloy model system Ni–Al–Co. Identification and quantification of this model is based in particular on the corresponding Ni–Al–Co embedded atom method (EAM) potential [3]. Simulation results imply both Cottrell- and Suzuki-type segregation of Co in γ and γ'. Significant segregation of Co to dislocation cores and faults in γ′ is also predicted, in agreement with APT results. Predicted as well is the drag of Co by γ dislocations entering and shearing γ'. Since solute elements such as Co generally prefer the γ phase, Co depletion in γ′ could be reversed by such dislocation drag. The resulting change in precipitate chemistry may in turn affect its stability and play a role in precipitate coarsening and rafting. © 2019 Acta Materialia Inc.

Elemental segregation to grain boundaries (GBs) can induce structural and chemical transitions at GBs along with significant changes in material properties. The presence of multiple principal elements interacting in high-entropy alloys (HEAs) makes the GB segregation and interfacial phase transformation a rather challenging subject to investigate. Here, we explored the temporal evolution of the chemistry for general high-angle GBs in a typical equiatomic FeMnNiCoCr HEA during aging heat treatment through detailed atom probe tomography (APT) analysis. We found that the five principal elements segregate heterogeneously at the GBs. More specifically, Ni and Mn co-segregate to some regions of the GBs along with the depletion of Fe, Co and Cr, while Cr is enriched in other regions of the GBs where Ni and Mn are depleted. The redistribution of these elements on the GBs follow a periodic characteristic, spinodal-like compositional modulation. The accumulation of elements at the GBs can create local compositions by shifting their state from a solid solution (like in the adjacent bulk region) into a spinodal regime to promote interfacial phase-like transitions as segregation proceeds. These results not only shed light on phase precursor states and the associated nucleation mechanism at GBs in alloy systems with multiple principal elements but also help to guide the microstructure design of advanced HEAs in which formation of embrittling phases at interfaces must be avoided. © 2019 Acta Materialia Inc.

The influence of the process parameters in Laser Beam Melting (LBM) on the element distribution and magnetic properties of permalloy (Ni 78.5 Fe 21.5 ) is studied. Iron and nickel powders are mixed in the respective proportions to build twenty-five permalloy samples. The process parameters for each sample are varied to achieve different volume energy densities. An increase of the saturation magnetization M S up to 14% of the samples with respect to the initial powder blend is found. For a volume energy density of 428 [Formula presented] we detect a stripe-like segregation of iron and nickel in the uppermost layer. In the volume a homogeneous element distribution is found. The segregation at the surface leads to a sizable uniaxial magnetic anisotropy. When using parameter combinations resulting in similar volume energy densities, we observe different surface morphologies depending on scan speed and laser power. The implications for creating tailored magnetic anisotropy directions in Fe-Ni soft magnets are discussed. © 2019 Elsevier B.V.

The microstructural evolution in the single crystal Ni-base superalloy ERBO/1 (CMSX 4 type) is investigated after load controlled low cycle fatigue (LCF) at 950 °C (load-ratio: 0.6, tensile stress range: 420–740 MPa, test frequency: 0.25 Hz, fatigue rupture life: about 1000 - 3000 cycles). Bulk topologically close packed (TCP) phase particles precipitated and were analyzed by three-dimensional focus ion beam slice and view imaging and analytical transmission electron microscopy. The particles did not precipitate homogenously but at locations with enhanced levels of local stresses/strains, such as isolated γ-channels subjected to cross channel stresses, shear bands and in front of micro cracks. The influence of stress/strain is furthermore apparent in the spatial arrangement and the shape of the TCP phase particles. Only μ-phase TCP particles were found by electron diffraction. Results of a structure-map analysis suggest that most of these TCP particles observed after LCF testing would not precipitate in thermodynamic equilibrium. In order to rationalize this effect, the atomic volume was analyzed that transition-metal (TM) elements take in unary fcc and in unary μ-phase crystal structures and found that all TM elements except Zr and V take a larger volume in a unary μ phase than in a unary fcc phase. This trend is in line with the observed localized precipitation of TCP phases that are rich in Ni and other late TM elements. The experimental and theoretical findings suggest consistently that formation of TCP particles in LCF tests is considerably influenced by the local tensile stress/strain states. © 2019 Acta Materialia Inc.

Selective laser melting (SLM) provides an economic approach to manufacturing Ni-base superalloy components for high-pressure gas turbines as well as repairing damaged blade sections during operation. In this study, two advanced processing routes are combined: SLM, to fabricate small specimens of the nonweldable CMSX-4, and hot isostatic pressing (HIP) with a rapid cooling rate as post-processing to heal defects while the target γ/γ´ microstructure is developed. An initial parametric study is carried out to investigate the influence of the SLM process parameters on the microstructure and defects occurring during SLM. Special emphasis is placed on understanding and characterizing the as-built SLM microstructures by means of high-resolution characterization techniques. The post-processing heat treatment is then optimized with respect to segregation and the γ/γ´ microstructure. © 2019 Elsevier B.V.

There are still debates regarding the mechanisms that lead to hot cracking in parts build by additive manufacturing (AM) of non-weldable nickel-based superalloys. This lack of in-depth understanding of the root causes of hot cracking is an impediment to designing engineering parts for safety-critical applications. Here, we deploy a near-atomic-scale approach to investigate the details of the compositional decoration of grain boundaries in the coarse-grained, columnar microstructure in parts built from a non-weldable nickel-based superalloy by selective electron-beam melting. The progressive enrichment in Cr, Mo and B at grain boundaries over the course of the AM-typical successive solidification and remelting events, accompanied by solid-state diffusion, causes grain boundary segregation induced liquation. This observation is consistent with thermodynamic calculations. We demonstrate that by adjusting build parameters to obtain a fine-grained equiaxed or a columnar microstructure with grain width smaller than 100 μm enables to avoid cracking, despite strong grain boundary segregation. We find that the spread of critical solutes to a higher total interfacial area, combined with lower thermal stresses, helps to suppress interfacial liquation. © 2019 Acta Materialia Inc.

Hydrogen embrittlement (HE) of several low-nickel austenitic stainless steels (AISI 300 series) was studied with special attention to the impact of strain induced α′-martensite. The susceptibility of the steels to HE is judged with respect to the relative reduction of area (RRA): The HE susceptibility is lower for larger RRA-values. Strain-induced martensite formation was evaluated within in the framework of the Olson-Cohen model, revealing a linear relationship between RRA and the probability β of martensite nucleus formation in the steels. In order to widen the scope of data evaluation to literature data, the consideration of a parameter alternative to β is required. It is demonstrated that among other parameters the Md30 temperature (Nohara), which assesses the stability against martensitic transformation, can serve as an indicator to predict HE of AISI 300 series steels. Regarding the Md30 temperature (Nohara), a trend-line with respect to the RRA-values is found. Thereby, the RRA-values of low-nickel austenitic stainless steels group into three distinct regimes; (1) for Md30 > −80 °C, where RRA-values decrease with increasing Md30 temperature, (2) at Md30 ≈ −80 °C, where RRA-values show a large variation (‘threshold band’), and (3) for Md30 < −80 °C, showing constant RRA-values of nearly 100%. Some RRA data points that deviate from the trend line can be explained by the special microstructure of the investigated samples. © 2019 Hydrogen Energy Publications LLC

Abstract: We have evaluated the applicability of Ni anodes in electrochemical conversion of H2S to form sulfur (polysulfides) and H2. Two different electrolytes containing sulfide were evaluated: a buffered solution of Na2HPO4 at pH 9.2, and a NaOH solution at pH 13. At pH 9.2, deposition of sulfur on the Ni anode was observed, resulting in a significant decrease in electrochemical performance. The composition, morphology, and thickness of the sulfur deposit, as determined by Raman spectroscopy and SEM, was found to strongly depend on the applied potential, and ranged from dense S8 films to highly porous spherical sulfur structures. Oxidation of the anode was also observed by conversion of Ni to NiS2. The formation of the sulfur film was prevented by performing the reaction at pH 13 in NaOH in the range of − 1.0 V to + 0.6 V versus Hg/HgO. It is proposed that at these highly basic pH values, sulfur is dissolved in the electrolyte in the form of polysulfides, such as S2 2− or S8 2−. When using Ni anodes some oxygen evolution was observed at the anode, in particular at pH 13, resulting in a Faradaic efficiency for sulfur removal of ~ 90%. Graphic Abstract: [Figure not available: see fulltext.]. © 2019, The Author(s).

A vital issue during selective laser melting of nonweldable polycrystalline nickel-base superalloys is the formation of microcracks. These are cracks occurring during the last stage of solidification and only at high angle grain boundaries (HAGBs). Solute enrichment to the remaining interdendritic liquid and its partial back-diffusion into the solid contributes to the crack nucleation mechanism. Here we use atom probe tomography coupled with transmission Kikuchi diffraction to determine the misorientation and chemical composition profiles across HAGBs (with and without cracks) and across crack-free low angle grain boundaries (LAGBs). The Gibbsian interfacial excess of solutes (mainly B, C, Si, and Zr) is at least two times higher at the HAGB compared to the LAGB. The chemical profiles show the opposite behavior to established model predictions of the last stage of solidification. Our diffusion calculations elucidate that the chemical profiles are influenced by both microsegregation (of Ti, Nb, and Si) during solidification and solid-state segregation (of B, C, and Zr) during cooling. The chemical profiles in the topmost layer indicate a negligible effect of remelting and reheating. Except for Ti-rich carbides, no secondary phases are found. Additionally, we study an alloy with a reduced content of Zr and Si (by at least 60 wt. %), relative to the standard IN738LC composition. We achieved a 99% reduction in crack length per unit area. However, the grain boundary enrichment of Zr and Si in the modified alloy was similar to the standard alloy. Based on these findings, we critically discuss the contribution of various mechanisms proposed for solidification cracking. © 2019 American Physical Society.

The microstructure-mechanical property relationships of a non-equiatomic FeMnCoCr high entropy alloy (HEA), which shows a single face-centered cubic (fcc) structure in the undeformed state, have been systematically investigated at room and cryogenic temperatures. Both strength and ductility increase significantly when reducing the probing temperature from 293 K to 77 K. During tensile deformation at 293 K, dislocation slip and mechanical twinning prevail. At 173 K deformation-driven athermal transformation from the fcc phase to the hexagonal close-packed (hcp) martensite is the dominant mechanism while mechanical twinning occurs in grains with high Schmid factors. At 77 K athermal martensitic transformation continues to prevail in addition to dislocation slip and twinning. The reduction in the mean free path for dislocation slip through the fine martensite bundles and deformation twins leads to the further increased strength. The joint activation of transformation and twinning under cryogenic conditions is attributed to the decreased stacking fault energy and the enhanced flow stress of the fcc matrix with decreasing temperature. These mechanisms lead to an elevated strain hardening capacity and an enhanced strength-ductility combination. The temperature-dependent synergy effects of martensite formation, twinning and dislocation plasticity originate from the metastability alloy design concept. This is realized by relaxing the equiatomic HEA constraints towards reduced Ni and increased Mn contents, enabling a non-equiatomic material with low stacking fault energy. These insights are important for designing strong and ductile Ni-saving alloys for cryogenic applications. © 2019 Elsevier B.V.

Metallic materials have enabled technological progress over thousands of years. The accelerated demand for structural (that is, load-bearing) alloys in key sectors such as energy, construction, safety and transportation is resulting in predicted production growth rates of up to 200 per cent until 2050. Yet most of these materials require a lot of energy when extracted and manufactured and these processes emit large amounts of greenhouse gases and pollution. Here we review methods of improving the direct sustainability of structural metals, in areas including reduced-carbon-dioxide primary production, recycling, scrap-compatible alloy design, contaminant tolerance of alloys and improved alloy longevity. We discuss the effectiveness and technological readiness of individual measures and also show how novel structural materials enable improved energy efficiency through their reduced mass, higher thermal stability and better mechanical properties than currently available alloys. © 2019, Springer Nature Limited.

Compounds and alloys of cobalt and nickel with some nonmetals (N, P, S, Se) and metalloids (C, B, C, As and Te) have emerged as very promising noble metal-free pre-catalysts for the oxygen evolution reaction (OER) in alkaline electrolytes. However, the exact role played by the non-metals and metalloids in promoting the OER is not well understood. A holistic understanding of the origin of the OER activity enhancement in these compounds is vital for their exploitation as models to inspire knowledge-guided design of improved OER catalysts. In this review, we elucidate the factors that govern the activity and stability of OER catalysts derived from MX compounds (M=Co or Ni, and X=nonmetal or metalloid), including the impact of surface electronic structure, M : X stoichiometry, material composition, structure and crystallinity, as well as the role of oxoanions on the properties of the electrochemical double layer and interaction energies of the reaction intermediates. Finally, we outline a few perspectives and research directions towards a deeper understanding of the role of the nonmetal and metalloid elements and design of improved OER catalysts. ©2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

A newly developed miniature specimen and respective fixture for high temperature low cycle fatigue testing of nickel based single crystal superalloys is presented. Miniaturization allows the preparation of test specimens in all main crystallographic orientations of the cubic nickel crystal using laboratory sized material samples and enables excellent utilization of the costly material. The specimen geometry is optimized by means of parameter studies employing numerical calculations such that for the main crystallographic orientations the stress concentration at the fillet between gauge length and specimen head is minimized, and failure is likely to occur within the gauge length. The designed fixture allows easy specimen mounting and provides sufficient support for applying an extensometer for strain measurement. Protective metallic coatings against oxidation can be applied on the specimen by plasma spraying for studying the effect of coatings on the fatigue lifetime. The functionality of the specimen geometry and fixture design for low cycle fatigue testing is demonstrated for temperatures up to 950 °C. © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The present work compares the microstructures and the creep properties of two types of single crystal Ni-base superalloy CMSX-4 materials (SXs). One was produced by conventional directional solidification Bridgman processing. The other was manufactured by selective electron beam melting (SEBM). The microstructures of the two types of materials are compared with emphasis placed on the large (dendritic/interdendritic regions) and small scale (γ-matrix/γ′-precipitates) microstructural heterogeneities, which characterize SX microstructures and their evolution during processing, heat treatment and creep. It is shown that heat treated SEBM materials have creep properties, which match or even outperform those of conventionally processed SX materials. Creep properties were assessed using a miniature creep test technique where [001] miniature tensile creep specimens were tested in the high temperature/low stress (1050 °C, 160 MPa) and in the low temperature/high stress (850 °C, 600 MPa) creep regimes. The creep behavior is interpreted based on microstructural results, which were obtained using analytical scanning and transmission electron microscopy (SEM and TEM). © 2019 The Authors

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.

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.

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

A non weldable nickel-based superalloy was fabricated by powder bed-based selective electron beam melting (S-EBM). The as-built samples exhibit a heterogeneous microstructure along the build direction. A gradient of columnar grain size as well as a significant gradient in the γ′ precipitate size were found along the build direction. Microstructural defects such as gas porosity inherited from the powders, shrinkage pores and cracks inherited from the S-EBM process were identified. The origins of those defects are discussed with a particular emphasis on crack formation. Cracks were consistently found to propagate intergranular and the effect of crystallographic misorientation on the cracking behavior was investigated. A clear correlation was identified between cracks and high angle grain boundaries (HAGB). The cracks were classified as hot cracks based on the observation of the fracture surface of micro-tensile specimens machined from as-built S-EBM samples. The conditions required to trigger hot cracking, namely, presence of a liquid film during the last stage of solidification and thermal stresses are discussed within the framework of additive manufacturing. Understanding the cracking mechanism enables to provide guidelines to obtain crack-free specimens of non-weldable Ni-based superalloys produced by S-EBM. © 2017 Acta Materialia Inc.

This work investigates the separate influence of porosity and γ/γ′-eutectics on the low-cycle fatigue life of a single-crystal Ni-base superalloy at high temperatures. A conventional vacuum furnace heat-treatment but also integrated heat-treatments in a hot isostatic press are applied to produce different material variants of the same alloy. High-resolution electron microscopy revealed that both pores and γ/γ′-eutectics act as crack starters, thus initiating early failure. Moreover, the results indicate that remaining γ/γ′-eutectics can weaken the fatigue resistance even more than pores. Furthermore, the results confirm the beneficial effect of proper integrated hot isostatic pressing heat-treatments on the fatigue performance. © 2018

Currently, additive manufacturing (AM) experiences significant attention in nearly all industrial sectors. AM is already well established in fields such as medicine or spare part production. Nevertheless, processing of high-performance nickel-based superalloys and especially single crystalline alloys such as CMSX-4® is challenging due to the difficulty of intense crack formation. Selective electron beam melting (SEBM) takes place at high process temperatures (~ 1000 °C) and under vacuum conditions. Current work has demonstrated processing of CMSX-4® without crack formation. In addition, by using appropriate AM scan strategies, even single crystals (SX SEBM CMSX-4®) develop directly from the powder bed. In this contribution, we investigate the mechanical properties of SX SEBM CMSX-4® prepared by SEBM in the as-built condition and after heat treatment. The focus is on hardness, strength, low cycle fatigue, and creep properties. These properties are compared with conventional cast and heat-treated material. © 2018 The Author(s)

The determination of the intrinsic properties of nanomaterials is essential for their optimization as electrocatalysts, however it poses great challenges from the standpoint of analytical tools and methods. Herein, we report a novel methodology that allows for a binder-free investigation of electrocatalyst nanoparticles. The potential-assisted immobilization of a non-noble metal catalyst, i.e., nickel-iron layered double hydroxide (NiFe LDH) nanoparticles, was employed to directly attach small nanoparticle ensembles from a suspension to the surface of etched carbon nanoelectrodes. The dimensions of this type of electrodes allowed for the immobilization of the catalyst material below the picogram scale and resulted in a high resolution towards the faradaic current response. In addition the effect of the electrochemical aging on the intrinsic activity of the catalyst was investigated in alkaline media by means of continuous cyclic voltammetry. A change in the material properties could be observed, which was accompanied by a substantial decrease in its intrinsic activity. [Figure not available: see fulltext.] © 2018, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature.

The high-entropy-alloy Al0.7CoCrFeNi (molar ratio) was prepared by vacuum arc melting followed by directional solidification (DS) with <001> oriented seed. The unique lamellar-dendrite microstructure was obtained over a wide cooling rate range. During solidification, Fe and Co are prone to segregate to the dendrite, while Cr and Al segregate to interdendrite. The solute pile-up of Cr and Al at the solid/liquid interface leads to the dendritic solidification. During the following cooling process, the BCC phase precipitates from the FCC dendrite to form the lamellar structure, while the ordered B2 phase precipitates from the interdendrite. Moreover, the lamellar spacing is significantly refined with increasing cooling rate, resulting in the higher hardness and compressive yield strength. Directional solidification is proved to be an efficient way to improve the mechanical properties of multi-phases high-entropy alloys. © 2017 Elsevier Ltd

Nanoscale solute segregation to or near lattice defects is a coupled diffusion and trapping phenomenon that occurs in superalloys at high temperatures during service. Understanding the mechanisms underpinning this crucial process will open pathways to tuning the alloy composition for improving the high-temperature performance and lifetime. Here, we introduce an approach combining atom probe tomography with high-end scanning electron microscopy techniques, in transmission and backscattering modes, to enable direct investigation of solute segregation to defects generated during high-temperature deformation such as dislocations in a heat-treated Ni-based superalloy and planar faults in a CoNi-based superalloy. Three protocols were elaborated to capture the complete structural and compositional nature of the targeted defect in the alloy. © 2018 The Author(s)

Shear testing can contribute to a better understanding of the plastic deformation of Ni-base superalloy single crystals. In the present study, shear testing is discussed with special emphasis placed on its strengths and weaknesses. Key mechanical and microstructural results which were obtained for the high-temperature (T ≈ 1000 °C) and low-stress (τ ≈ 200 MPa) creep regime are briefly reviewed. New 3D stereo STEM images of dislocation substructures which form during shear creep deformation in this regime are presented. It is then shown which new aspects need to be considered when performing double shear creep testing at lower temperatures (T < 800 °C) and higher stresses (τ > 600 MPa). In this creep regime, the macroscopic crystallographic [11−2](111) shear system deforms significantly faster than the [01−1](111) system. This represents direct mechanical evidence for a new planar fault nucleation scenario, which was recently suggested (Wu et al. in Acta Mater 144:642–655, 2018). The double shear creep specimen geometry inspired a micro-mechanical in-situ shear test specimen. Moreover, the in-situ SEM shear specimen can be FIB micro-machined from prior dendritic and interdendritic regions. Dendritic regions, which have a lower γ′ volume fraction, show a lower critical resolved shear stress. © 2018 The Author(s)

The Ni(P2N2)2 catalysts are among the most efficient non-noble-metal based molecular catalysts for H2 cycling. However, these catalysts are O2 sensitive and lack long term stability under operating conditions. Here, we show that in a redox silent polymer matrix the catalyst is dispersed into two functionally different reaction layers. Close to the electrode surface is the "active" layer where the catalyst oxidizes H2 and exchanges electrons with the electrode generating a current. At the outer film boundary, insulation of the catalyst from the electrode forms a "protection" layer in which H2 is used by the catalyst to convert O2 to H2O, thereby providing the "active" layer with a barrier against O2. This simple but efficient polymer-based electrode design solves one of the biggest limitations of these otherwise very efficient catalysts enhancing its stability for catalytic H2 oxidation as well as O2 tolerance. © 2018 The Author(s).

The segregation of solutes at dislocations in a polycrystalline and a single crystal nickel-based superalloy is studied. Our observations confirm the often assumed but yet unproven diffusion along dislocations via pipe diffusion. Direct observation and quantitative, near-atomic scale segregation of chromium and cobalt at dislocations within γ' precipitates and at interfacial dislocations leading to the partial or complete dissolution of γ' precipitates at elevated temperatures is presented. Our results allow us to elucidate the physical mechanism by which pipe diffusion initiates the undesirable dissolution of γ' precipitates. © 2017 Acta Materialia Inc.

Mo-Si-B alloys are potential creep resistant materials for accessing harsh loading scenarios beyond Ni-based superalloys due to their excellent mechanical performance at ultra-high temperatures (> 1200 °C). Here, we report on the fabrication through laser additive manufacturing of a Mo rich Mo-Si-B alloy with and without dispersion of oxide (La2O3) particles. The major phase in the solidified material is dendritic α-Mo. The inter-dendritic regions contain a mixture of the Mo5Si3 (T1) + Mo5SiB2 (T2) phases, and not the expected equilibrium Mo3Si + Mo5SiB2 (T2) phases. This combination of phases is shown to yield improved high temperature creep resistance but was only accessible through by addition of Nb, W or Ti that substitute Mo in the intermetallic phases. Whereas here it is attributed to the large undercooling in the small melt pool produced during laser processing. We show that this phase mixture, upon annealing, is stable at 1200 °C for 200 h. We also demonstrate successful dispersion of oxide particles mainly in the inter-dendritic regions leading to a high indentation fracture toughness of ∼18 MPa√m at room temperature. Toughening originates from crack trapping in the ductile α-Mo and the formation of micro-cracks and crack deflection in the vicinity of oxide particles. © 2018 Acta Materialia Inc.

To reveal the operating mechanisms of plastic deformation in an FCC high-entropy alloy, the activation volumes in CrMnFeCoNi have been measured as a function of plastic strain and temperature between 77 K and 423 K using repeated load relaxation experiments. At the yield stress, σy, the activation volume varies from ∼60 b3 at 77 K to ∼360 b3 at 293 K and scales inversely with yield stress. With increasing plastic strain, the activation volume decreases and the trends follow the Cottrell-Stokes law, according to which the inverse activation volume should increase linearly with σ−σy (Haasen plot). This is consistent with the notion that hardening due to an increase in the density of forest dislocations is naturally associated with a decrease in the activation volume because the spacing between dislocations decreases. The values and trends in activation volume agree with theoretical predictions that treat the HEA as a high-concentration solid-solution-strengthened alloy. These results demonstrate that this HEA deforms by the mechanisms typical of solute strengthening in FCC alloys, and thus indicate that the high compositional/structural complexity does not introduce any new intrinsic deformation mechanisms. © 2017 Acta Materialia Inc.

Abstract: A continuously operated flow setup with fixed-bed reactor and online gas analysis enabled kinetic investigations of catalysts for the carbon dioxide reforming of methane under industrially relevant conditions at temperatures up to 1000 °C and at pressures up to 20 bar. A coaxial reactor design consisting of an inner- and an outer highly alloyed steel tube allowed obtaining axial temperature profiles by means of a moveable thermocouple. A NiAl2O4-based catalyst was tested at 820 °C and pressures of 1, 10 or 20 bar and compared to a conventional Ni catalyst used for steam reforming of methane. A significant cold spot was detected even when using only 10 mg of catalysts diluted in 1 g of silicon carbide. The specifically designed NiAl2O4/Al2O3 dry reforming catalyst with a high dispersion of the active Ni0 phase was found to be far superior to the conventional steam reforming catalyst. Graphical Abstract: [Figure not available: see fulltext.] © 2018, Springer Science+Business Media, LLC, part of Springer Nature.

Co-Ni-Ga high-temperature shape memory alloys (HT-SMAs) are well-known candidate materials for damping applications at elevated temperatures. Recent studies showed that upon heat treatment in stress-induced martensite under compressive loads transformation temperatures can be increased significantly, qualifying Co-Ni-Ga for HT-actuation. The increase in transformation temperatures is related to a change in chemical order recently validated via neutron diffraction experiments. Since SMAs show distinct tension-compression asymmetry in terms of theoretical transformation strains and bearable stresses, understanding the impact of martensite aging in tension is crucial for future applications. The current results indicate that martensite aging in tension provides for a further improvement in functional properties. © 2018 The Author(s).

Different Ni/ZrO2 catalysts were prepared and tested for the hydrodeoxygenation (HDO) reaction of guaiacol. It was shown that the preparation mode of the ZrO2 support has a significant influence on the catalytic results, as remaining elements like Si and Na from the preparation can change the material properties. The influence of Si and Na onto these material properties, which were especially surface acidity and oxygen vacancy concentration, could be clarified. It could be also rationalized, how the change of these properties affects the results of the HDO reaction. Furthermore, it was demonstrated that the oxygen vacancy concentration is an important factor for the catalytic performance, although this property has hardly been considered in the design of HDO catalysts so far. La doping was found to be an efficient strategy to tune the oxygen vacancy concentration, and by using this approach the catalytic performance of the catalyst could be improved remarkably. © 2018

A set of advanced single crystalline γ′ strengthened Co-base superalloys with at least nine alloying elements (Co, Ni, Al, W, Ti, Ta, Cr, Si, Hf, Re) has been developed and investigated. The objective was to generate multinary Co-base superalloys with significantly improved properties compared to the original Co-Al-W-based alloys. All alloys show the typical γ/γ′ two-phase microstructure. A γ′ solvus temperature up to 1174 °C and γ′ volume fractions between 40 and 60 pct at 1050 °C could be achieved, which is significantly higher compared to most other Co-Al-W-based superalloys. However, higher contents of Ti, Ta, and the addition of Re decrease the long-term stability. Atom probe tomography revealed that Re does not partition to the γ phase as strongly as in Ni-base superalloys. Compression creep properties were investigated at 1050 °C and 125 MPa in 〈001〉 direction. The creep resistance is close to that of first generation Ni-base superalloys. The creep mechanisms of the Re-containing alloy was further investigated and it was found that the deformation is located preferentially in the γ channels although some precipitates are sheared during early stages of creep. The addition of Re did not improve the mechanical properties and is therefore not considered as a crucial element in the design of future Co-base superalloys for high temperature applications. Thermodynamic calculations describe well how the alloying elements influence the transformation temperatures although there is still an offset in the actual values. Furthermore, a full set of elastic constants of one of the multinary alloys is presented, showing increased elastic stiffness leading to a higher Young’s modulus for the investigated alloy, compared to conventional Ni-base superalloys. The oxidation resistance is significantly improved compared to the ternary Co-Al-W compound. A complete thermal barrier coating system was applied successfully. © 2018, The Minerals, Metals & Materials Society and ASM International.

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.

This work provides a comparative and comprehensive study of the indentation hardness and indentation modulus of iron-rich borides and carboborides of types Fe2B, Fe3(C,B), and Fe23(C,B)6. In addition, the hardness and elastic modulus of Cr-rich M7C are investigated for comparative purposes. We investigated the impact of increasing B content and indentation size effect (ISE). The phases of interest were stabilized in cast Fe-C-B alloys that varied with respect to the B / (B + C) ratio and heat treatment. The resulting microstructures were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD), and wavelength X-ray spectroscopy (WDS). Dynamic in-situ nanoindentation experiments based on the method of continuous stiffness measurement (CSM) were coupled to SEM and EBSD investigations to determine the mechanical properties of the individual borides and carboborides as a function of the indentation depth. The results were compared to values obtained for the Cr-rich M7C3 carbide. It was found that the hardness of the B-rich Fe3(C,B) phase is considerably higher than pure Fe3C and increases with increasing B content. The ISE was present in all investigated phases, and the hardness decreased as a function of indentation depth. The hardness at infinite indentation depth H0 was estimated according to the model of Nix and Gao. The Fe2B phase was found to be the hardest phase (H0 = 19.04 GPa), followed by M7C3 (H0 = 16.43 GPa), Fe3(C,B) (H0 = 11.18 to 12.24 GPa), and Fe23(C,B)6 (H0 = 10.39 GPa). © 2017 Elsevier Inc.

The present work studies the nucleation of planar faults in the early stages of low temperature (750 °C) and high stress (800 MPa) creep of a Ni-base single crystal superalloy (SX). Two families of 60° dislocations with different Burgers vectors were detected in the transmission electron microscope (TEM). These can react and form a planar fault in the γ′ phase. A 2D discrete dislocation model helps to rationalize a sequence of events which lead to the nucleation of a planar fault. First, one 60° channel dislocation approaches another 60° interface dislocation with a different Burgers vector. At a distance of 5 nm, it splits up into two Shockley partials. The interface dislocation is pushed into the γ′-phase where it creates a small antiphase boundary. It can only move on when the leading Shockley partial joins it and creates an overall 1/3<112> superdislocation. This process is fast and therefore is difficult to observe. The results obtained in the present work contribute to a better understanding of the processes which govern the early stages of low temperature and high stress primary creep of SX. © 2017 Acta Materialia Inc.

The study is focused on Ni-ion release rates from NiTi surfaces exposed in the cell culture media and human vascular endothelial cell (HUVEC) culture environments. The NiTi surface layers situated in the depth of 70 μm below a NiTi oxide scale are affected by interactions between the NiTi alloys and the bio-environments. The finding was proved with use of inductively coupled plasma mass spectrometry and electron microscopy experiments. As the exclusive factor controlling the Ni-ion release rates was not only thicknesses of the oxide scale, but also the passivation depth, which was two-fold larger. Our experimental data strongly suggested that some other factors, in addition to the Ni concentration in the oxide scale, admittedly hydrogen soaking deep below the oxide scale, must be taken into account in order to rationalize the concentrations of Ni-ions released into the bio-environments. The suggested role of hydrogen as the surface passivation agent is also in line with the fact that the Ni-ion release rates considerably decrease in NiTi samples that were annealed in controlled hydrogen atmospheres prior to bio-environmental exposures. © 2017 Elsevier B.V.

Rejuvenation of the initially hot isostatic pressing (HIP) heat-treated single-crystal Ni-base superalloy (SX) ERBO/1 was examined experimentally and via phase field simulation to establish rejuvenation treatments as a cost-effective alternative for another interval of service life. Creep was performed at 950 °C and 350 MPa, and the specimens were crept to 0.6 pct (creep rate minimum) or 2 pct strain, respectively. A slight coarsening of the γ/γ′ microstructure was observed experimentally and via simulation at 0.6 pct and rafting at 2 pct strain. The damaged microstructures were rejuvenated in a novel hot isostatic press that provides fast quenching rates before the same specimens were recrept under the same initial creep conditions. High-resolution microscopy proves that the rejuvenation re-establishes the original γ/γ′ microstructure in the dendrite core of the precrept specimens (0.6 and 2 pct). However, the interdendritic areas of the 2 pct precrept and rejuvenated specimen still contain elongated γ′ particles enwrapped by interfacial dislocation networks that survived the applied rejuvenation. The subsequent experimental and simulated creep tests after rejuvenation demonstrated that the creep behavior is only reproducible by the proposed rejuvenation for specimens that had crept until the end of the primary creep regime. © 2018 The Minerals, Metals & Materials Society and ASM International

We characterized the morphology, substructure and crystallography of lenticular martensite in a Fe-Ni-C alloy by means of electron backscatter diffraction and scanning electron microscopy. Electron backscatter diffraction maps were used to determine the orientation relationship between austenite and martensite across large regions of the microstructure. We employed orientation distribution functions as a statistical representation method for the observed orientation relationships. High-resolution point-to-point scans were used to normalize the effects of the orientation changes in the austenite caused by the plastic deformation during the formation of lenticular martensite. The analysis revealed that most of the transformation in this material follows an orientation relationship close to the one proposed by Greninger and Troiano. © 2017 Acta Materialia Inc.

The present work introduces a novel circular notched miniature tensile creep (CNMTC) specimen which is used to study the influence of notches on creep and of multiaxial stress states on microstructural evolution in Ni-based single crystal (SX) superalloys. It is briefly discussed how mild circular notches affect the stress state in the notch root of a tensile bar during elastic loading. Then the stress redistribution under creep conditions is calculated using the finite element method (FEM), assuming isotropic material behavior. Two series of interrupted creep experiments with the Ni-based single crystal superalloy ERBO1 (CMSX-4 type) were then performed at 950 °C, with flat uniaxial miniature tensile creep (FUMTC) and CNMTC <100> specimens, respectively. The evolution of cavities and microcracks in both types of specimens was carefully analyzed after 81, 169, and 306 h. In the uniaxial experiments, a growth of cast pores and the formation of new creep cavities were observed. These degradation processes were much less pronounced in the circular notched specimens. The results of the present work are discussed in the light of previous findings on the influence of multiaxial stress states on creep in single crystal superalloys. © 2017 Elsevier B.V.

We report first-principles calculations for determining the phase relationships in multi-component cathode materials. We investigate the effect of delithiation on the phase stability, chemical potential, and open circuit voltage for a selection of cathode materials based on Li-Mn-Ni oxides at various temperatures. Entropic contributions are included by calculating the phonon frequencies in the harmonic approximation. The open circuit voltage in multi-component systems is estimated by a convex hull approach. We confirm that spinel-like phases are predominant during the charging process of layered Li-Mn-O cathode materials and that the addition of Ni reduces the spinel content. The analysis of phase stability upon delithiation suggests that the Li2MnO3 component in the Li2MnO3·Li(Mn,Ni)O2 electrode material should not exceed 60% and that the amount of Ni in the LiMnO2 component should be above 40 at% for minimizing spinel-type phase formation and minimizing oxygen formation. Using the computed structural stability at room temperature, we derive property maps for the design of Li-Mn-Ni-O cathode materials. © The Royal Society of Chemistry 2018.

The electrochemical oxidation of the biorefinery product 5-(hydroxymethyl)furfural (HMF) to 2,5-furandicarboxylic acid (FDCA), an important platform chemical for the polymer industry, is receiving increasing interest. FDCA-based polymers such as polyethylene 2,5-furandicarboxylate (PEF) are sustainable candidates for replacing polyethylene terephthalate (PET). Herein, we report the highly efficient electrocatalytic oxidation of HMF to FDCA, using Ni foam modified with high-surface-area nickel boride (NixB) as the electrode. Constant potential electrolysis in combination with HPLC revealed a high faradaic efficiency of close to 100 % towards the production of FDCA with a yield of 98.5 %. Operando electrochemistry coupled to ATR-IR spectroscopy indicated that HMF is oxidized preferentially via 5-hydroxymethyl-2-furancarboxylic acid rather than via 2,5-diformylfuran, which is in agreement with HPLC results. This study not only reports a low-cost active electrocatalyst material for the electrochemical oxidation of HMF to FDCA, but additionally provides insight into the reaction pathway. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

The development of new Ni-base superalloys with a complex composition consisting of eight or more alloying elements is a challenging task. The experimental state-of-the-art development cycle is based on the adaption of already existing compositions. Although new alloy compositions with potentially improved material properties are expected to be similar to already known superalloys, this procedure impedes efficiently finding these compositions in the large multi-dimensional design-space of all alloying elements. Modern alloy development combines numerical optimization methods with experimental validation to guide the development towards promising compositions. In this work, an improved numerical multi-criteria optimization tool using CALPHAD calculations and semi-empirical models for alloy development is presented. The model improvements to its predecessor are described and the successful application for the development of rhenium-free single-crystal Ni-base superalloys ERBO/13 and ERBO/15 is revisited. The optimization tool is described and the designed alloys are discussed regarding phase stability. Finally, a possible phase stability model extending the optimization tool and improving the alloy composition predictions is presented. © 2018, The Author(s).

An in-situ SEM micromechanical test technique is used to investigate the response of a Ni-based single crystal superalloy to double shear loading. The present work shows that micro double shear testing can detect mechanical differences between interdendritic and dendritic regions with γ′-volume fractions of 77% and 72%, respectively, i.e., the interdendritic regions exhibit a larger flow stress than the dendritic regions. These micromechanical differences are apparent when micro double shear specimens are oriented for single-slip while they appear to be overshadowed by dislocation interactions, when multiple-slip is promoted. Sudden deformation events are observed to occur concomitantly with the formation of shear steps (localized plastic deformation) at the surface of the shear zones during single-slip. The micro double shear specimens oriented for single-slip show very low work-hardening. In contrast, much higher stresses are required to plastically deform micro double shear specimens oriented for multiple-slip which exhibit stronger work-hardening. No sudden deformation events could be detected for multiple-slip which results in a more homogeneous deformation of the shear zones (absence of localized plastic deformation). © 2018 Acta Materialia Inc.

A novel hybrid core-shell structure of ZnO nanowires (NWs)/Ni as a pseudocapacitor electrode was successfully fabricated by atomic layer deposition of a nickel shell, and its capacitive performance was systemically investigated. Transmission electron microscopy and X-ray photoelectron spectroscopy results indicated that the NiO was formed at the interface between ZnO and Ni where the Ni was oxidized by ZnO during the ALD of the Ni layer. Electrochemical measurement results revealed that the Ti/ZnO NWs/Ni (1500 cycles) electrode with a 30 nm thick Ni-NiO shell layer had the best supercapacitor properties including ultrahigh specific capacitance (∼2440 F g-1), good rate capability (80.5%) under high current charge-discharge conditions, and a relatively better cycling stability (86.7% of the initial value remained after 750 cycles at 10 A g-1). These attractive capacitive behaviors are mainly attributed to the unique core-shell structure and the combined effect of ZnO NW arrays as short charge transfer pathways for ion diffusion and electron transfer as well as conductive Ni serving as channel for the fast electron transport to Ti substrate. This high-performance Ti/ZnO NWs/Ni hybrid structure is expected to be one of a promising electrodes for high-performance supercapacitor applications. © 2017 American Chemical Society.

The mechanical properties of face-centered cubic (fcc) metals are influenced by physical parameters of the material, such as the stacking fault energy (SFE). It is known that a low SFE improves the strain hardening, thus increasing the abrasive wear resistance over a wide temperature range. Therefore, investigating the SFE is highly important for the characterization of the physical properties of materials at elevated temperatures. In the present study, the SFE of several austenitic stainless steels was determined by using a calculation model based on Calphad data for investigating the SFE depending on temperature. It can be shown that the lowest SFE value was calculated for the system Fe-27Cr-22Ni including interstitial elements (C+N < 0.1 mass%). This constitution was found by increasing the Cr content to a maximum considering the thermal austenite stability. In this context, the influence on the SFE and austenitic stability of the main alloying elements (Cr, Ni) were examined in detail. To determine the SFE values experimentally, alloys were produced on a laboratory scale and analyzed using X-ray diffraction line-profile analysis (XRD-LP). The results show good match between the calculated and measured SFE values. The calculations show that an increase of the Cr/Ni ratio decreases the SFE in FeCrNi alloys. Moreover, the represented calculation model is suitable for estimating the SFE over a wide temperature range, avoiding costly and time-consuming experiments. © 2018 Acta Materialia Inc.

Hydrodeoxygenation (HDO) of lignocellulose-derived pyrolysis oils offers an option to produce fuel substitutes. However, catalyst deactivation and stability constitute a significant issue. Herein, the dependence of stability and activity of Ni2P/SiO2 HDO catalysts on the support surface polarity is addressed in detail. The support surface polarity was adjusted by copolymerizing tetraethyl orthosilicate (TEOS) with different types and amounts of organosilanes by a sol–gel process in the presence of nickel nitrate and citric acid. After thermal treatment under an inert atmosphere, Ni/SiO2 precursors were formed. They were converted into Ni2P/SiO2 catalysts by using NaH2PO2 as a PH3 source. The catalyst surface polarity was characterized by inverse gas chromatography measurements of the free energy of methanol adsorption, and specific and dispersive surface energies derived from polar and nonpolar probe molecule adsorption. The correlation between catalyst performance and support surface polarity indicates that, to prevent deactivation of the catalyst by water under reaction conditions, the affinity of the support towards polar substances must be decreased below a threshold value. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

For the purpose of good reproduction and prediction of creep deformation of nickel-base single crystal superalloys at intermediate temperatures, a phenomenological creep model is developed, which accounts for the typical γ/γ′ microstructure and the individual thermally activated elementary deformation processes in different phases. The internal stresses from γ/γ′ lattice mismatch and deformation heterogeneity are introduced through an efficient method. The strain hardening, the Orowan stress, the softening effect due to dislocation climb along γ/γ′ interfaces and the formation of dislocation ribbons, and the Kear-Wilsdorf-lock effect as key factors in the main flow rules are formulated properly. By taking the cube slip in slip systems and twinning mechanisms into account, the creep behavior for [110] and [111] loading directions are well captured. Without specific interaction and evolution of dislocations, the simulations of this model achieve a good agreement with experimental creep results and reproduce temperature, stress and crystallographic orientation dependences. It can also be used as the constitutive relation at material points in finite element calculations with complex boundary conditions in various components of superalloys to predict creep behavior and local stress distributions. © 2018 IOP Publishing Ltd.

This study investigated the influence of segregations on hydrogen environment embrittlement (HEE) of AISI 304L type austenitic stainless steels. The microstructure of tensile specimens, that were fabricated from commercially available AISI 304L steels and tested by means of small strain-rate tensile tests in air as well as hydrogen gas at room temperature, was investigated by means of combined EDS and EBSD measurements. It was shown that two different austenitic stainless steels having the same nominal alloy composition can exhibit different susceptibilities to HEE due to segregation effects resulting from different production routes (continuous casting/electroslag remelting). Local segregation-related variations of the austenite stability were evaluated by thermodynamic and empirical calculations. The alloying element Ni exhibits pronounced segregation bands parallel to the rolling direction of the material, which strongly influences the local austenite stability. The latter was revealed by generating and evaluating two-dimensional distribution maps for the austenite stability. The formation of deformation-induced martensite was shown to be restricted to segregation bands with a low Ni content. Furthermore, it was shown that the formation of hydrogen induced surface cracks is strongly coupled with the existence of surface regions of low Ni content and accordingly low austenite stability. In addition, the growth behavior of hydrogen-induced cracks was linked to the segregation-related local austenite stability. © 2018 The Author(s).

In order to design more powerful electrocatalysts, developing our understanding of the role of the surface structure and composition of widely abundant bulk materials is crucial. This is particularly true in the search for alternative hydrogen evolution reaction (HER) catalysts to replace platinum. We report scanning electrochemical cell microscopy (SECCM) measurements of the (111)-crystal planes of Fe4.5Ni4.5S8, a highly active HER catalyst. In combination with structural characterization methods, we show that this technique can reveal differences in activity arising from even the slightest compositional changes. By probing electrochemical properties at the nanoscale, in conjunction with complementary structural information, novel design principles are revealed for application to rational material synthesis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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

Inspired by our recent finding that Fe4.5Ni4.5S8 rock is a highly active electrocatalyst for HER, we set out to explore the influence of the Fe:Ni ratio on the performance of the catalyst. We herein describe the synthesis of (FexNi1-x)9S8 (x = 0-1) along with a detailed elemental composition analysis. Furthermore, using linear sweep voltammetry, we show that the increase in the iron or nickel content, respectively, lowers the activity of the electrocatalyst toward HER. Electrochemical surface area analysis (ECSA) clearly indicates the highest amount of active sites for a Fe:Ni ratio of 1:1 on the electrode surface pointing at an altered surface composition of iron and nickel for the other materials. Specific metal-metal interactions seem to be of key importance for the high electrocatalytic HER activity, which is supported by DFT calculations of several surface structures using the surface energy as a descriptor of catalytic activity. In addition, we show that a temperature increase leads to a significant decrease of the overpotential and gain in HER activity. Thus, we showcase the necessity to investigate the material structure, composition and reaction conditions when evaluating electrocatalysts. © 2017 American Chemical Society.

Miniature tensile creep specimens are used to investigate the effect of mild circular notches on microstructural evolution during [001] tensile creep of a Ni-base single crystal superalloy. Creep deformed material states from a uniaxial (950 °C, uniaxial stress: 300 MPa) and a circular notched creep specimen (950 °C, net section stress in notch root: 300 MPa) are compared. For both types of tests, creep experiments were interrupted after 81, 169 and 306 h. Quantitative scanning electron microscopy (SEM) is used to assess the evolution of the γ/γ′-microstructure from rafting to topological inversion. Scanning transmission electron microscopy (STEM) was applied to study the evolution of dislocation densities during creep. As a striking new result it is shown that in circular notched specimen, the microstructural evolution is well coupled to the kinetics of the stress redistribution during creep. Rafting, the directional coarsening of the γ′-phase, and the increase of γ-channel dislocation density, start in the notch root before the center of the specimen is affected. When stresses in the circular notched specimens are fully redistributed, the microstructural differences between the notch root and the center of the circular notched specimen disappear. The comparison of the mechanical data and the microstructural findings in uniaxial and circular notched specimens contribute to a better understanding of the role of mild notches, of stress multiaxiality and of strain accumulation in the microstructure evolution of single crystal Ni-base superalloys during creep. The results obtained in the present work are discussed in the light of previous work published in the literature. © 2018 Acta Materialia Inc.

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

For several decades, the formation of carbon(C)-rich domains upon room temperature aging of supersaturated martensite has been a matter of debate. C-rich tweed-like patterns are observed to form after short aging times at room temperature and coarsen upon further aging. Here, we present a systematic atomic-scale investigation of carbide formation in Fe-15Ni-1C (wt.%) martensite after two to three years of isothermal room temperature aging by a combination of atom probe tomography and transmission electron microscopy. Owing to the sub-zero martensite start temperature of −25 °C, a fully austenitic microstructure is maintained at room temperature and the martensitic phase transformation is initiated during quenching in liquid nitrogen. In this way, any diffusion and redistribution of C in martensite is suppressed until heating up the specimen and holding it at room temperature. The microstructural changes that accompany the rearrangement of C atoms have been systematically investigated under controlled isothermal conditions. Our results show that after prolonged room temperature aging nanometer-sized, plate-shaped η-Fe2C carbides form with a macroscopic martensite habit plane close to {521}. The orientation relationship between the η-Fe2C carbides and the parent martensite grain (α′) follows [001]α’//[001]η, (1¯10) α’//(020)η. The observation of η-Fe2C–carbide formation at room temperature is particularly interesting, as transition carbides have so far only been reported to form above 100 °C. After three years of room temperature aging a depletion of Fe is observed in the η carbide while Ni remains distributed homogenously. This implies that the substitutional element Fe can diffuse several nanometers in martensite at room temperature within three years. © 2018

SrTiO3 is a well-known photocatalyst inducing overall water splitting when exposed to UV irradiation of wavelengths <370 nm. However, the apparent quantum efficiency of SrTiO3 is typically low, even when functionalized with nanoparticles of Pt or Ni@NiO. Here, we introduce a simple solid-state preparation method to control the incorporation of magnesium into the perovskite structure of SrTiO3. After deposition of Pt or Ni@NiO, the photocatalytic water-splitting efficiency of the Mg:SrTiOx composites is up to 20 times higher compared to SrTiO3 containing similar catalytic nanoparticles, and an apparent quantum yield (AQY) of 10 % can be obtained in the wavelength range of 300–400 nm. Detailed characterization of the Mg:SrTiOx composites revealed that Mg is likely substituting the tetravalent Ti ion, leading to a favorable surface–space–charge layer. This originates from tuning of the donor density in the cubic SrTiO3 structure by Mg incorporation and enables high oxygen-evolution rates. Nevertheless, interfacing with an appropriate hydrogen evolution catalyst is mandatory and non-trivial to obtain high-performance in water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Synthetic pentlandite (Fe4.5Ni4.5S8) is a promising electrocatalyst for hydrogen evolution, demonstrating high current densities, low overpotential, and remarkable stability in bulk form. The depletion of sulfur from the surface of this catalyst during the electrochemical reaction has been proposed to be beneficial for its catalytic performance, but the role of sulfur vacancies and the mechanism determining the reaction kinetics are still unknown. We have performed electrochemical operando studies of the vibrational dynamics of pentlandite under hydrogen evolution reaction conditions using 57Fe nuclear resonant inelastic X-ray scattering. Comparing the measured Fe partial vibrational density of states with density functional theory calculations, we have demonstrated that hydrogen atoms preferentially occupy substitutional positions replacing pre-existing sulfur vacancies. Once all vacancies are filled, the protonation proceeds interstitially, which slows down the reaction. Our results highlight the beneficial role of sulfur vacancies in the electrocatalytic performance of pentlandite and give insights into the hydrogen adsorption mechanism during the reaction. © 2017 American Chemical Society.

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

Due to their large latent heats, pseudoelastic Ni–Ti-based shape memory alloys (SMAs) are attractive candidate materials for ferroic cooling, where elementary solid-state processes like martensitic transformations yield the required heat effects. The present work aims for a chemical and microstructural optimization of Ni–Ti for ferroic cooling. A large number of Ni–Ti-based alloy compositions were evaluated in terms of phase transformation temperatures, latent heats, mechanical hysteresis widths and functional stability. The aim was to identify material states with superior properties for ferroic cooling. Different material states were prepared by arc melting, various heat treatments and thermo-mechanical processing. The cooling performance of selected materials was assessed by differential scanning calorimetry, uniaxial tensile loading/unloading, and by using a specially designed ferroic cooling demonstrator setup. A Ni(Formula presented.)Ti(Formula presented.)Cu5V(Formula presented.) SMA was identified as a potential candidate material for ferroic cooling. This material combines extremely stable pseudoelasticity at room temperature and a very low hysteresis width. The ferroic cooling efficiency of this material is four times higher than in the case of binary Ni–Ti. © 2017 World Scientific Publishing Company

Transients in the composition of Ni@NiOx core-shell co-catalysts deposited on SrTiO3 are discussed on the basis of state-of-the-art continuous analysis of photocatalytic water splitting, and post-XPS and TEM analyses. The formation of excessive hydrogen (H2:O2 ≫ 2) in the initial stages of illumination demonstrates oxidation of Ni(OH)2 to NiOOH (nickel oxyhydroxide), with the latter catalyzing water oxidation. A disproportionation reaction of Ni and NiOOH, yielding Ni(OH)2 with residual embedded Ni, occurs when illumination is discontinued, which explains repetitive transients in (excess) hydrogen and oxygen formation when illumination is reinitiated. (Chemical Equation Presented). © 2017 American Chemical Society.

The authors uses laser additive manufacturing (LAM) as a combinatorial method for synthesizing microstructurally and compositionally piecewise graded bulk alloys. Authors fabricate blocks consisting of a sequence of ≈500μm thick tool steel layers, each with different chemical composition, by laser metal deposition where alloy powders are deposited layer-wise on a substrate. The reference materials are a Cr-Mo-V hot working tool steel and a Ni-based maraging steel. The layers between them consist of corresponding blends of the two materials with varying composition from layer to layer (alloy volume fractions 80:20, 60:40, 40:60, and 20:80). The bulk alloy is hot rolled and heat treated. Subsequently each layer is characterized for microstructure, chemical composition and mechanical properties using electron back scatter diffraction, tensile testing, and indentation. The approach is an efficient high-throughput method enabling rapid probing of novel compositional alloy blends. It can be applied for finding new alloys both, by LAM and for LAM. For the tool steel blends synthesized here, authors observe that the Cr-Mo-V tool steel, when mixed with the Ni-base maraging steel, can be continuously tuned for a strength-ductility profile in the range of 800-1650MPa strength and 15-25% tensile elongation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Due to the layer-by-layer build-up of additively manufactured parts, the deposited material experiences a cyclic re-heating in the form of a sequence of temperature pulses. In the current work, this “intrinsic heat treatment (IHT)” was exploited to induce the precipitation of NiAl nanoparticles in an Fe-19Ni-xAl (at%) model maraging steel, a system known for rapid clustering. We used Laser Metal Deposition (LMD) to synthesize compositionally graded specimens. This allowed for the efficient screening of effects associated with varying Al contents ranging from 0 to 25 at% and for identifying promising concentrations for further studies. Based on the existence of the desired martensitic matrix, an upper bound for the Al concentration of 15 at% was defined. Owing to the presence of NiAl precipitates as observed by Atom Probe Tomography (APT), a lower bound of 3–5 at% Al was established. Within this concentration window, increasing the Al concentration gave rise to an increase in hardness by 225 HV due to an exceptionally high number density of 1025 NiAl precipitates per m3, as measured by APT. This work demonstrates the possibility of exploiting the IHT of the LMD process for the production of samples that are precipitation strengthened during the additive manufacturing process without need for any further heat treatment. © 2017

A CrMnFeCoNi high-entropy alloy was investigated by nanoindentation from room temperature to 400 °C in the nanocrystalline state and cast plus homogenized coarse-grained state. In the latter case a âŒ100)-orientated grain was selected by electron back scatter diffraction for nanoindentation. It was found that hardness decreases more strongly with increasing temperature than Young's modulus, especially for the coarse-grained state. The modulus of the nanocrystalline state was slightly higher than that of the coarse-grained one. For the coarse-grained sample a strong thermally activated deformation behavior was found up to 100-150 °C, followed by a diminishing thermally activated contribution at higher testing temperatures. For the nanocrystalline state, different temperature dependent deformation mechanisms are proposed. At low temperatures, the governing processes appear to be similar to those in the coarse-grained sample, but with increasing temperature, dislocation-grain boundary interactions likely become more dominant. Finally, at 400 °C, decomposition of the nanocrystalline alloy causes a further reduction in thermal activation. This is rationalized by a reduction of the deformation controlling internal length scale by precipitate formation in conjunction with a diffusional contribution. © 2017 Materials Research Society.

The element Re is known to be a very potent strengthener concerning the creep properties of Ni-base superalloys. In this paper the influence of Re on the properties of new γ′-strengthened Co-base superalloys is addressed. Atom probe tomography reveals that Re partitions preferentially to the γ phase, but not as pronounced as in ni-base superalloys. Nanoindentation and micro-pillar compression tests of the γ′ phase indicate an increase of the hardness and the critical resolved shear stress caused by a considerable concentration of Re in the γ′ phase. Creep investigations show that the positive effect of Re is by far not as pronounced as in Ni-base superalloys. Several effects, which can contribute to this behavior, such as the lower Re concentration in γ and hence a slightly reduced effective diffusion coefficient, a smaller diffusion barrier of Re in Co compared to Ni, a slightly lower lattice misfit and γ′ volume fraction of the Re-containing alloy, are discussed. © Materials Research Society 2017.

High-throughput methods were used to investigate a Ni-Co-Al thin film materials library, which is of interest for structural and functional applications (superalloys, shape memory alloys). X-ray diffraction (XRD) measurements were performed to identify the phase regions of the Ni-Co-Al system in its state after annealing at 600 °C. Optical, electrical, and magneto-optical measurements were performed to map functional properties and confirm XRD results. All results and literature data were used to propose a ternary thin film phase diagram of the Ni-Co-Al thin film system. © 2017 American Chemical Society.

LaNiO3 perovskite is an interesting precursor for Ni/La2O3 catalysts for the dry reforming of methane at high temperatures. Precursors have been synthesized by co-precipitation without, with 2.5 at%, and with 5 at% Ru doping. The presence of Ru leads to a stabilization of the perovskite structure and hinders the decomposition into NiO and Ruddlesden-Popper mixed oxides Lan+1NinO3n+1, which was observed for the Ru-free sample upon calcination at 1000 °C (n = 3). Upon reduction in hydrogen, a mechanism involving at least two steps was observed and the first major step was identified as the partial reduction of the precursor leading to a LaNiO2.5-like intermediate. The second major step is the reduction to Ni metal supported on La2O3 independent of the Ru content of the catalyst. In the presence of Ru, indications for Ni-Ru alloy formation and for a higher dispersion of the metallic phase were found. The catalytic activity in DRM of the catalyst containing 2.5% Ru was superior to the catalysts with more or without Ru. Furthermore, the propensity of coke formation was reduced by the presence of Ru. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We investigated hydrogen embrittlement in Ni-based superalloy 718 by tensile testing at slow strain rate (10−4 s−1) under continuous electrochemical hydrogen charging. Hydrogen-assisted cracking mechanisms were studied via electron backscatter diffraction (EBSD) analysis and electron channeling contrast imaging (ECCI). In order to elucidate the effects of stress or strain in the cracking mechanisms, material conditions with different strength levels were investigated, including samples in solution annealed (as water quenched) and 780 °C age-hardened states. The microstructure observations in the vicinity of the cracks enabled us to establish correlations between the microstructure, crack initiation sites, and crack propagation pathways. Fracture in the hydrogen-charged samples was dominated by localized plastic deformation. Strain-controlled transgranular cracking was caused by shear localization due to hydrogen-enhanced localized plasticity (HELP) and void nucleation and coalescence along {111} slip planes in both, the solution annealed and age-hardened materials. Stress-assisted intergranular cracking in the presence of hydrogen was only observed in the high strength age-hardened material, due to slip localization at grain boundaries, grain boundary triple junction cracking, and δ/γ-matrix interface cracking. To investigate the effect of δ-phase in crack propagation along grain boundaries, the over-aged state (aged at 870 °C) with different precipitation conditions for the δ-phase was also investigated. Observations confirmed that presence of δ-phase promotes hydrogen-induced intergranular failure by initializing micro-cracks from δ/γ interfaces. © 2017 Acta Materialia Inc.

Herein, we report on the versatile reactions of CH3C(CH2PPh2)3 as well as CH3Si(CH2PPh2)3 derived Ni-complexes. While Ni[CH3C(CH2PPh2)3] complexes reveal high stability, the Ni[CH3Si(CH2PPh2)3] analogs show rapid decomposition at room temperature and afford the unprecedented pseudo-tetrahedral phosphino methanide complex 5. We provide a detailed electronic structure of 5 from X-ray absorption and emission spectroscopy data analysis in combination with DFT calculations, as well as from comparison with structurally related complexes. A mechanistic study for the formation of complex 5 by reaction with BF4 − is presented, based on a comparison of experimental data with quantum chemical calculations. We also show a simple route towards isolable Ni(i)-complexes on the gram scale. © The Royal Society of Chemistry.

While bimetallic azacryptands are known to selectively coordinate CO2, there is little knowledge on how different substitution patterns of the azacryptand cage structure influence CO2 coordination. Stopped-flow UV-vis spectroscopy, electrochemical analysis and DFT calculations were performed on a series of dinickel azacryptands and showed different rates of CO2 coordination to the complexes. We herein present data showing that the different flexibility of the azacryptands is directly responsible for the difference in the CO2 uptake capability of dinickel azacryptand complexes. © 2017 The Royal Society of Chemistry.

Prompted by the impact of Ni-based support materials on the intrinsic activity of electrocatalysts, we investigated the influence of partial Co substitution by Ni during the reductive thermal synthesis of cobalt-cobalt phosphide nanoparticles from triphenylphosphine complexes. The obtained catalysts were characterised by X-ray diffraction and electrochemistry. Increasing the amount of Ni in the precursor complexes leads to materials with lower overpotential for the OER at low current densities, and lower Tafel slopes. Co nanoparticles, which are only formed in materials with low Ni content, increase the intrinsic material conductivity and reduce the OER overpotential at high current densities. © 2017

We introduce a new class of high-entropy alloys (HEAs), i.e., quinary (five-component) dual-phase (DP) HEAs revealing transformation-induced plasticity (TRIP), designed by using a quantum mechanically based and experimentally validated approach. Ab initio simulations of thermodynamic phase stabilities of Co20Cr20Fe40-xMn20Nix (x = 0–20 at. %) HEAs were performed to screen for promising compositions showing the TRIP-DP effect. The theoretical predictions reveal several promising alloys, which have been cast and systematically characterized with respect to their room temperature phase constituents, microstructures, element distributions and compositional homogeneity, tensile properties and deformation mechanisms. The study demonstrates the strength of ab initio calculations to predict the behavior of multi-component HEAs on the macroscopic scale from the atomistic level. As a prototype example a non-equiatomic Co20Cr20Fe34Mn20Ni6 HEA, selected based on our ab initio simulations, reveals the TRIP-DP effect and hence exhibits higher tensile strength and strain-hardening ability compared to the corresponding equiatomic CoCrFeMnNi alloy. © 2017 Acta Materialia Inc.

The overriding obstacle to mass production of hydrogen from water as the premium fuel for powering our planet is the frustratingly slow kinetics of the oxygen evolution reaction (OER). Additionally, inadequate understanding of the key barriers of the OER is a hindrance to insightful design of advanced OER catalysts. This study presents ultrathin amorphous high-surface area nickel boride (NixB) nanosheets as a low-cost, very efficient and stable catalyst for the OER for electrochemical water splitting. The catalyst affords 10 mA cm-2 at 0.38 V overpotential during OER in 1.0 m KOH, reducing to only 0.28 V at 20 mA cm-2 when supported on nickel foam, which ranks it among the best reported nonprecious catalysts for oxygen evolution. Operando X-ray absorption fine-structure spectroscopy measurements reveal prevalence of NiOOH, as well as Ni-B under OER conditions, owing to a Ni-B core at nickel oxyhydroxide shell (Ni-B at NiOxH) structure, and increase in disorder of the NiOxH layer, thus revealing important insight into the transient states of the catalyst during oxygen evolution. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nucleation is a key step during crystallization, but a complete understanding of the fundamental atomistic processes remains elusive. We investigate the mechanism of nucleation during solidification in nickel for various undercoolings using transition path sampling simulations. The temperature dependence of the free energy barriers and rate constants that we obtain is consistent with the predictions of classical nucleation theory and experiments. However, our analysis of the transition path ensemble reveals a mechanism that deviates from the classical picture of nucleation: the growing solid clusters have predominantly non-spherical shapes and consist of face-centered-cubic and random hexagonal-close-packed coordinated atoms surrounded by a cloud of prestructured liquid. The nucleation initiates in regions of supercooled liquid that are characterized by a high orientational order with structural features that predetermine the polymorph selection. These results provide atomistic insight not only into the nucleation mechanism of nickel but also into the role of the preordered liquid regions as precursors for crystallization. © 2017 Author(s).

Carbochlorination, a solvent-free top-down process, is a novel pathway for the hierarchization of zeolites. In contrast to other methods no further washing steps are required. The employed method should serve as a model system for the “upcycling” of coked and deactivated zeolites accumulated by the industry. In order to establish a basic understanding of the process, zeolite H-Y was taken as a model system and a thorough investigation of important reaction parameters, like chlorination temperature, time and concentration, carbon loading, and Si/Al ratio, was performed. Under optimized conditions, we have been able to hierarchize H-Y with high yield, doubling the mesopore volume while maintaining the crystallinity and surface area. © The Royal Society of Chemistry.

We systematically studied the microstructure, mechanical and physical properties of hyper-eutectic Fe – TiB2 high modulus steels (20 vol% TiB2) with (Si, Mn, Ni) and Cu additions for the formation of G-phase and Cu precipitates during ageing treatments. Alloying with Si, Mn and Ni led predominantly to pronounced solid solution strengthening, reaching tensile strength (UTS) values up to 1100 MPa after quenching. While G-phase formation could be observed in aged materials, its preferential formation on grain boundaries significantly deteriorated ductility. Its effects on strength were partially balanced by a decrease of grain boundary density. Additions of 1 and 2 wt% Cu, respectively, led to lower strength in the as quenched state, but also to significant strengthening via ageing. The peak ageing conditions as well as the Cu particle structure and size are comparable to values reported for Cu strengthened interstitial free steels and Fe-Cu alloys. Both alloying additions slightly lowered the specific elastic modulus of the HMS, most pronounced for Cu addition with a drop of about 3 GPa cm3 g− 1 per wt% and also promoted embrittlement. Microstructure-property relationships and consequences for future alloy design, especially towards more ductile hypo-eutectic HMS, are outlined and discussed. © 2017

A three-dimensional (3D) discrete dislocation dynamics (DDD) creep model is developed to investigate creep behavior under uniaxial tensile stress along the crystallographic [001] direction in Ni-base single crystal superalloys, which takes explicitly account of dislocation glide, climb and vacancy diffusion, but neglects phase transformation like rafting of γ′ precipitates. The vacancy diffusion model takes internal stresses by dislocations and mismatch strains into account and it is coupled to the dislocation dynamics model in a numerically efficient way. This model is helpful for understanding the fundamental creep mechanisms in superalloys and clarifying the effects of dislocation glide and climb on creep deformation. In cases where the precipitate cutting rarely occurs, e.g. due to the high anti-phase boundary energy and the lack of superdislocations, the dislocation glide in the γ matrix and the dislocation climb along the γ/γ′ interface dominate plastic deformation. The simulation results show that a high temperature or a high stress both promote dislocation motion and multiplication, so as to cause a large creep strain. Dislocation climb accelerated by high temperature only produces a small plastic strain, but relaxes the hardening caused by the filling γ channels and lets dislocations further glide and multiply. The strongest variation of vacancy concentration occurs in the horizontal channels, where more mixed dislocations exit and tend to climb. The increasing internal stresses due to the increasing dislocation density are easily overcome by dislocations under a high external stress that leads to a long-term dislocation glide accompanied by multiplication. © 2017 Elsevier Ltd

Ni-base single-crystal turbine blades are exposed to a combination of high temperatures and high stresses during their service life in high-pressure turbines of aero engines or stationary gas turbines. This unavoidably leads to various internal microstructural changes such as rafting and the formation of cavities. This study introduces a creep-rejuvenation-creep test cycle using one miniature Ni-base single-crystal creep specimen. A novel hot isostatic press providing high quenching rates was applied to rejuvenate the damaged microstructure of the specimen after the first high-temperature creep degradation before the same specimen was repeatedly creep-tested under the same initial creep conditions. After rejuvenating, microstructural results obtained from high-resolution microscopy prove that the creep cavities were closed, dislocation densities were re-set, and the original but now slightly finer γ/γ′-microstructure was restored without any recrystallization. The subsequent creep test of the rejuvenated specimen demonstrated that the proposed rejuvenation procedure in this work is a suitable method to reproduce the initial creep behavior and to thus prolong the lifetime of an already crept Ni-base single-crystal specimen. © 2017 Elsevier Ltd

Yttria stabilized zirconia (YSZ) is often applied as thermal barrier coating on metal parts as e.g. turbine blades made of nickel base super alloys. The coating process in combination with the preconditioning of the substrate material induces characteristic residual stress distributions in the coating system consisting of topcoat, bondcoat and the substrate material. Knowledge about the residual stress depth distribution in the coating and at the interfaces down to the substrate material is essential for the assessment of the mechanical integrity and the reliability of the coating. In this regard the stability of the microstructure and the residual stresses is of particular interest; hence this forms the scope of our investigations. Yttria (8 wt.%) stabilized zirconia with a NiCoCrAlY bondcoat was deposited by atmospheric plasma spraying (APS) at different spray conditions on a nickel base super alloy substrate material. The coatings were subjected to different heat-treatment processes, i.e. static aging and cyclic thermal loadings. Through surface scanning using neutron diffraction was carried out for the as sprayed condition and for the thermally loaded samples. Based on the measured diffraction data the stability of the microstructure (phases) and the residual strain/stresses through the depths of the coating system were assessed. © 2017 Elsevier B.V.

Ni-base superalloys are materials which are designed to resist extreme thermal and mechanical conditions. In this regard, an essential factor is their microstructure consisting of γ′ precipitates embedded in a γ matrix. The application of superalloys at high temperatures can however induce the topological phase inversion, where the γ′-phase topologically becomes the matrix phase, resulting in subpar material properties. In this work, the topological inversion is analyzed via experiment and phase-field simulation. The evolution of the microstructure has been quantified in the second generation single crystal Ni-base superalloy ERBO/1, which belongs to the family of CMSX-4, submitted to long-term aging at 1100° C for up to 250 h. Phase-field simulations carried out using a multi phase-field approach deliver insight into the microstructure evolution driven by the loss of coherency of the γ′ precipitates, which is induced by the accumulation of dislocations at the γ/γ′ interfaces. The obtained simulation results are in good agreement with the experimental results, and indicate that the mechanisms causing the topological inversion are linked to the accommodation of the lattice misfit, which enables coalescence and ripening of γ′ precipitates. © 2016 Acta Materialia Inc.

The scaling behavior of Ti-Ni-Cu shape memory thin-film micro- and nanowires of different geometry is investigated with respect to its influence on the martensitic transformation properties. Two processes for the highthroughput fabrication of Ti-Ni-Cu micro- to nanoscale thin film wire libraries and the subsequent investigation of the transformation properties are reported. The libraries are fabricated with compositional and geometrical (wire width) variations to investigate the influence of these parameters on the transformation properties. Interesting behaviors were observed: Phase transformation temperatures change in the range from 1 to 72 °C (austenite finish, (Af), 13 to 66 °C (martensite start, Ms) and the thermal hysteresis from -3.5 to 20 K. It is shown that a vanishing hysteresis can be achieved for special combinations of sample geometry and composition. © 2017 American Chemical Society.

Engineering of controlled hybrid nanocomposites creates one of the most exciting applications in the fields of energy materials and environmental science. The rational design and in situ synthesis of hierarchical porous nanocomposite sheets of nitrogen-doped graphene oxide (NGO) and nickel sulfide (Ni7S6) derived from a hybrid of a well-known nickel-based metal-organic framework (NiMOF-74) using thiourea as a sulfur source are reported here. The nanoporous NGO/MOF composite is prepared through a solvothermal process in which Ni(II) metal centers of the MOF structure are chelated with nitrogen and oxygen functional groups of NGO. NGO/Ni7S6 exhibits bifunctional activity, capable of catalyzing both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) with excellent stability in alkaline electrolytes, due to its high surface area, high pore volume, and tailored reaction interface enabling the availability of active nickel sites, mass transport, and gas release. Depending on the nitrogen doping level, the properties of graphene oxide can be tuned toward, e.g., enhanced stability of the composite compared to commonly used RuO2 under OER conditions. Hence, this work opens the door for the development of effective OER/HER electrocatalysts based on hierarchical porous graphene oxide composites with metal chalcogenides, which may replace expensive commercial catalysts such as RuO2 and IrO2. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We investigated the temporal degradation of glass moulding dies, made of cemented tungsten carbide coated with PtIr on an adhesive Cr or Ni interlayer, by electron microscopy and atom probe tomography. During the exposure treatments at 630 °C under an oxygen partial pressure of 1.12 × 10−23 bar, Cr (Ni) was found to diffuse outwards via grain boundaries in the PtIr, altering the surface morphology. Upon dissolution of the interlayer, the WC substrate also started degrading. Extensive interdiffusion processes involving PtIr, Cr (Ni) and WC took place, leading to the formation of intermetallic phases and voids, deteriorating the adhesion of the coating. © 2017 The Authors

The growth of metal–organic framework (ZIF-67) nanocrystals on nickel foam (NF), followed by carbonization in diluted H2, leads to a nitrogen-doped carbon-nanotube-grafted cobalt/carbon polyhedra film on NF. The obtained material serves as a highly active binder-free electrocatalyst for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER), enabling high-performance alkaline (0.1 m KOH) water electrolysis with potentials of 1.62 and 0.24 V, respectively, at OER and HER current densities of 10 mA cm−2. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores. © the Owner Societies 2016.

In the present work, we use a miniature test procedure to investigate the tensile creep behaviour of the single crystal superalloy ERBO1. We test precisely oriented [0 0 1], [1 1 0] and [1 1 1] creep specimens and determine the stress and the temperature dependence of characteristic creep rates in limited stress and temperature regimes, where the stress and temperature dependence of characteristic creep rates can be well described by power law and Arrhenius type of relations, with stress exponents n and apparent activation energies Qapp. n-values increase with stress and decrease with temperature. Qapp-values, on the other hand, increase with increasing temperature and decrease with increasing stress. Creep curve shapes gradually evolve from the high temperature low stress to the low temperature high stress (LTHS) regime. This implies that there is a gradual change in elementary deformation and softening mechanisms, which is qualitatively confirmed using transmission electron microscopy. While at high temperatures different loading directions only have a moderate influence on creep, there is a very strong effect of loading direction at low temperatures. The [1 1 0] tests show the fastest deformation rates and the shortest rupture times. In the LTHS creep regime, we confirm the double minimum (DM) type of creep behaviour, which was previously reported but never explained. Further work is required to rationalise DM-creep. The implications of this type of creep behaviour on scatter and on extrapolation of creep data is discussed in the light of previous results published in the literature. © 2016 Informa UK Limited, trading as Taylor & Francis Group.

Individual Ni(OH)2 nanoparticles deposited on carbon nanoelectrodes are investigated in non-ensemble measurements with respect to their energy storage properties and electrocatalysis for the oxygen evolution reaction (OER). Charging by oxidation of Ni(OH)2 is limited by the diffusion of protons into the particle bulk and the OER activity is independent of the particle size. © 2016 The Royal Society of Chemistry.

We introduce a novel alloying and processing scheme for high strength steels, which allows for precise and cost-effective cold forming due to high fractions of metastable austenite, and a subsequent low-distortion, coating-preserving strengthening through martensitic transformation induced by low temperature treatments. As the constitution is thus synchronised with the processing requirements, we refer to these materials as Transitory Constitution Steels. Suitable alloy compositions were identified by high throughput screenings through the exemplarily material systems Fe-5Ni-0.3C-(3-15)Mn and Fe-13.5Cr-6Mn-2Cu-0.2C-(0-2)Ni (wt.%) using combinatorial bulk metallurgical methods. The transformation behaviour, mechanical properties and underlying microstructural phenomena were studied in more detail after upscaling of selected compositions. The steel Fe-13.5Cr-6Mn-1.5Cu-0.2C (wt.%) exhibited an increase in yield strength from 300 to 1050. MPa after immersion into liquid nitrogen, as well as an ultimate tensile strength of more than 1700. MPa at a total elongation of more than 9%. Despite the ultra high strength, no embrittlement induced by Laser beam welding was observed, highlighting the inherent weldability of steels synthesised by the alloying and processing scheme presented here. Possibilities for flexible alloy design and processing variations are discussed. © 2015 Elsevier Ltd.

We systematically study the morphology, size and dispersion of TiB2 particles formed in-situ from Fe-Ti-B based melts, as well as their chemical composition, crystal structure and mechanical properties. The effects of 5 wt.% additions of Cr, Ni, Co, Mo, W, Mn, Al, Si, V, Ta, Nb and Zr, respectively, as well as additional annealing treatments, were investigated in order to derive guidelines for the knowledge based alloy design of steels with an increased stiffness/density ratio and sufficiently high ductility. All alloying elements were found to increase the size of the coarse primary TiB2 particles, while Co led to the most homogeneous size distribution. The size of the eutectic TiB2 constituents was decreased by all alloying additions except Ni, while their aspect ratio was little affected. No clear relation between chemical composition, crystal structure and mechanical properties of the particles could be observed. Annealing of the as-cast alloys slightly increased the size of the primary particles, but at the same time strongly spheroidised the eutectics. Additions of Co and Cr appear thus as the best starting point for designing novel in-situ high modulus metal matrix composite steels, while using Mn in concert with thermo-mechanical processing is most suited to adapt the matrix' microstructure and optimise the particle/matrix co-deformation processes. © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

High-entropy alloys are an intriguing new class of metallic materials that derive their properties from being multi-element systems that can crystallize as a single phase, despite containing high concentrations of five or more elements with different crystal structures. Here we examine an equiatomic medium-entropy alloy containing only three elements, CrCoNi, as a single-phase face-centred cubic solid solution, which displays strength-toughness properties that exceed those of all high-entropy alloys and most multi-phase alloys. At room temperature, the alloy shows tensile strengths of almost 1 GPa, failure strains of ∼70% and KJIc fracture-toughness values above 200 MPa m1/2; at cryogenic temperatures strength, ductility and toughness of the CrCoNi alloy improve to strength levels above 1.3 GPa, failure strains up to 90% and KJIc values of 275 MPa m1/2. Such properties appear to result from continuous steady strain hardening, which acts to suppress plastic instability, resulting from pronounced dislocation activity and deformation-induced nano-twinning. © 2016, Nature Publishing Group. All rights reserved.

The front cover artwork is provided by Ib Chorkendorff, Dowon Bae, and co-workers at the Technical University of Denmark (Denmark). The image highlights a time-dependent improvement in the water oxidation reaction of a back-side illuminated c-Si-based photoanode protected by a co-sputtered thin film of NiCoOX with iron incorporation. Read the full text of the Article at 10.1002/celc.201500554. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

High-resolution characterization techniques are combined with thermodynamic calculations (CALPHAD) to rationalize microstructural features of single crystal Ni-base superalloys. Considering the chemical compositions of dendritic and interdendritic regions one can explain differences in γ′-volume fractions. Using thermodynamic calculations one can explain, why γ-nanoparticles are observed in the central regions of large cuboidal γ′-particles and why tertiary γ′-nanoparticles form in the γ-channels. The chemical compositions of the γ-channels and of the newly formed γ-particles differ because of the Gibbs–Thomson pressure which acts on the small particles. With increasing size of secondary γ′-particles, their shape changes from spherical to cuboidal. Some general thermodynamic aspects including the temperature dependencies of the Gibbs free energy G, the enthalpy H, and the entropy S and site occupancies in the ordered L12 (γ′) phase are considered. The importance of cooling rate after homogenization is discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

In the present study the cyclic deformation behavior within differently oriented grains in Fe-34.8Mn-13.5Al-7.4Ni (at.%) shape memory polycrystals featuring a bamboo-like structure was investigated. In cyclic tensile tests up to 50 cycles, the degree of degradation in pseudoelasticity was evaluated and contributing elementary mechanisms are discussed. The results reveal rapid cyclic degradation in the bamboo-like samples. The unexpected stabilization of parent phase in reverse transformed areas and the proceeding activation of new martensite variants in subsequent cycles were found to be the prevailing degradation mechanisms. Dislocation activity is found to be the most detrimental factor. © 2015 Elsevier Ltd. All rights reserved.

We describe and study the thermal profiles experienced by various age-hardenable alloys during laser additive manufacturing (LAM), employing two different manufacturing techniques: selective laser melting and laser metal deposition. Using scanning electron microscopy and atom probe tomography, we reveal at which stages during the manufacturing process desired and undesired precipitation reactions can occur in age-hardenable alloys. Using examples from a maraging steel, a nickel-base superalloy and a scandium-containing aluminium alloy, we demonstrate that precipitation can already occur during the production of the powders used as starting material, during the deposition of material (i.e. during solidification and subsequent cooling), during the intrinsic heat treatment effected by LAM (i.e. in the heat affected zones) and, naturally, during an ageing post-heat treatment. These examples demonstrate the importance of understanding and controlling the thermal profile during the entire additive manufacturing cycle of age-hardenable materials including powder synthesis. © 2016, The Author(s).

The interdiffusivity of Al and the transition metal solutes Ti, V, Cr, Mn, Fe, Nb, Mo, Ru, Ta, W, and Re in fcc Co is characterized at 1373 K, 1473 K and 1573 K by binary diffusion couples. The experimental results are complemented by first-principles calculations in combination with kinetic Monte Carlo simulations to investigate the diffusion of Re, W, Mo and Ta in fcc Co. The interdiffusion coefficients of alloying elements in fcc Co are generally smaller than in fcc Ni, but the correlation between interdiffusion coefficients and the atomic number of metal solutes is comparable in Co and Ni. With increasing atomic number and decreasing atomic radii the interdiffusion coefficients of the investigated elements, except for Mn and Fe, decrease strongly. The trends in the diffusivity determined by experiment and simulation are in excellent agreement. Re is the slowest diffusing element in fcc Co among the investigated elements. The electronic structure calculations indicate that this is caused by strong directional bonds between Re and neighboring Co atoms. The overall lower diffusivity of solute atoms in Co as compared to Ni suggests that diffusion controlled processes could be slower in Co-base superalloys. © 2016 Acta Materialia Inc. All rights reserved.

Low temperature (750°C) and high stress (800 MPa) creep curves of single crystal superalloy ERBO/1 tensile specimens loaded in the (001) direction show two creep rate minima. Strain rates decrease towards a first sharp local creep rate minimum at 0.1% strain (reached after 30 min). Then deformation rates increase and reach an intermediate maximum at 1% (reached after 1.5 h). Subsequently, strain rates decrease towards a global minimum at 5% (260 h), before tertiary creep (not considered in the present work) leads to final rupture. We combine high resolution miniature creep testing with diffraction contrast transmission electron microscopy and identify elementary processes which govern this double-minimum type of creep behavior. We provide new quantitative information on the evolution of microstructure during low temperature and high stress creep, focusing on γ-channel dislocation activity and stacking fault shear of the γ′-phase. We discuss our results in the light of previous work published in the literature and highlight areas in need of further work. © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Dry reforming of methane (DRM) has been studied for many years as an attractive option to produce synthesis gas. However, catalyst deactivation by coking over nonprecious-metal catalysts still remains unresolved. Here, we study the influence of structural and compositional properties of nickel catalysts on the catalytic performance and coking propensity in the DRM. A series of bulk catalysts with different Ni contents was synthesized by calcination of hydrotalcite-like precursors NixMg0.67-xAl0.33(OH)2(CO3)0.17·mH2O prepared by constant-pH coprecipitation. The obtained Ni/MgAl oxide catalysts contain Ni nanoparticles with diameters between 7 and 20 nm. High-resolution transmission electron microscopy (HR-TEM) revealed a nickel aluminate overgrowth on the Ni particles, which could be confirmed by Fourier transform infrared (FTIR) spectroscopy. In particular, catalysts with low Ni contents (5 mol %) exhibit predominantly oxidic surfaces dominated by Ni2+ and additionally some isolated Ni0 sites. These properties, which are determined by the overgrowth, effectively diminish the formation of coke during the DRM, while the activity is preserved. A large (TEM) and dynamic (microcalorimetry) metallic Ni surface at high Ni contents (50 mol %) causes significant coke formation during the DRM. © 2016 American Chemical Society.

Despite the importance of martensitic transformations of Ni-Mn-Ga Heusler alloys for their magnetocaloric and shape-memory properties, the martensitic part of their phase diagrams is not well determined. Using an ab initio approach that includes the interplay of lattice and vibrational degrees of freedom we identify an intermartensitic transformation between a modulated and a nonmodulated phase as a function of excess Ni and Mn content. Based on an evaluation of the theoretical findings and experimental x-ray diffraction data for Mn-rich alloys, we are able to predict the phase diagram for Ni-rich alloys. In contrast to other mechanisms discussed for various material systems in the literature, we herewith show that the intermartensitic transformation can be understood solely using thermodynamic concepts. © 2016 American Physical Society.

The mechanical properties of γ′-strengthened Co-Ni-Al-W-Cr model superalloys extending from pure Ni-base to pure Co-base superalloys have been assessed. Differential scanning calorimetry measurements and thermodynamic calculations match well and show that the γ′ solvus temperature decreases with increasing Co-content. The γ/γ′ lattice misfit is negative on the Ni- and positive on the Co-rich side. High Ni-contents decelerate the oxidation kinetics up to a factor of 15. The creep strength of the Ni-base alloy increases by an order of magnitude with additions of Co before it deteriorates strongly upon higher additions despite an increasing γ′ volume fraction. © 2015 Elsevier Ltd. All rights reserved.

In Ni-base superalloys, the addition of refractory elements such as Cr, Mo, Co, W, and Re is necessary to increase the creep resistance. Nevertheless, these elements induce the formation of different kinds of intermetallic phases, namely, the topologically close-packed (TCP) phases. This work focuses on intermetallic phases present in the second-generation single-crystal (SX) Ni-base superalloy ERBO/1. In the as-cast condition, the typical γ/γ′ structure is accompanied by undesirable intermetallic phases located in the interdendritic regions. The nature of these precipitates as well as their thermal stability between 800 and 1200 °C has been investigated by isothermal heat treatments. The investigation techniques include DSC, SEM, EDX, and TEM. The experimental information is complemented by (1) comparison with a structure map to link the local chemical composition with phase stability, as well as (2) thermodynamic calculations based on the CALPHAD method to determine the occurrence and composition of phases during solidification and in equilibrium conditions. The TCP phases Laves, µ and σ were identified in various temperature/time ranges. © 2015, Springer Science+Business Media New York.

We put a spotlight on the exceptional magnetic properties of the metamagnetic Heusler alloy (Ni, Co)-Mn-Sn by means of first principles simulations. In the energy landscape we find a multitude of local minima, which belong to different ferrimagnetic states and are close in total magnetization and energy. All these magnetic states correspond to the local high spin state of the Mn atoms with different spin alignments and are related to the magnetic properties of Mn. Compared to pure Mn, the magneto-volume coupling is reduced by Ni, Co and Sn atoms in the lattice and no local low-spin Mn states appear. For the cubic phase we find a ferromagnetic ground state whereas the global energy minimum is a tetragonal state with a complicated spin structure and vanishing magnetization which so far has been overlooked in simulations. © 2016 IOP Publishing Ltd.

We investigated the hydrogen distribution and desorption behavior in an electrochemically hydrogen-charged binary Ni-Nb model alloy to study the role of δ phase in hydrogen embrittlement of alloy 718. We focus on two aspects, namely, (1) mapping the hydrogen distribution with spatial resolution enabling the observation of the relations between desorption profiles and desorption sites; and (2) correlating these observations with mechanical testing results to reveal the degradation mechanisms. The trapping states of hydrogen in the alloy were globally analyzed by Thermal Desorption Spectroscopy (TDS). Additionally, spatially resolved hydrogen mapping was conducted using silver decoration, Scanning Kelvin Probe Force Microscopy (SKPFM) and Secondary Ion Mass Spectrometry (SIMS): The Ag decoration method revealed rapid effusion of hydrogen at room temperature from the γ-matrix. The corresponding kinetics was resolved in both, space and time by the SKPFM measurements. At room temperature the hydrogen release from the γ-matrix steadily decreased until about 100 h and then was taken over by the δ phase from which the hydrogen was released much slower. For avoiding misinterpretation of hydrogen signals stemming from environmental effects we also charged specimens with deuterium. The deuterium distribution in the microstructure was studied by SIMS. The combined results reveal that hydrogen dissolves more preferably inside the γ-matrix and is diffusible at room temperature while the δ phase acts as a deeper trapping site for hydrogen. With this joint and spatially resolving approach we observed the microstructure- and time-dependent distribution and release rate of hydrogen with high spatial and temporal resolution. Correlating the obtained results with mechanical testing of the hydrogen-charged samples shows that hydrogen enhanced decohesion (HEDE) occurring at the δ/matrix interfaces promotes the embrittlement. © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

We apply the exact-muffin-tin-orbitals (EMTO) method to investigate structural properties, formation enthalpies, mechanical stability and polycrystalline moduli in Ni-Re, Ni-Cr and Cr-Re disordered fcc, bcc and hcp phases. Substitutional disorder is treated by using the coherent potential approximation (CPA). We predict the alloy lattice parameters in good agreement with the experiment. We find a continuous softening, as a function of Cr composition, of the tetragonal shear modulus C′ in fcc Ni-Cr phase indicating mechanical instability in Cr-rich Ni-Cr alloys. On the other hand, we show that the mechanical stability of fcc Ni-Re alloys persists through the whole composition range. We observe an intriguing behaviour of the Young's modulus vs. the intrinsic ductility curve in Ni-rich Ni-Re fcc phase. © 2016 Elsevier B.V. All rights reserved.

We report a simple, facile, and safe route for preparation of cobalt-cobalt phosphide (Co/Co2P) nanoparticles and demonstrate their application as efficient low-cost catalysts for electrochemical water splitting. The catalyst achieves good performance in catalyzing both the cathode and anode half-cell water-splitting reactions in 1.0 M KOH and the hydrogen evolution reaction in an acidic electrolyte, 0.5 M H2SO4. For the oxygen evolution reaction in 1.0 M KOH, a current of 10 mA cm(-2) was attained at 0.39 V overpotential on a glassy carbon electrode, while an overpotential of 0.19 V was attained at 50 mA cm(-2) when the catalyst was supported on nickel foam.

This work investigates the origin of creep dislocations in a Ni-base, single crystal superalloy subject to creep at an intermediate stress and temperature. Employing high angular resolution electron backscatter diffraction (HR-EBSD), electron channeling contrast imaging under controlled diffraction conditions (cECCI) and discrete dislocation dynamics (DDD) modelling, it is shown that low-angle boundaries - which correspond to dendrite boundaries or their residues after annealing - are not the major sources of creep dislocations. At the onset of creep deformation, they are the only active sources. Creep dislocations are emitted from them and percolate into the dislocation-depleted crystal. However, the percolation is very slow. As creep deformation proceeds, before the boundary-originated dislocations move further than a few micrometers away from their source boundary, individual dislocations that are spread throughout the undeformed microstructure become active and emit avalanches of creep dislocations in boundary-free regions, i.e. regions farther than a few micrometer away from boundaries. Upon their activation, the density of creep dislocations in boundary-free regions soars by two orders of magnitude; and the entire microstructure becomes deluged with creep dislocations. The total area of boundary-free regions is several times the total area of regions covered by boundary-originated creep dislocations. Therefore, the main sources of creep dislocations are not low-angle boundaries but individual, isolated dislocations in boundary-free regions. © 2016 Acta Materialia Inc.

Release of Ni1+ ions from NiTi alloy into tissue environment, biological response on the surface of NiTi and the allergic reaction of atopic people towards Ni are challengeable issues for biomedical application. In this study, composite coatings of hydroxyapatite-silicon multi walled carbon nano-tubes with 20 wt% Silicon and 1 wt% multi walled carbon nano-tubes of HA were deposited on a NiTi substrate using electrophoretic methods. The SEM images of coated samples exhibit a continuous and compact morphology for hydroxyapatite-silicon and hydroxyapatite-silicon-multi walled carbon nano-tubes coatings. Nano-indentation analysis on different locations of coatings represents the highest elastic modulus (45.8 GPa) for HA-Si-MWCNTs which is between the elastic modulus of NiTi substrate (66.5 GPa) and bone tissue (≈30 GPa). This results in decrease of stress gradient on coating-substrate-bone interfaces during performance. The results of nano-scratch analysis show the highest critical distance of delamination (2.5 mm) and normal load before failure (837 mN) as well as highest critical contact pressure for hydroxyapatite-silicon-multi walled carbon nano-tubes coating. The cell culture results show that human mesenchymal stem cells are able to adhere and proliferate on the pure hydroxyapatite and composite coatings. The presence of both silicon and multi walled carbon nano-tubes (CS3) in the hydroxyapatite coating induce more adherence of viable human mesenchymal stem cells in contrast to the HA coated samples with only silicon (CS2). These results make hydroxyapatite-silicon-multi walled carbon nano-tubes a promising composite coating for future bone implant application. © 2016 Elsevier Ltd.

Herein we report a dinickel azacryptand complex that enables fast, selective, and tight CO2 binding from air. Exploiting the affinity of the cavitand towards azides, CO2 release was observed. Despite the stability of the azido complex, UV irradiation under atmospheric conditions proved to be a suitable pathway for N3- replacement by CO2. © The Royal Society of Chemistry 2016.

The effect of interfaces on the magnetic properties of multilayers is analyzed forNi2MnGa/Ni2MnSn system using density functional theory. The Ni spin moments at the interface change by about 30% compared to the bulk value, whereas the effect on the Mn spin moments is much less pronounced. A similar strong effect is also observed for the Ni orbital moments at the interface. The magneto-crystalline anisotropy of the multilayer systems can be understood by the additive contribution of the respective values of strained bulk materials. © 2016 World Scientific Publishing Company.

Polysulfide shuttling is a crucial factor in lithium sulfur batteries responsible for capacity fading and degradation. Liquid phase adsorption in combination with nuclear magnetic resonance and X-ray photoelectron spectroscopy are used to elucidate and quantify polysulfide retention in typical porous cathode materials used in lithium sulfur batteries without cell assembly to achieve a more fundamental understanding of liquid phase adsorption phenomena as a responsible mechanism for polysulfide retention. The individual impact of each pore size increment is quantified on the polysulfide adsorption (PSA). Ultramicropores show eight times higher PSA (1.48 mmol cm−3) than mesopores. Strong heteroatom-doped ultramicropores show even stronger interactions with polysulfides leading to 25 times higher adsorption compared to hydrophobic mesopores. These findings allow to precisely tailor pore structure and heteroatom distribution of cathode materials for next generation lithium sulfur batteries with prolonged cycle life and reduced capacity fading. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Solid oxide fuel cells (SOFCs) directly convert the chemical energy of fuels into electrical energy with high efficiency. Under certain conditions oxygen can diffuse to the Ni/8 mol% Y2O3-doped ZrO2 substrate of anode-supported SOFCs, then the nickel re-oxidizes, leading to cracks in the electrolyte and cell failure thus limiting the durability of SOFCs. In order to improve the stability of SOFCs with respect to oxidation, the inner surface of the porous substrate is coated with a ZrO2 oxidation resistance layer using atomic layer deposition (ALD) with the precursors tetrakis(ethylmethylamino)zirconium (TEMAZ) and molecular oxygen. This TEMAZ/O2-ZrO2 ALD process has not yet been reported in the literature and hence, the development of the process is described in this paper. The inner surface of the porous substrate is coated with ZrO2 and the film thickness is compared with theoretical predictions, verifying the ALD model. Furthermore, the coating depth can be estimated using a simple analytical equation. The ALD ZrO2 film protects the nickel in the substrate against oxidation for at least 17 re-oxidation/re-reduction cycles. The ZrO2 inner surface coating is a highly promising candidate for enhancing the resistance of SOFCs to re-oxidation because of the excellent oxidation resistance and good cycling stability of the film. © 2016 Elsevier B.V.

The spin-space averaging formalism is applied to compute atomic forces and phonon spectra for magnetically excited states of fcc nickel. Transverse and longitudinal magnetic fluctuations are taken into account by a combination of magnetic special quasi random structures and constrained spin-density-functional theory. It turns out that for fcc Ni interatomic force constants and phonon spectra are almost unaffected by both kinds of spin fluctuations. Given the computational expense to simulate coupled magnetic and atomic fluctuations, this insight facilitates computational modeling of magnetic alloys such as Ni-based superalloys. © 2016 IOP Publishing Ltd.

Electrical double-layer capacitors, lithium-ion batteries, and fuel cells are among the most important devices for storage and conversion of electrochemical energy. Further improvement of these systems and their single components is needed to meet the future requirements in terms of higher energy and power densities. In all of these devices, the interactions between carbonaceous materials and electrolyte components play crucial roles. In electrical double-layer capacitors and lithium-ion batteries, electrolyte ions get in direct contact with carbon electrode materials for energy storage. In fuel cells, carbon-supported electrode catalysts and polymeric membranes are among the most important components. For a directed improvement of these devices, a profound understanding of the processes taking place on the carbon–electrolyte interfaces is crucial. Especially nuclear magnetic resonance spectroscopy is qualified for the characterization of these interactions due to its chemical specificity, the local nature of NMR-relevant interactions, the possibility to investigate both amorphous and crystalline compounds, and the potential to monitor dynamic processes that occur over a wide timescale. This review addresses recent NMR spectroscopic investigations of the interactions between electrolytes and carbon materials in electrical double-layer capacitors, lithium-ion batteries, and fuel cells. Structures and properties of the most important carbon nanomaterials relevant for these devices are discussed, and the general principles of the electrochemical energy storage systems are introduced. Fundamental principles as well as hardware aspects of in situ and ex situ NMR measurements are addressed. The relationships between the properties of the carbon materials, the electrochemical characteristics, and the NMR data are explained. NMR spectroscopy as the profound analytical method is considered in combination with the operating principles of the electrochemical energy storage devices. © 2016 Elsevier Ltd

The need for sustainable catalysts for an efficient hydrogen evolution reaction is of significant interest for modern society. Inspired by comparable structural properties of [FeNi]-hydrogenase, here we present the natural ore pentlandite (Fe 4.5 Ni 4.5 S 8) as a direct rock' electrode material for hydrogen evolution under acidic conditions with an overpotential of 280 mV at 10 mA cm -2. Furthermore, it reaches a value as low as 190 mV after 96 h of electrolysis due to surface sulfur depletion, which may change the electronic structure of the catalytically active nickel-iron centres. The rock' material shows an unexpected catalytic activity with comparable overpotential and Tafel slope to some well-developed metallic or nanostructured catalysts. Notably, the rock' material offers high current densities (≤650 mA cm -2) without any loss in activity for approximately 170 h. The superior hydrogen evolution performance of pentlandites as rock' electrode labels this ore as a promising electrocatalyst for future hydrogen-based economy.

Three-electrode cells are essential in understanding battery materials under operando conditions. A three-electrode, battery-type Swagelok cell for electrochemical studies of secondary alkaline batteries, in particular Ni-Zn batteries, is presented. The relevance of the three-electrode battery-type cell (i.e. sealed and non-flooded) configuration is demonstrated as analytical tool with three observations: 1)The Ni electrode is shown to limit the system in the first cycles, while the Zn electrode becomes limiting in subsequent cycles. 2)Non-woven separators (NWSs) clearly improve the performance of the battery. Besides the known fact of hindering the dendritic growth of Zn, NWSs inhibit the evolution of oxygen and hydrogen at the positive and negative electrodes. 3)The kinetics of the Ni electrode is much slower than that of the Zn electrode, as derived from the charge-transfer resistance of the Ni electrode, which is substantially larger than that of the Zn electrode. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel Cr containing Co-Al-W base superalloys were studied by atom probe tomography and neutron diffraction. Cr is found to predominantly partition to the gamma matrix and decrease partitioning of W to gammaprime. Furthermore, Cr significantly enhances the gammaprime volume fraction, decreases the gamma/gammaprime lattice misfit and deteriorates the creep resistance. Addition of Ni to the Cr containing alloys affects partitioning of W and Al, further decreases the lattice misfit and results in the formation of irregularly shaped precipitates. Al, W and Cr tend to occupy the ‘B'sublattice in the gammaprime-A3B phase (L12 type), while Co and Ni reside in the ‘A' sublattice. © 2016 Institute of Materials.

Electrocatalysts that can reversibly reduce oxygen and oxidise water are of prime importance for the advancement of new emerging electrochemical energy storage and conversion systems. We present in this work the application of scanning electrochemical microscopy (SECM) for characterisation of bifunctional catalysts. By using model bifunctional catalysts based on oxides of cobalt (CoxOy) and nickel (NixOy) embedded in nitrogen-doped carbon (NC), we specifically show the unique ability of using SECM to determine a range of the important electrocatalytic parameters including the selectivity of the oxygen reduction reaction (ORR), the initial mechanistic steps during the oxygen evolution reaction (OER), and the onset potential for both ORR and OER in a single experiment. We were able to observe directly that prior to oxygen evolution, local depletion of oxygen occurs at the SECM tip during redox transition accompanying most likely metal oxyhydroxide formation thus enabling direct in situ observation of the initial mechanistic steps of the OER. © 2015, Springer-Verlag Berlin Heidelberg.

This study focuses on the synthesis and electrochemical performance (i.e, activity and stability) of advanced electrocatalysts for the oxygen reduction reaction (ORR), made of Pt-Ni nanoparticles embedded in hollow graphitic spheres (HGS). The mechanism of the confined space alloying, that is, the controlled alloying of bimetallic precursors with different compositions (i.e., Pt3Ni, PtNi, and PtNi3) within the HGS mesoporous shell, was examined in detail. It was found that the presence of platinum during the reduction step, as well as the application of high annealing temperatures (at least 850°C for 3.5h in Ar), are necessary conditions to achieve the complete encapsulation and the full stability of the catalysts. The evolution of the activity, the electrochemical surface area, and the residual alloy composition of the Pt-Ni@HGS catalysts was thoroughly monitored (at the macro- and nanoscale level) under different degradation conditions. After the initial activation, the embedded Pt-Ni nanoparticles (3-4 nm in size) yield mass activities that are 2- to 3.5-fold higher than that of pure Pt@HGS (depending on the alloy composition). Most importantly, it is demonstrated that under the normal operation range of an ORR catalyst in PEM-FCs (potential excursions between 0.4 and 1.0 VRHE) both the nanoparticle-related degradation pathways (particle agglomeration) and dealloying phenomena are effectively suppressed, irrespectively of the alloy composition. Thus, the initial enhanced activity is completely maintained over an extended degradation protocol. In addition, owing to the peculiar configuration of the catalysts consisting of space-confined nanoparticles, it was possible to elucidate the impact of the dealloying process (as a function of alloy composition and severity of the degradation protocols) separately from other parallel phenomena, providing valuable insight into this elusive degradation mechanism. (Graph Presented). © 2016 American Chemical Society.

The creep behavior of a single-crystal Ni-base superalloy in two microstructural states is compared. One is obtained by casting followed by a conventional heat treatment. The other results from the same nominal heat treatment integrated into a hot isostatic pressing process. The microstructure after HIP differed from that in the conventional route in two respects. First, the γ′ particles are smaller and the γ channels are narrower. Second, after HIP, the number density of pores is lower and the pore sizes are smaller. The HIP microstructure improves creep in two respects: the finer γ/γ′-microstructure results in lower minimum creep rates. Moreover, the shrinkage of cast porosity during HIP delays the nucleation and growth of micro cracks and results in higher rupture strains in the low-temperature high stress regime. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Solid state refrigeration processes, such as magnetocaloric and electrocaloric refrigeration, have recently shown to be a promising alternative to conventional compression refrigeration. A new solid state elastocaloric refrigeration process using the latent heats within Shape Memory Alloys (SMA) could also hold potential in this field. This work investigates the elastocaloric effects in Ni-Ti-based superelastic Shape Memory Alloy (SMA) systems for use in an elastocaloric cooling processes. Ni-Ti alloys exhibits large latent heats and a small mechanical hysteresis, which may potentially lead to the development of an efficient environmentally friendly solid-state cooling system, without the need for ozone-depleting refrigerants. A systematic investigation of the SMA is conducted using a novel custombuilt scientific testing platform specifically designed to measure cooling process related phenomena. This testing system is capable of performing tensile tests at high rates as well as measuring and controlling the solid-state heat transfer between SMA and heat source/heat sink. Tests are conducted following a cooling process related training cycle where the material has achieved stabilized behavior. First, a characterization of the elastocaloric material properties is performed followed by an investigation of the material under cooling process conditions. A comprehensive monitoring of the mechanical and thermal parameters enables the observation of temperature changes during mechanical cycling of the SMA at high strain rates. These observations can be used to study the rate dependent efficiency of the elastocaloric material. The measurement of the temperature of both the heat source/heat sink and the SMA itself, as well as the required mechanical work during a running cooling process, reveals the influence of the operating conditions on the elastocaloric effect of the material. Furthermore investigations of the process efficiency at different thermal boundary conditions (temperature of heat source/heat sink), indicates that the process is dependent on the boundary conditions which have to be controlled in order to optimize the efficiency. © Copyright 2015 by ASME.

The precipitation of topologically close packed (TCP) phases is detrimental for the high temperature strength of high refractory Ni-based superalloys. The beneficial influence of Ru with respect to this so called instability is nowadays well accepted. In the present paper the precipitation of topologically close packed (TCP) phases is studied quantitatively in two experimental alloys (one Ru-free and one with addition of Ru) to clarify the mechanism of the Ru effect. It is confirmed that the TCP phase precipitates undergo sequential phase transformation with the tetragonal σ-phase precipitating first. Ru retards the phase transformation and leads to decreased equilibrium volume fraction of TCP phases. The results clearly indicate that Ru decreases the driving force for TCP phase precipitation. Investigations of crystallography and chemistry of the TCP/matrix interface point to an additional effect by increase of misfit strain energy. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Bioactive peptides from food proteins such as natural ACE (angiotensin-converting enzyme)-inhibitors have attracted particular attention for their potential to prevent hypertension. ACE-inhibiting peptides were enriched from food protein hydrolysates prepared from α-lactalbumin and lysozyme by selective adsorption on microporous activated carbons. For the eluate, it was shown by liquid chromatography that the strongest inhibitor isoleucyl-tryptophan was enriched by a factor of 11.2 compared to the initial α-lactalbumin hydrolysate. Natural inhibitors derived from lysozyme hydrolysates (e.g., alanyl-tryptophan) were successfully enriched as well. Identification of the enriched peptide fraction by mass spectroscopy revealed the hydrophobic character of the enriched peptides. The molecular weight distribution of the enriched peptide fraction can be controlled by the pore size distribution of the chosen adsorbent, which was proven by size exclusion chromatography of enriched peptide fractions derived from three different model carbons differing in their pore size. The selective enrichment of natural ACE-inhibitors from the α-lactalbumin hydrolysate lead to a 6 times stronger in vitro ACE-inhibition demonstrating the high potential as ingredients for hypotensive functional foods with reduced side effects. © 2015 Elsevier Ltd. All rights reserved.

In the present work, we show how conventional and advanced mechanical, chemical, and microstructural methods can be used to characterize cast single crystal Ni-base superalloy (SX) plates across multiple length scales. Two types of microstructural heterogeneities are important, associated with the castmicrostructure (dendrites (D) and interdendritic (ID) regions - large scale heterogeneity) and with the well-known γ/γ′ microstructure (small scale heterogeneity). Using electron probe microanalysis (EPMA), we can showthat elements such as Re, Co, andCr partition to the dendrites while ID regions contain more Al, Ta, and Ti. Analytical transmission electron microscopy and atom probe tomography (APT) show that Al, Ta, and Ti partition to the γ′ cubes while g channels show higher concentrations of Co, Cr, Re, andW.We can combine large scale (EPMA) and small-scale analytical methods (APT) to obtain reasonable estimates for γ′ volume fractions in the dendrites and in the ID regions. The chemical and mechanical properties of the SX plates studied in the present work are homogeneous, when they are determined from volumes with dimensions, which are significantly larger than the dendrite spacing. For the SX plates (140mm x 100mm x 20mm) studied in the present work this holds for the average chemical composition as well as for elastic behavior and local creep properties. We highlight the potential of HRTEM and APT to contribute to a better understanding of the role of dislocations during coarsening of the γ′ phase and the effect of cooling rates after high temperature exposure on the microstructure. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA.

Due to its transformation behavior, Co-Ni-Ga represents a very promising high temperature shape memory alloy (HT SMA) for applications at elevated temperatures. Co-Ni-Ga single crystals show a fully reversible pseudoelastic shape change up to temperatures of 400 °C. Unfortunately, polycrystalline Co-Ni-Ga suffers from brittleness and early fracture mainly due to intergranular constraints. In the current study, different thermo-mechanical processing routes produced various microstructures which differ in grain size and texture. A bicrystalline bamboo-like grain structure results in the highest reversible transformation strains and excellent cyclic stability. Moreover, solution-annealed and hot-rolled conditions also showed cyclic stability. Using in situ high-resolution electron microscopy, the elementary processes, which govern the microstructural evolution during pseudoelastic cycling were investigated and the mechanisms that govern structural and functional degradation were identified. The observations documented in the present work suggest that the formation of the ductile γ-phase on and near grain boundaries as well as the activation of multiple martensite variants at grain boundaries are beneficial for improved cyclic performance of polycrystalline Co-Ni-Ga HT SMAs. © 2015 Elsevier B.V. All rights reserved.

We have performed ab initio electronic structure calculations and Monte Carlo simulations of frustrated ferroic materials where complex magnetic configurations and chemical disorder lead to rich phase diagrams. With lowering of temperature, we find a ferromagnetic phase which transforms to an antiferromagnetic phase at the magnetostructural (martensitic) phase transition and to a cluster spin glass at still lower temperatures. The Heusler alloys Ni-(Co)-Mn-(Cr)-(Ga, Al, In, Sn, Sb) are of particular interest because of their large inverse magnetocaloric effect associated with the magnetostructural transition and the influence of Co/Cr doping. Besides spin glass features, strain glass behavior has been observed in Ni-Co-Mn-In. The numerical simulations allow a complete characterization of the frustrated ferroic materials including the Fe-Rh-Pd alloys. © Owned by the authors, published by EDP Sciences, 2015.

In the present work we investigate three mechanical and microstructural aspects of high temperature and low stress creep of the single crystal superalloy LEK 94. First, we compare the tensile creep behavior of specimens loaded in precise [001] and [110] directions and show that tensile creep specimens with precise [110] directions show significantly lower minimum creep rates. However, small deviations from precise [110] orientations result in a significant increase of creep rate. Second, we use a novel SEM technique to measure dislocation densities. We show that after short periods of creep, dislocation densities in dendritic regions are always higher than in interdendritic regions. This finding is probably associated with wider γ-channels, higher concentrations of W and Re and higher misfit stresses in the γ-channels of dendrites. Finally, we show that internal stresses associated with solidification can drive complex rafting processes during high temperature exposure, which differ between dendrite cores and interdendritic regions. © 2014 Elsevier B.V.

The magnetic and magnetocaloric properties of Ni-Co-Mn-(Ga, In, Sn) Heusler intermetallics are discussed on the basis of ab initio and Monte Carlo calculations. The main emphasis is on the different reference spin states and magnetic exchange coupling constants of high-temperature austenite and low-temperature martensite which are very important for the calculation of magnetocaloric effect. The origin of metamagnetic behavior is considered in the framework of orbital resolved magnetic exchange parameters of austenite and martensite. The decomposition of exchange constants on orbital contributions has shown that a strong ferromagnetic interaction of magnetic moments in austenite is caused by the more itinerant d-electrons with t2g states while a strong antiferromagnetic interaction in martensite is associated with the more localized eg states. In addition, the appearance of a paramagnetic gap between magnetically weak martensite and ferromagnetically ordered austenite can be realized because of strong competition of magnetic exchange interactions. As a result, large magnetization drop and giant inverse magnetocaloric effect can be achieved across the magnetostructural phase transition. ©2015 Elsevier B.V. All rights reserved.

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.

The depth-dependent chemical constitution of Ti51Ni38Cu11 thin films of different total film thickness from 400 to 50-nm was characterized using X-ray photoelectron spectroscopy (XPS). It was analyzed how reaction layers, which form on the surface of the film significantly change the chemical composition of the transforming phase, which leads in turn to altered phase transformation properties. For thinner films, the deviation from the nominal chemical composition increases. For a film thickness of 50-nm, a Ti loss of ≈9-at% is observed. The Ni content is increased by ≈5-at%, whereas the Cu content stays relatively constant for films of different thickness. The results are summarized in a layer model, which supports designing nanoscale shape memory thin films. Ti51Ni38Cu11 thin films of different film thickness are investigated regarding the influence of the reaction layers on the chemical composition of the transforming phase and the corresponding functional properties. A model is proposed describing the different reaction layers on the surface of the thin film and at the substrate/thin film interface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-temperature shape memory alloys are attractive for efficient solid state actuation. A key criterion for shape memory alloys is the martensite start temperature. The current study introduces a concept for increasing this temperature of alloys initially not suited for high-temperature actuation. Aging of stress-induced martensite, referred to as SIM-aging in the current work, is able to increase the martensite start temperature by about 130 °C as demonstrated in the present study for a Co-Ni-Ga shape memory alloy. The increase of transformation temperatures can be explained based on the concept of symmetry-conforming short-range order. Following SIM-aging the Co-Ni-Ga alloy shows cyclic actuation stability at elevated temperatures. While martensite aging has always been viewed as detrimental in the past, it can actually be exploited to design new classes of high-temperature shape memory alloys with excellent properties. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

New γ'-strengthened Co-base superalloys show an interesting potential for high temperature applications. However, protective coatings are needed as for Ni-base superalloys to ensure sufficient oxidation and corrosion resistance. Therefore the properties of a commercial coating on a multinary new γ'-strengthened Co-base superalloy have been studied. Especially the influence of the coating process on the substrate also after long term annealing is discussed. It was found that the highly deformed areas at the coating-substrate interface indicated by a high local misorientation and caused by the sandblasting process led to a recrystallization of the interdiffusion zone during the age hardening heat treatment. A chemical gradient of γ and γ' promoting elements was found in the interdiffusion zone causing a change in hardness as measured by nanoindentation. Depending on the composition two separate recrystallized regions formed in the interdiffusion zone, one with single phase γ-(Co,Ni) and the other with a cellular two phase microstructure of discontinuously grown γ and γ'. © 2015 Elsevier B.V.

Thin-film materials libraries of the intermetallic model system Ni-Al-Cr were fabricated and their oxidation behavior was studied by compositional, optical, electrical, and structural high-throughput characterization methods. The study reveals the compositional regions of the binary and ternary compositions which withstand longest to annealing in air (up to 700 C), and are, therefore, resistant to oxidation and delamination under these conditions. A complete ternary thin-film phase diagram for the Ni-Al-Cr system in its state after 9 h annealing in air at 500 C was determined. Optical high-throughput characterization is shown to be valid for rapid identification of oxidizing phases. Generally, the initially metallic phases show different oxidation behavior in air. We find that the ternary compositions are more resistant to oxidation than the binary phases. Compositions around Ni25Al12.5Cr62.5 were found to show very good oxidation resistance. These results were supported by additional information from corresponding electrical and optical property investigations. The presented high-throughput approach is generic for the efficient study of multinary thin-film materials in harsh environments. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

The demand for increased efficiency of industrial gas turbines and aero engines drives the search for the next generation of materials. Promising candidates for such new materials are Co-based superalloys. We characterize the microsegregation and solidification of a multi-component Co-based superalloy and compare it to a ternary Co–Al–W compound and to two exemplary Ni-based superalloys by combining the experimental characterization of the as-cast microstructures with complementary modelling of phase stability. On the experimental side, we characterize the microstructure and precipitates by electron microscopy and energy-dispersive X-ray spectroscopy and determine the element distributions and microsegregation coefficients by electron probe microanalysis (EPMA). On the modelling side, we carry out solidification simulations and a structure map analysis in order to relate the local chemical composition with phase stability. We find that the microsegregation coefficients for the individual elements are very similar in the investigated Co-based and Ni-based superalloys. By interpreting the local chemical composition from EPMA with the structure map, we effectively unite the set of element distribution maps to compound maps with very good contrast of the dendritic microstructure. The resulting compound maps of the microstructure in terms of average band filling and atomic-size difference explain the formation of topologically close-packed phases in the interdendritic regions. We identify B2, C14, and D024 precipitates with chemical compositions that are in line with the structure map. © 2015, Springer Science+Business Media New York.

In the present study we investigate the creep behavior of a Ni-base single crystal superalloy. We evaluate the stress and temperature dependence of the minimum creep rate, which shows a power law type of stress dependence (characterized by a stress exponent n) and an exponential type of temperature dependence (characterized by an apparent activation energy Qapp). Under conditions of high temperature (1323K) and low stress (160MPa) creep, n and Qapp are determined as 5.3 and 529kJ/mol, respectively. For lower temperatures (1123K) and higher stresses (600MPa) the stress exponent n is higher (8.5) while the apparent activation energy of creep is lower (382kJ/mol). We show that there is a general trend: stress exponents n increase with increasing stress and decreasing temperature, while higher apparent activation energies are observed for lower stresses and higher temperatures. We use density functional theory (DFT) to calculate the activation energy of diffusion for Re in a binary Ni-Re alloy with low Re-concentrations. The resulting energy is almost a factor 2 smaller than the apparent activation energy of creep. We explain why it is not straightforward to rationalize the temperature dependence of creep merely on the basis of the diffusion of one alloying element. We show that the evolution of the microstructure also must be considered. © 2015 Elsevier B.V.

Two Ni-based superalloys (one Ru-free and one containing 1 at.% Ru) were comparatively studied by Atom Probe Tomography and complimentary techniques. Ru addition impedes precipitation of the σ phase at 950 °C. Ru partitions nearly equally to the γ and σ phase. Neither reverse elemental partitioning nor destabilization of the γ' phase is detected when adding Ru. We propose an increase in the γ/σ lattice misfit caused by Ru as a major reason for impeded nucleation of the σ phase. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

In the present work we study the formation of grooves and ledges (typical size: <100 nm) at γ/γ′ interfaces of single crystal Ni-base superalloys. We highlight previous work which documents the presence of such interface irregularities and shows that their number and size increases during high temperature exposure and creep. We use diffraction contrast stereo transmission electron microscopy (TEM) to provide new evidence for the presence of ledges and grooves near dislocations at γ/γ′ interfaces after heat treatment and creep. We present a 2D model of the interfacial region which shows how dislocation stress fields alter local chemical potentials and drive diffusional fluxes which result in the formation of a groove. The results of the numerical study yield realistic groove sizes in relevant time scales. The results obtained in the present study suggest that the formation of grooves and ledges represents an elementary process which needs to be considered when rationalizing the kinetics of rafting, the directional coarsening of the γ′ phase. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The chemical and morphological stability of size- and shape-selected octahedral PtNi nanoparticles (NP) were investigated after different annealing treatments up to a maximum temperature of 700 °C in a vacuum and under 1 bar of CO. Atomic force microscopy was used to examine the mobility of the NPs and their stability against coarsening, and X-ray photoelectron spectroscopy to study the surface composition, chemical state of Pt and Ni in the NPs, and thermally and CO-induced atomic segregation trends. Exposing the samples to 1 bar of CO at room temperature before annealing in a vacuum was found to be effective at enhancing the stability of the NPs against coarsening. In contrast, significant coarsening was observed when the sample was annealed in 1 bar of CO, most likely as a result of Ni(CO)4 formation and their enhanced mobility on the support surface. Sample exposure to CO at room temperature prior to annealing led to the segregation of Pt to the NP surface. Nevertheless, oxidic PtOx and NiOx species still remained at the NP surface, and, irrespective of the initial sample pretreatment, Ni surface segregation was observed upon annealing in a vacuum at moderate temperature (T < 300 °C). Interestingly, a distinct atomic segregation trend was detected between 300 and 500 °C for the sample pre-exposed to CO; namely, Ni surface segregation was partially hindered. This might be attributed to the higher bonding energy of CO to Pt as compared to Ni. Annealing in the presence of 1 bar CO also resulted in the initial surface segregation of Ni (T < 400 °C) as long as PtOx and NiOx species were available on the surface as a result of the higher affinity of Ni for oxygen. Above 500 °C, and regardless of the sample pretreatment, the diffusion of Pt atoms to the NP surface and the formation of a Ni-Pt alloy are observed. © 2015 American Chemical Society.

Herein, we present the synthesis of nickel complexes with tripodal phosphine ligands, CH3Si(CH2PPh2)3 and CH3C(CH2PPh2)3, and their application as catalysts in Sonogashira cross-coupling reactions in water. Although both types of nickel complexes are based on similar tripodal ligands, the Si-derived compounds adopt stable tetrahedral coordination geometries, whereas the C-derived counterparts adopt a square-planar coordination environment. This structural and electronic difference has an important effect on the catalytic properties of the complexes. Our study demonstrates that C-derived complexes are catalytically inactive, whereas the complexes [CH3Si(CH2PPh2)3NiX2] (X = Cl-, Br-) are competent catalysts for cross-coupling reactions of aryl halides with phenylacetylenes. This investigation reveals the importance of structural tuning on catalysis and strongly supports the theory that tetrahedral (PR3)2NiCl2 complexes are the active species in Sonogashira cross-coupling reactions. Two tripodal phosphines CH3E(CH2PPh2)3 (E = C, Si) are applied as ligands in Ni-catalyzed cross-coupling reactions; various coordination modes at the Ni center can be achieved. For the first time, experimental evidence is provided to prove that tetrahedral instead of planar (PR3)2NiCl2 moieties are required to perform effective Sonogashira coupling reactions. Copyright © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The diffusion coefficients of interstitial hydrogen in bulk Fe and Ni crystals have been calculated over a wide range of temperatures employing first-principles methods based on density functional theory. Quantum mechanical effects have been included by means of the semiclassical transition state theory and the small-polaron model of Flynn and Stoneham. Our results show that to include such effects is crucial for a quantitative simulation of H diffusion in bcc Fe even at room temperature, while in the case of fcc Ni this is less important. The comparison with other theoretical approaches as well as with experimental studies emphasizes the main advantages of the present approach: it is quantitatively accurate and computationally efficient. © 2015 American Physical Society.

Abstract In this work, the interaction of hydrogen with high-angle GBs in nickel has been investigated by means of density functional theory simulations. Two distinct types of GBs have been considered: the Σ3(111)[1¯10] with a close-packed interface structure and the Σ5(210)[001] with a less dense interface structure consisting of open structural units. Our calculations reveal that these two GBs have a markedly different interaction behavior with atomic hydrogen. The close-packed Σ3 GB neither traps H nor enhances its diffusion, but instead acts as a two-dimensional diffusion barrier. In contrast, the Σ5 GB provides numerous trapping sites for H within the open structural units as well as easy migration pathways for H diffusion along the GB plane that can enhance the H diffusivity by about two orders of magnitude compared to bulk Ni. The obtained results are analysed in detail and compared with available experimental and other theoretical data. © 2015 Acta Materialia Inc.

The present work reviews previous research on the evolution of porosity. It presents new results from a detailed study on the evolution of porosity during casting, heat treatment and creep of a single crystal Ni-base superalloy subjected to uniaxial tensile creep at 1050 °C and 160 MPa in [001] and [110] directions. A quantitative metallographic study was performed on carefully polished metallographic cross sections, monitoring sampling fields of 4500 × 1000 μm2 using the back scatter contrast of an analytical scanning electron microscope; evolutions of pore sizes and pore form factors were analyzed and all important details which were previously revealed in a synchrotron study could be reproduced. In addition, it was observed that micro cracks form at larger cast pores. They interlink and thus initiate final rupture. The [110] tensile creep tests showed lower rupture strains than the [001] experiments. In agreement with earlier work, this can be rationalized on the basis of aligned porosity along primary dendrites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In the present work the thermal expansion and the elastic properties of second generation nickel-base superalloy single crystals ERBO/1 (CMSX-4 variation) and LEK94 have been studied between about 100 K and 1273 K using dilatometry and resonant ultrasound spectroscopy, respectively. Inhomogeneity related to the large scale microstructure of the samples can act as a potential source of scatter for the propagation of ultrasonic waves. This can be overcome by choosing samples of sufficient size so that they appear as homogeneous media at the scale of the elastic wave length. Our final results are in good agreement with data reported in literature for similar alloy systems. In particular, the elastic material properties are only weekly affected by moderate variations in chemical composition and microstructure. Taking into account literature data for other superalloys like CMSX-4, we derive general polynomial functions which describe the temperature dependence of the elastic moduli E〈100〉, E〈110〉 and E〈111〉 in nickel-base superalloys to within about ±3%. It was also observed that the alloys ERBO/1 and LEK94 show weak but significant anomalies in both thermal expansion and temperature coefficients of elastic constants above about 900 K. These anomalies are probably related to the gradual dissolution of the γ′-precipitates at higher temperatures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Iron phthalocyanine-based materials have been used herein as efficient catalysts for the ammonia decomposition reaction. These materials showed high activity, even superior to that showed by the commercial nickel-based catalyst and iron-doped carbon nanotubes, which were used as benchmarks in this study. Catalyst stability under reaction conditions appeared satisfactory, because no deactivation phenomena were observed. The type of the phthalocyanine precursor did not affect the catalytic performance; however, the preparation method had a strong effect. If the resulting material was exposed to the reaction conditions, some structural modification occurred. No clear correlation between phase composition and activity could be established because similar nitrogen content and similar crystalline domains in the sample led to different behaviors. However, the results of extensive characterization suggested that catalytic activities and conversion profiles were most likely dependent on material textural properties and thus on the preparation method used. The accessibility of iron species seems to be limited for catalysts prepared under vacuum. These phenomena are most likely responsible for the activation profile and for the low catalytic activity typical of these materials. In contrast, higher accessibility of iron species, typical of materials prepared under argon, would lead to improved and stable catalytic performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We have developed an electrochemical sensor for nitric oxide that is based on multi-layers of nickel(II) phthalocyaninetetrasulfonate and a polyamidoamine dendrimer assembled on the surface of a carbon-fiber microelectrode. This sensor responds to nitric oxide at a working potential of 800 mV with a sensitivity of 5.54 pA∙μM‾1 which, however, depends on the dendrimer layer position deposited on the microelectrode. The limit of detection is as low as 5.5 μM at a signal-to-noise ratio of 3. The electrode exhibits good selectivity for nitric oxide over common interferents including dopamine, nitrite, hydrogen peroxide, norepinephrine, epinephrine and ascorbic acid. [Figure not available: see fulltext.] © 2014, European Union.

A new approach to produce highly porous carbide-derived carbon nanospheres of 20-200 nm diameter based on a novel soft-templating technique is presented. A platinum catalyst is used for the cross-linking of liquid (allylhydrido)polycarbosilane polymer chains with para-divinylbenzene within oil-in-water miniemulsions. Quantitative implementation of the pre-ceramic polymer can be achieved allowing precise control over the resulting materials. After pyrolysis and high-temperature chlorine treatment, the resulting particles offer a spherical shape, very high specific surface area (up to 2347 m2 g-1), and large micro/mesopore volume (up to 1.67 cm3 g-1). The internal pore structure of the nanospheres is controllable by the composition of the oil phase within the miniemulsions. The materials are highly suitable to be used as supercapacitor electrodes with high specific capacitances in aqueous 1 M Na2SO4 solution (110 F g-1) and organic 1 M tetraethylammonium tetrafluoroborate in acetonitrile (130 F g-1). © The Royal Society of Chemistry 2015.

Three-dimensional discrete dislocation dynamics (DDD) simulations in combination with the phase-field method are performed to investigate the influence of different realistic Ni-base single crystal superalloy microstructures with the same volume fraction of γ;precipitates on plastic deformation at room temperature. The phase-field method is used to generate realistic microstructures as the boundary conditions for DDD simulations in which a constant high uniaxial tensile load is applied along different crystallographic directions. In addition, the lattice mismatch between the γand γ;phases is taken into account as a source of internal stresses. Due to the high antiphase boundary energy and the rare formation of superdislocations, precipitate cutting is not observed in the present simulations. Therefore, the plastic deformation is mainly caused by dislocation motion in γ; matrix channels. From a comparison of the macroscopic mechanical response and the dislocation evolution for different microstructures in each loading direction, we found that, for a given γ;phase volume fraction, the optimal microstructure should possess narrow and homogeneous γ; matrix channels. © 2015 IOP Publishing Ltd Printed in the UK.

Damage tolerance can be an elusive characteristic of structural materials requiring both high strength and ductility, properties that are often mutually exclusive. High-entropy alloys are of interest in this regard. Specifically, the single-phase CrMnFeCoNi alloy displays tensile strength levels of ∼1 GPa, excellent ductility (∼60-70%) and exceptional fracture toughness (KJIc >200 MPa √m). Here through the use of in situ straining in an aberration-corrected transmission electron microscope, we report on the salient atomistic to micro-scale mechanisms underlying the origin of these properties. We identify a synergy of multiple deformation mechanisms, rarely achieved in metallic alloys, which generates high strength, work hardening and ductility, including the easy motion of Shockley partials, their interactions to form stacking-fault parallelepipeds, and arrest at planar slip bands of undissociated dislocations. We further show that crack propagation is impeded by twinned, nanoscale bridges that form between the near-tip crack faces and delay fracture by shielding the crack tip.

Cobalt-based superalloys with a γ/γ' microstructure were discovered in 2006 and are currently being investigated as an alternative to nickel-based superalloys for high-temperature, high-load applications in gas turbine blades. They promise a better castability combined with a similar creep strength. Superalloy turbine blades are commonly coated with oxidation resistant bond coats. For this reason their compatibility needs to be studied. Co-9Al-9W specimens with a γ/γ' microstructure were coated with either a nickel-based or cobalt-based MCrAlY bond coat using vacuum plasma spraying. After aging at 900. °C in air for up to 500. h no decomposition of the γ' phase was found in the bulk superalloy. The interdiffusion zone shows several different W-rich topologically close-packed phases arising from the dissolution of the γ' phase in this region. The W-rich phases are identified to be μ phase for both bond coats and R phase for the nickel-based bond coat only. Their total volume is higher for the nickel-based bond coat. Therefore the cobalt-based bond coat is better suited for the Co-based superalloy substrate. Room temperature hardness and Young's modulus were measured using nanoindentation in the initial state and after heat treatment. A significantly higher Young's modulus was found for the cobalt-based bond coat. © 2015 Elsevier B.V..

CrMnCoFeNi is a FCC high-entropy alloy (HEA) that exhibits strong temperature dependence of strength at low homologous temperatures in sharp contrast to pure FCC metals like Ni that show weak temperature dependence. To understand this behavior, elastic constants were determined as a function of temperature. From 300 K down to 55 K, the shear modulus (G) of the HEA changes by only 8%, increasing from 80 to 86 GPa. This temperature dependence is weaker than that of FCC Ni, whose G increases by 12% (81-91 GPa). Therefore, the uncharacteristic temperature-dependence of the strength of the HEA is not due to the temperature dependence of its shear modulus. © 2014 Elsevier Ltd. All rights reserved.

Ni-base superalloys are used for turbine blades, which operate in the creep range at temperatures above 1000 °C. One of the objectives of modern materials science is to analyze the combination of elementary deformation and microstructural coarsening processes and to identify physically based micromechanical models which allow one to predict the mechanical behavior on the macroscale. High-temperature creep of single-crystal Ni-base superalloys is governed by dislocation plasticity in the well-known γ/γ′-microstructure. For a comprehensive description of plasticity, it is important to understand the nucleation, glide and climb of superdislocations in the γ′-phase. The rate-controlling dislocation processes have to be identified and therefore a reliable Burgers vector analysis of superdislocations is essential. Superdislocations exhibit complex dislocation cores, typically comprising superpartial dislocations and planar defects. Therefore, conventional Burgers vector analysis based on the invisibility criterion often fails, due to the presence of pronounced residual contrast. In the present work, large-angle convergent-beam electron diffraction (LACBED) is employed for Burgers vector determination of two characteristic superdislocations, of the standard <1 1 0> and the more complex <1 0 0> type. LACBED results are compared with results obtained using the conventional invisibility analysis. While both techniques work for the standard superdislocation, the conventional analysis fails to analyze the <1 0 0> superdislocation, which shows pronounced residual contrast even under conditions of g · b = 0 and g · b × u = 0. In contrast, the LACBED technique allows for an unambiguous determination of the Burgers vector, including its magnitude and absolute sense. In the present study, the use of LACBED to identify dislocations in the complex microstructure of an Ni-base superalloy is outlined and the better performance of LACBED as compared to the conventional gb-analysis is discussed. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A mechanism is presented which opposes coalescence of γ′-precipitates in Ni-base superalloys. The mechanism is based on the non-linear behaviour of the elastic energy in γ-channels, caused by the misfit strain between matrix and precipitate, as a function of the channel width. Variation of the channel width causes a disjoining pressure dependent on the density of misfit dislocations. © 2015 Taylor & Francis.

We report the first proof of concept for a non-aqueous semi-solid flow battery (SSFB) based on Na-ion chemistry using P2-type NaxNi0.22Co0.11Mn0.66O2 and NaTi2(PO4)3 as positive and negative electrodes, respectively. This concept opens the door for developing a new low-cost type of non-aqueous semi-solid flow batteries based on the rich chemistry of Na-ion intercalating compounds. © The Royal Society of Chemistry 2015.

The interaction of dislocations with precipitates is an essential strengthening mechanism in metals, as exemplified by the superior high-temperature strength of Ni-base superalloys. Here we use atomistic simulation samples generated from atom probe tomography data of a single crystal superalloy to study the interactions of matrix dislocations with a γ′ precipitate in molecular dynamics simulations. It is shown that the precipitate morphology, in particular its local curvature, and the local chemical composition significantly alter both, the misfit dislocation network which forms at the precipitate interface, and the core structure of the misfit dislocations. Simulated tensile tests reveal the atomic scale details of many experimentally observed dislocation-precipitate interaction mechanisms, which cannot be reproduced by idealized simulation setups with planar interfaces. We thus demonstrate the need to include interface curvature in the study of semicoherent precipitates and introduce as an enabling method atom probe tomography-informed atomistic simulations. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

During stress-free thermal analysis with differential scanning calorimetry (DSC), nickel titanium (NiTi) shape memory alloys show a thermal hysteresis which is affected by cooling/heating rates. Moreover, the Ni content of near equiatomic alloys governs the phase transition temperatures. This contribution aims at establishing a constitutive equation which can account for these effects, building on earlier work by Müller, Achenbach and Seelecke (MAS). To be specific, we discuss our new method with a focus on NiTi alloys. As in the original MAS model, our approach is rooted in a non-convex free energy representation and rate equations are utilized to incorporate history dependence during non-equilibrium processes. The relaxation times of these rate equations are determined by characteristic transformation probabilities which in turn are governed by the free energy landscape of our system. We show how the model can be parameterized to rationalize experimental DSC data observed for NiTi samples of variable composition and measured at variable cooling/heating rates. The good agreement between model predictions and experimental results suggests that thermal hystereses are not only related to interfacial strain energy effects but also affected by the transient character of the transformation process incorporating specific thermal relaxation times. Our analysis shows that we observe strong hysteretic effects when the cooling/heating rates exceed these characteristic relaxation rates. © 2014, Springer-Verlag Berlin Heidelberg.

In the present work we explain the concentration dependence of the martensite start temperature (MS) in Ni-Ti-based shape memory alloys (SMAs). We briefly review the present level of understanding and show that there is a need for further work. We then investigate the strong dependence of MS on alloy composition in binary Ni-Ti, ternary Ni-Ti-X (X = Cr, Cu, Hf, Pd, V, Zr) and quaternary Ni-Ti-Cu-Y (Y = Co, Pd) SMAs. For binary Ni-Ti, we combine differential scanning calorimetry experiments with insight gained through the application of the density functional theory (DFT) to show that heats of transformation ΔH decrease as Ni concentrations increase from 50.0 to 51.2 at.%. This causes a shift in the Gibbs free energy curves of austenite GA(T) and martensite GM(T), which in turn results in a lower MS temperature. Our DFT results suggest that the strong decrease of ΔH is caused by a stabilization of the B2 phase by structural relaxations around Ni antisite atoms, together with a gradual destabilization of B19′. The martensite start temperatures and the latent heats of transformation for binary, ternary and quaternary Ni-Ti-based SMAs are closely related. We observe smaller latent heats when the geometrical differences between the crystal structures of austenite and martensite decrease. © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

In austenitic stainless steel nitrogen stabilizes the austenitic phase improves the mechanical properties and increases the corrosion resistance. Nitrogen alloying enables to produce austenitic steels without the element nickel which is high priced and classified as allergy inducing. A novel production route is nitrogen alloying of CrMn-prealloyed steel powder via the gas phase. This is beneficial as the nitrogen content can be adjusted above the amount that is reached during conventional casting. A problem which has to be overcome is the oxide layer present on the powder surface which impedes both the sintering process and the uptake of nitrogen. This study focuses on whether heat treatment under pure nitrogen is an appropriate procedure to enable sintering and nitrogen uptake by reduction of surface oxides. X-ray photoelectron spectroscopy (XPS) in combination with scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS) are used to investigate the surface of powdered FeMn19Cr17C0.4N heat treated under nitrogen atmosphere. The analyses showed reduction of iron oxides already at 500 °C leading to oxide-free metallic surface zones. Mn and Cr oxides are reduced at higher temperatures. Distinct nitrogen uptake was registered, and successful subsequent sintering was reached. Copyright © 2014 John Wiley & Sons, Ltd.

Addition of Re in nickel-based superalloys results in an increase of the creep life. However, Re is also known to segregate to the dendrite core and to promote the formation of topologically closed packed (TCP) phases. In the present work, the local segregation of Re was studied in the heat treated and creep deformed state of a nickel-based superalloy. Tensile creep deformation at 1050°C resulted in the formation of TCP phases in the dendritic regions. Characterization using TEM confirmed the presence of μ phase that grows on {111} planes. Measurements with a nanoindenting AFM show that the μ phase is harder and shows less work hardening than both the γ and the γ' phases. Furthermore, in the creep deformed state the hardness of the matrix phase is very similar in the dendrite core and in interdendritic areas, although Re is still enriched in the dendrite core. It is shown that Re is consumed in the dendrite core by the TCP phases. © 2015 Elsevier B.V.

Metal-free nitrogen modified carbon catalysts (NC) are very closely related to MNC catalysts which contain a transition metal(s) (M), usually Fe or Co as an essential constituent. We investigated the influence of metal inclusions on the activity of nitrogen-doped carbon black in the electrocatalysis of the oxygen reduction reaction (ORR). A reference metal-free NC catalyst was prepared by pyrolysis of a polypyrrole/Vulcan XC72 composite at 800 °C for 2 h under helium. Controlled amounts of Co, Fe, Mn and Ni in low concentrations were then introduced into NC by impregnating it with the corresponding meso-tetra(4-pyridyl) porphyrin metal complex followed by further pyrolysis at 650 °C for 2 h under helium. The resulting catalysts were investigated for ORR using rotating disk electrode and rotating-ring disk electrode voltammetry in 0.1 M KOH. Additionally, the rate of decomposition of hydrogen peroxide by the different catalysts was determined in order to probe the influence of the metal inclusions on the mechanism and selectivity of the ORR. The results show that Fe, Co and Mn inclusions cause a substantial decrease of the overpotential of the reaction and enhance the catalytic current, whereas the presence of Ni has a poisoning effect on ORR. In the presence of Fe, the catalysts apparently reduce oxygen selectively to OH- in a direct four electron transfer process as opposed to the two-step, two electron pathway involving hydrogen peroxide as an intermediate for the case of the NC catalyst. © 2013 Elsevier Ltd.

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.

We optimize the magnetic and structural properties of Ni(Co,Cu)MnSn Heusler alloys for the magnetocaloric effect (MCE) by means of density functional theory combined with Monte Carlo simulations of a classical Heisenberg model. NiMnSn alloys show a drop of magnetization at the martensitic phase transition, which leads to the inverse MCE. We find either disordered or frustrated magnetic configurations directly below the martensitic transition temperature. However, the jump of magnetization at the magnetostructural transition is small as the austenite is in a ferrimagnetic state and not fully magnetized. For Co and Cu substitution, the structural phase transition temperature shifts to lower temperatures. In particular, Co substitution is promising, as the magnetization of the austenite increases by additional ferromagnetic interactions, which enhances the jump of magnetization. © 2014 IEEE.

This work focuses on the synthesis, characterization and testing of mixed protonic-electronic conducting membrane materials for H2 separation from gas mixtures capable of operating in a membrane reactor at temperatures higher than 600°C. La5.5WO12-δ and selected substituted barium zirconates with stoichiometries BaCe0.5Zr0.4Y0.1O3-δ and BaCe0.2Zr0.7Yb0.08Ni0.02O3-δ were therefore characterized and tested under coal-gasification-related conditions at 600-900°C. Sintered samples of the synthesized substituted barium zirconates were characterized by measuring the total conductivity and the thermal expansion coefficients. Also particle size distributions, BET surface-areas and elemental analysis of the starting powders, including commercial La5.5WO12-δ were specified. The compounds were exposed to syngas with steam, as well as to an atmosphere mainly consisting of CO2. The microstructure and phase composition of the membrane materials were studied by SEM, EDX and XRD before and after exposure. BaCe0.2Zr0.7Yb0.08Ni0.02O3-δ shows a very promising chemical stability from 600°C to 900°C and La5.5WO12-δ at 900°C. © 2014 Elsevier Ltd.

In this study we present a large scale numerical simulation of γ-γ′ microstructure evolution in Ni-base superalloy using the multi-phase field method in three dimensions. We numerically simulated precipitation hardening heat treatment cycles. Large scale three dimensional simulations are necessary in order to get sufficient statistics for predicting the morphological evolution, average γ′ precipitate size, precipitates size distribution over time and ripening exponent for a given temperature and composition. A detailed analysis of obtained result is presented emphasising the effect of elastic interaction on the coarsening kinetics in Ni-base superalloy. The study is performed using the phase-field modelling library "OpenPhase" which is based on a multi-phase field multi-component model. © 2014 Owned by the authors, published by EDP Sciences.

The catalytic performance of a Ni/MgAlOx catalyst was investigated in the high temperature CO2 reforming of CH4. The catalyst was developed using a Ni, Mg, Al hydrotalcite-like precursor obtained by co-precipitation. Despite the high Ni loading of 55 wt%, the synthesized Ni/MgAlOx catalyst possessed a thermally stable microstructure up to 900 °C with Ni nanoparticles of 9 nm. This stability is attributed to the embedding nature of the oxide matrix, and allows increasing the reaction temperature without losing active Ni surface area. To evaluate the effect of the reaction temperature on the reforming performance and the coking behavior, two different reaction temperatures (800 and 900 °C) were investigated. At both temperatures the prepared catalyst showed high rates of CH4 consumption. The higher temperature promotes the stability of the catalyst performance due to mitigation of the carbon formation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The present work deals with the thermomechanical fatigue and low-cycle fatigue behavior of C-263 in two different material conditions. Microstructural characteristics and fracture modes are investigated with light and electron microscopy. The experimental results indicate that viscoplastic deformations depend on the heat treatment or rather on the current state of the microstructure. The measured data are used to adjust the parameters of a Chaboche type model and a fracture-mechanics based model for fatigue lifetime prediction. The Chaboche model is able to describe the essential phenomena of time and temperature dependent cyclic plasticity including the complex cyclic hardening during thermo-cyclic loading of both material conditions with a unique set of material parameters. This could be achieved by including an additional internal variable into the Chaboche model which accounts for changes in the precipitation microstructure during high temperature loading. Furthermore, the proposed lifetime model is well suited for a common fatigue life prediction of both investigated heats. The deformation and lifetime models are implemented into a user defined material routine. In this work, the material routine is applied for the lifetime prediction of a critical power plant component using the finite element method. © 2014 Owned by the authors, published by EDP Sciences.

In situ high pressure 129Xe NMR spectroscopy in combination with volumetric adsorption measurements were used for the textural characterization of different carbon materials with well-defined porosity including microporous carbide-derived carbons, ordered mesoporous carbide-derived carbon, and ordered mesoporous CMK-3. Adsorption/desorption isotherms were measured also by NMR up to relative pressures close to p/p0 = 1 at 237 K. The 129Xe NMR chemical shift of xenon adsorbed in porous carbons is found to be correlated with the pore size in analogy to other materials such as zeolites. In addition, these measurements were performed loading the samples with n-nonane. Nonane molecules preferentially block the micropores. However, 129Xe NMR spectroscopy proves that the nonane also influences the mesopores, thus providing information about the pore system in hierarchically structured materials. © 2014 American Chemical Society.

Carbide-derived carbon (CDC) aerogel monoliths with very high porosity are synthesized starting from polymeric precursors. Cross-linking by platinum-catalyzed hydrosilylation of polycarbosilanes followed by supercritical drying yields preceramic aerogels. After ceramic conversion and silicon extraction in hot chlorine gas, hierarchically porous carbon materials with specific surface areas as high as 2122 m2 g-1 and outstanding total pore volumes close to 9 cm3 g-1 are obtained. Their pore structure is controllable by the applied synthesis temperature as shown by combined nitrogen (-196 °C) and carbon dioxide (0 °C) measurements coupled with electron microscopic methods. The combination of large micropore volumes and the aerogel-type pore system leads to advanced adsorption properties due to a combination of large storage capacities and effective materials transport in comparison with purely microporous reference materials as shown by thermal response measurements. This journal is © the Partner Organisations 2014.

Materials produced by selective laser melting (SLM) experience a thermal history that is markedly different from that encountered by conventionally produced materials. In particular, a very high cooling rate from the melt is combined with cyclical reheating upon deposition of subsequent layers. Using atom-probe tomography (APT), we investigated how this nonconventional thermal history influences the phase-transformation behavior of maraging steels (Fe-18Ni-9Co-3.4Mo-1.2Ti) produced by SLM. We found that despite the "intrinsic heat treatment" and the known propensity of maraging steels for rapid clustering and precipitation, the material does not show any sign of phase transformation in the as-produced state. Upon aging, three different types of precipitates, namely (Fe,Ni,Co)3(Ti,Mo), (Fe,Ni,Co)3(Mo,Ti), and (Fe,Ni,Co)7Mo6 (μ phase), were observed as well as martensite-to-austenite reversion around regions of the retained austenite. The concentration of the newly formed phases as quantified by APT closely matches thermodynamic equilibrium calculations. Copyright © 2014 Materials Research Society.

Ordered mesoporous carbide-derived carbon (OM-CDC) with a specific surface area as high as 2900 m2 g-1 was used as a model system in a supercapacitor setup based on an ionic liquid (IL; 1-ethyl-3-methylimidazolium tetrafluoroborate) electrolyte. Our study systematically investigates the effect of surface functional groups on IL-based carbon supercapacitors. Oxygen and chlorine functionalization was achieved by air oxidation and chlorine treatment, respectively, to introduce well-defined levels of polarity. The latter was analyzed by means of water physisorption isotherms at 298 K, and the functionalization level was quantified with X-ray photoelectron spectroscopy. While oxygen functionalization leads to a decreased capacitance at higher power densities, surface chlorination significantly improves the rate capability. A high specific capacitance of up to 203 F g-1 was observed for a chlorinated OM-CDC sample with a drastically increased rate capability in a voltage range of ±3.4 V. © 2014 American Chemical Society.

The Cr-Ni-Re system was investigated over the whole composition range using combinatorial fabrication methods combined with high-throughput characterization techniques in order to establish its thin film phase diagram. After annealing at 940 and 1100°C, the phase equilibrium was reached in the Ni-rich part of the ternary in agreement with the published bulk phase diagram. Annealing the materials library at 940°C is not sufficient to achieve the equilibrium state in the Re-rich part of the system, however by annealing the materials library at 1100°C the formation of expected phases (three solid-solutions and a topologically close packed compound) could be observed. As a result of this study, a thin film phase diagram of the complete Cr-Ni-Re at 1100°C was established, which is well comparable to the bulk phase diagram. This shows that the combinatorial thin film phase diagram approach is feasible and especially promising for materials systems with expensive and/or high melting point constituents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical Kroll-carbons (KCs) with combined micro- and mesopore systems are prepared from silica and alumina templates by a reductive carbochlorination reaction of fumed silica and alumina nanoparticles inside a dense carbon matrix. The resulting KCs offer specific surface areas close to 2000 m2 g-1 and total pore volumes exceeding 3 cm3 g-1, resulting from their hierarchical pore structure. High micropore volumes of 0.39 cm3 g-1 are achieved in alumina-based KCs due to the enhanced carbon etching reaction being mainly responsible for the evolution of porosity. Mesopore sizes are uniform and precisely controllable over a wide range by the template particle dimensions. The possibility of directly recycling the process exhaust gases for the template synthesis and the use of renewable carbohydrates as the carbon source lead to a scalable and efficient alternative to classical hard- and soft templating approaches for the production of mesoporous and hierarchical carbon materials. Silica- and alumina-based Kroll-carbons are versatile electrode materials in electrochemical double-layer capacitors (EDLCs). Specific capacitances of up to 135 F g-1 in an aqueous electrolyte (1 M sulfuric acid) and 174 F g-1 in ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate) are achieved when measured in a symmetric cell configuration up to voltages of 0.6 and 2.5 V, respectively. 90% of the capacitance can be utilized at high current densities (20 A g -1) and room temperature rendering Kroll-carbons as attractive materials for EDLC electrodes resulting in high capacities and high rate performance due to the combined presence of micro- and mesopores. This journal is © the Partner Organisations 2014.

Nb occupancy in the austenite B2-NiTi matrix and Ti2Ni phase in Ni-Ti-Nb shape memory alloys was investigated by aberration-corrected scanning transmission electron microscopy and precession electron diffraction. In both cases, Nb atoms were found to prefer to occupy the Ti rather than Ni sites. A projector augmented wave method within density functional theory was used to calculate the atomic and electronic structures of the austenitic B2-NiTi matrix phase and the Ti2Ni precipitates both with and without addition of Nb. The obtained formation energies and analysis of structural and electronic characteristics explain the preference for Ti sites for Nb over Ni sites. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The paper discusses the stabilization of the martensite in Ni2MnGa at finite temperatures that is caused by the substitution of Ni by Pt. For this purpose a recently developed ab initio based formalism employing density functional theory is applied. The free energies of the relevant austenite and martensite phases of Ni1.75Pt0.25MnGa are determined incorporating quasiharmonic phonons and fixed-spin magnons. In addition the dependence of the transition temperatures on the Pt concentration is investigated. Though our results are in qualitative agreement with estimates based on ground-state energies, they clearly demonstrate that a proper treatment of finite temperature contributions is important to predict the martensitic transition quantitatively. © 2014, ASM International.

Multiphase alloys in the Mo-Si-B system are potential high-temperature structural materials due to their good oxidation and creep resistance. Since they suffer from relatively high densities, the current study focuses on the influence of density-reducing Ti additions on creep and oxidation behavior at temperatures above 1273 K (1000 C). Two alloys with compositions of Mo-12.5Si-8.5B-27.5Ti and Mo-9Si-8B-29Ti (in at. pct) were synthesized by arc melting and then homogenized by annealing in vacuum for 150 hours at 1873 K (1600 C). Both alloys show similar creep behavior at stresses of 100 to 300 MPa and temperatures of 1473 K and 1573 K (1200 C and 1300 C), although they possess different intermetallic volume fractions. They exhibit superior creep resistance and lower density than a state-of-the-art Ni-base superalloy (single-crystalline CMSX-4) as well as other Mo-Si-B alloys. Solid solution strengthening due to Ti was confirmed by Vickers hardness measurements and is believed to be the reason for the significant increase in creep resistance compared to Mo-Si-B alloys without Ti, but with comparable microstructural length scales. The addition of Ti degrades oxidation resistance relative to a Mo-9Si-8B reference alloy due to the formation of a relatively porous duplex layer with titania matrix enabling easy inward diffusion of oxygen. © 2013 The Minerals, Metals & Materials Society and ASM International.

Superelastic Shape Memory Alloys (SMA) are typically used in applications where the martensitic phase transformation is exploited for its reversible, large deformation such as medical applications (e.g. stents). In this work, we focus on the mechanical and thermal behavior of a Nickel-Titanium SMA strip in bending mode. One possible application of this mode is to provide a restoring force when used in joints of SMA wire actuator systems making the need for an antagonistic SMA actuator redundant. In these applications mentioned above, typically only the mechanical properties are of interest while the temperature is considered constant, even though the martensitic phase transformation in SMA is a thermomechanically coupled process. As a part of the DFG (German Research Association) Priority Programme SPP1599 "Ferroic Cooling" which aims at advancing the development of solid state cooling devices, we have an equally large interest for the thermal evolution of Nickel-Titanium SMA during deformation and its induced phase transformation. In this paper we investigate the thermal and the mechanical response of a SMA beam during bending experiments in which the deformation is induced by holding one end of a SMA strip fixed while the other end is subject to a prescribed deflection. Sensors and high speed thermal cameras are used to capture reaction forces, deformations and temperature changes. We compare these experimental results with numerical simulation results obtained from Finite Element simulations where a thermo-mechanically coupled SMA model is implemented into a finite deformation framework. © 2014 by ASME.

In a genome-wide scan, we show that 30 variants in 25 genomic regions are associated with risk of TN breast cancer. Women carrying many of the risk variants may have 4-fold increased risk relative to women with few variants.Triple-negative (TN) breast cancer is an aggressive subtype of breast cancer associated with a unique set of epidemiologic and genetic risk factors. We conducted a two-stage genome-wide association study of TN breast cancer (stage 1: 1529 TN cases, 3399 controls; stage 2: 2148 cases, 1309 controls) to identify loci that influence TN breast cancer risk. Variants in the 19p13.1 and PTHLH loci showed genome-wide significant associations (P < 5 x 10(-) (8)) in stage 1 and 2 combined. Results also suggested a substantial enrichment of significantly associated variants among the single nucleotide polymorphisms (SNPs) analyzed in stage 2. Variants from 25 of 74 known breast cancer susceptibility loci were also associated with risk of TN breast cancer (P < 0.05). Associations with TN breast cancer were confirmed for 10 loci (LGR6, MDM4, CASP8, 2q35, 2p24.1, TERT-rs10069690, ESR1, TOX3, 19p13.1, RALY), and we identified associations with TN breast cancer for 15 additional breast cancer loci (P < 0.05: PEX14, 2q24.1, 2q31.1, ADAM29, EBF1, TCF7L2, 11q13.1, 11q24.3, 12p13.1, PTHLH, NTN4, 12q24, BRCA2, RAD51L1-rs2588809, MKL1). Further, two SNPs independent of previously reported signals in ESR1 [rs12525163 odds ratio (OR) = 1.15, P = 4.9 x 10(-) (4)] and 19p13.1 (rs1864112 OR = 0.84, P = 1.8 x 10(-) (9)) were associated with TN breast cancer. A polygenic risk score (PRS) for TN breast cancer based on known breast cancer risk variants showed a 4-fold difference in risk between the highest and lowest PRS quintiles (OR = 4.03, 95% confidence interval 3.46-4.70, P = 4.8 x 10(-) (69)). This translates to an absolute risk for TN breast cancer ranging from 0.8% to 3.4%, suggesting that genetic variation may be used for TN breast cancer risk prediction.

The structural stability of topologically close-packed phases in binary transition metal alloys is investigated with a combination of first-principles calculations based on density-functional theory and the Bragg-Williams-Gorsky approximation for the description of the configurational entropy. For a variety of different (i) exchange-correlation functionals, (ii) pseudopotentials, and (iii) relaxation schemes, for the relevant phases in Re-X (X = Ta, V, W) binary systems, we compare the energy of formation at T = 0 K, as well as the phase diagrams and site occupancies at finite temperatures. We confirm previous findings that the configurational entropy plays a stabilising role for complex phases in these systems at elevated temperatures. Small differences in the calculated energy of formation for different exchange-correlation functionals, pseudopotentials and relaxation schemes are expected, but give rise to qualitatively different phase diagrams. We employ these differences in order to estimate the order of magnitude of the standard deviation necessary in the qualitatively-reliable calculation of phase diagrams and site occupancies. In an attempt to determine the accuracy that is required to assure a qualitatively correct prediction of phase diagrams, we modify our first-principles results numerically by random variations with the determined standard deviation as maximum amplitude. Taking the order of site occupancies and the set of stable phases as simple criteria for a qualitatively correct prediction, we find that the accuracy required for the energy of formation of the individual configurations in these systems is approximately 5 meV/atom (≈0.5 kJ/mol at). © 2013 Elsevier B.V. All rights reserved.

An understanding of the high temperature mechanics experienced in Thermal Barrier Coatings (TBC) during cycling conditions would be highly beneficial to extending the lifespan of the coatings. This study will present results obtained using synchrotron x-rays to measure depth resolved strains in the various layers of TBCs under thermal mechanical loading and a superposed thermal gradient. Tubular specimens, coated with Yttria Stabilized Zirconia (YSZ) and an aluminum containing nickel alloy as a bond coat both through Electron Beam - Physical Vapor Deposition (EB-PVD), were subjected to external heating and controlled internal cooling generating a thermal gradient across the specimen's wall. Temperatures at the external surface were in excess of 1000°C. Throughout high temperature testing, 2-D high-resolution XRD strain measurements are taken at various locations through the entire depth of the coating layers. Across the YSZ a strain gradient was observed showing higher compressive strain at the interface to the bond coat than towards the surface. This behavior can be attributed to the specific microstructure of the EB-PVD-coating, which reveals higher porosity at the outer surface than at the interface to the bond coat, resulting in a lower in plane modulus near the surface. This location at the interface displays the most significant variation due to applied load at room temperature with this effect diminishing at elevated uniform temperatures. During thermal cycling with a thermal gradient and mechanical loading, the bond coat strain moves from a highly tensile state at room temperature to an initially compressive state at high temperature before relaxing to zero during the high temperature hold. The results of these experiments give insight into previously unseen material behavior at high temperature which can be used to develop an increased understanding of various failure modes and their causes. Copyright © 2014 by ASME.

Colloid-based chemical synthesis methods of bimetallic alloy nanoparticles (NPs) provide good monodispersity, yet generally show a strong variation of the resulting mean particle size with alloy composition. This severely compromises accurate correlation between composition of alloy particles and their size-dependent properties. To address this issue, a general CO adsorption-assisted capping ligand-free solvothermal synthesis method is reported which provides homogeneous bimetallic NPs with almost perfectly constant particle size over an unusually wide compositional range. Using Pt-Ni alloy NPs as an example, we show that variation of the reaction temperature between 160 and 240 °C allows for precise control of the resulting alloy particle bulk composition between 15 and 70 atomic % Ni, coupled with a constant mean particle size of ∼4 nm. The size-confining and Ni content-controlling role of CO during the nucleation and growth processes are investigated and discussed. Data suggest that size-dependent CO surface chemisorption and reversible Ni-carbonyl formation are key factors for the achievement of a constant particle size and temperature-controlled Ni content. To demonstrate the usefulness of the independent control of size and composition, size-deconvoluted relations between composition and electrocatalytic properties are established. Refining earlier reports, we uncover intrinsic monotonic relations between catalytic activity and initial Ni content, as expected from theoretical considerations. © 2014 American Chemical Society.

Interaction of Re, Ta, W and Mo solutes with vacancies and their diffusion in fcc Ni is investigated by density-functional theory in combination with kinetic Monte Carlo simulations. Interaction energies are calculated for the first six neighbor shells around the solutes and a complete set of diffusion barriers for these shells is provided. Further, diffusion coefficients for the four elements in Ni as well as for vacancies in the presence of these elements are calculated. The calculated solute diffusion coefficients based on our ab initio data are found to compare favorably to experimental values. The mobility of the vacancies as a key factor in dislocation climb is only minimally influenced by the solute atoms within the dilute limit. © 2014 IOP Publishing Ltd.

The creep anisotropy of the single crystal superalloy LEK 94 deformed in tension along [0 0 1] and [1 1 0] directions at 1293 K and 160 MPa was investigated. Elementary microstructural processes which are responsible for a higher increase in creep rates with strain during [1 1 0] as compared to [0 0 1] tensile loading were identified. [1 1 0] tensile creep is associated with a higher number of γ′ phase cutting events, where two dislocations with equal Burgers vectors of type <1 1 0> jointly shear the γ′ phase. The resulting <2 2 0>-type superdislocation can move by glide. In contrast, during [0 0 1] tensile loading, two dislocations with different <1 1 0>-type Burgers vectors must combine for γ′ phase cutting. The resulting <2 0 0>-type superdislocations can only move by a combination of glide and climb. The evolution of dislocation networks during creep determines the nature of the γ′ phase cutting events. The higher [1 1 0] creep rates at strains exceeding 2% result from a combination of a higher number of cutting events (density of mobile dislocations in γ′) and a higher superdislocation mobility (<2 2 0>glide) in the γ′ phase. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The efficient identification of compositional areas of interest in thin film materials systems fabricated by combinatorial deposition methods is essential in combinatorial materials science. We use a combination of compositional screening by EDX together with high-throughput measurements of electrical and optical properties of thin film libraries to determine efficiently the areas of interest in a materials system. Areas of interest are compositions which show distinctive properties. The crystallinity of the thus determined areas is identified by X-ray diffraction. Additionally, by using automated nanoindentation across the materials library, mechanical data of the thin films can be obtained which complements the identification of areas of interest. The feasibility of this approach is demonstrated by using a Ni-Al thin film library as a reference system. The obtained results promise that this approach can be used for the case of ternary and higher order systems. © 2014 American Chemical Society.

Polymer-based carbide-derived carbons (CDCs) with combined micro- and mesopores are prepared by an advantageous sacrificial templating approach using poly(methylmethacrylate) (PMMA) spheres as the pore forming material. Resulting CDCs reveal uniform pore size and pore shape with a specific surface area of 2434 m2 g-1 and a total pore volume as high as 2.64 cm3 g-1. The bimodal CDC material is a highly attractive host structure for the active material in lithium-sulfur (Li-S) battery cathodes. It facilitates the utilization of high molarity electrolytes and therefore the cells exhibit good rate performance and stability. The cathodes in the 5 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolyte show the highest discharge capacities (up to 1404 mA h gs-1) and capacity retention (72% after 50 cycles at C/5). The unique network structure of the carbon host enables uniform distribution of sulfur through the conductive media and at the same time it facilitates rapid access for the electrolyte to the active material. This journal is © the Partner Organisations 2014.

Derivatives of the commercial alloy CMSX-4 were directionally solidified and characterized with respect to their final dendrite microstructure. The results indicate that Ni-based superalloys with high segregation levels show significant instability in secondary dendrite arms and an increased tendency for tertiary arm formation, respectively. Phase-field simulations were used to explore the impact of chemical composition on morphological instability and tertiary arm formation during the directional solidification of Ni-based superalloys. It is found that an increase in specific alloying elements in the overall alloy composition leads to pronounced segregation at the end of solidification. This causes strong growth restriction of the secondary arms and triggers tertiary arm formation. The proposed mechanism explains experimental microstructures found in modifications of the base alloy CMSX-4. © 2014 IOP Publishing Ltd.

Coking dynamics of Ni-based and Ni-free catalysts were studied in a magnetic suspension thermobalance under methane dry reforming conditions. Ni-rich catalysts undergo strong coking featured with a surface saturation point where the coking rate is drastically reduced. Catalyst resistance towards coking may be enhanced by using noble-metal-based Ni-free precursors or decreasing the Ni content in the catalytic system. The post reaction performed temperature-programmed oxidation experiment of the coked catalyst is diffusion-limited due to large amounts of formed carbon. © 2014 Wiley-VCH Verlag GmbH & Co. KGaA.

A thin film composition gradient library of the Ni-Cu alloy system is generated through an electrodeposition technique using a complexing citrate electrolyte bath in a modified Hull cell. Energy dispersive X-ray spectroscopy, scanning electron microscopy and automated X-ray diffraction are performed to assess composition, surface morphology, and crystallographic structure of the deposited film as a function of the lateral position on the materials library. The results confirmed deposition of single phase polycrystalline f.c.c. Ni-Cu alloy system with varied lateral composition and lattice parameter, afcc as well. © 2014 The Electrochemical Society. All rights reserved.

We present a physics-based constitutive model of dislocation glide in metals that explicitly accounts for the redistribution of dislocations due to their motion. The model parameterizes the complex microstructure by dislocation densities of edge and screw character, which either occur with monopolar properties, i.e. a single dislocation with positive or negative line sense, or with dipolar properties, i.e. two dislocations of opposite line sense combined. The advantage of the model lies in the description of the dislocation density evolution, which comprises the usual rate equations for dislocation multiplication and annihilation, and formation and dissociation of dislocation dipoles. Additionally, the spatial redistribution of dislocations by slip is explicitly accounted for. This is achieved by introducing an advection term for the dislocation density that turns the evolution equations for the dislocation density from ordinary into partial differential equations. The associated spatial gradients of the dislocation slip render the model nonlocal. The model is applied to wedge indentation in single-crystalline nickel. The simulation results are compared to published experiments (Kysar et al., 2010) in terms of the spatial distribution of lattice rotations and geometrically necessary dislocations. In agreement with experiment, the predicted dislocation fluxes lead to accumulation of geometrically necessary dislocations around a vertical geometrical border with a high orientation gradient below the indenter that is decisive for the overall plastic response. A local model variant without dislocation transport is not able to predict the influence of this geometrical transition zone correctly and is shown to behave markedly softer. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

B2 NiMn and Ni2MnAl Heusler nanoprecipitates are designed via elastic misfit stabilization in Fe-Mn maraging steels by combining transmission electron microscopy (TEM) correlated atom probe tomography (APT) with ab initio simulations. Guided by these predictions, the Al content of the alloys is systematically varied, and the influence of the Al concentration on structure stability, size and distribution of precipitates formed during ageing at 450 °C is studied using scanning electron microscopy-electron backscatter diffraction, TEM and APT. Specifically, the Ni2MnAl Heusler nanoprecipitates exhibit the finest sizes and highest dispersion and hence lead to significant strengthening. The formation of the different types of precipitates and their structure, size, dispersion and effect on the mechanical properties of the alloys are discussed. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ti-Ni-Au thin film materials libraries were prepared from multilayer precursors by combinatorial sputtering. The materials libraries were annealed at 500, 600, and 700 °C for 1 h and then characterized by high-throughput methods to investigate the relations between composition, structure and functional properties. The identified relations were visualized in functional phase diagrams. The goal is to identify composition regions that are suitable as high temperature shape memory alloys. Phase transforming compositions were identified by electrical resistance measured during thermal cycles in the range of -20 and 250 °C. Three phase transformation paths were confirmed: (1) B2-R, (2) B2-R-B19', and (3) B2-B19. For the materials library annealed at 500 °C only the B2-R transformation was observed. For the materials libraries annealed at 600 and 700 °C, all transformation paths were observed. High transformation temperatures (Ms ≈100 °C) were only obtained by annealing at 600 or 700 °C, and with compositions of Ti ≈ 50 at. % and Au > 20 at. %. This is the composition range that undergoes B2-B19 transformation. The phase transformation behaviors were explained according to the compositional and annealing temperature dependence of phase/structure formation, as revealed by X-ray diffraction analysis of the materials libraries. © 2014 American Chemical Society.

Highly stable Ni catalysts with varying Ni contents up to 50 mol% originating from hydrotalcite-like precursors were applied in the dry reforming of methane at 800 and 900 °C. The integral specific rate of methane conversion determined after 10 h on stream was 3.8 mmol s-1 g cat -1 at 900 °C. Due to the outstanding high activity, a catalyst mass of just 10 mg had to be used to avoid operating the reaction in thermodynamic equilibrium. The resulting WHSV was as high as 1.44 × 106 ml gcat -1 h-1. The observed axial temperature distribution with a pronounced cold spot was analyzed by computational fluid dynamics simulations to verify the strong influence of this highly endothermic reaction. Transmission electron microscopy and temperature-programmed oxidation experiments were used to probe the formation of different carbon species, which was found to depend on the catalyst composition and the reaction temperature. Among the formed carbon species, multi-walled carbon nanofibers were detrimental to the long-term stability at 800 °C, whereas their formation was suppressed at 900 °C. The formation of graphitic carbon at 900 °C originating from methane pyrolysis played a minor role. The methane conversion after 100 h of dry reforming at 900 °C compared to the initial one amounted to 98% for the 25 mol% Ni catalyst. The oxidative regeneration of the catalyst was achieved in the isothermal mode using only carbon dioxide in the feed. © the Partner Organisations 2014.

Fe-based alloys are used extensively in many structural applications including under irradiation conditions in the nuclear industry. In this study, model Fe-Cr, Fe-Ni and Fe-Cr-Ni alloys that are the basis of many structural steels were synthesized as single crystals and characterized. The compositions investigated were Fe-15Cr, Fe-30Cr, Fe-30Ni and Fe-15Cr-15Ni (at%). Several key mechanical properties were determined which will be useful in further studies of irradiation/deformation-induced defects. Incipient plasticity and slip characteristics were investigated by nanoindentation on (001) and (1-10) surfaces, and hardness, modulus, pop-in behavior and theoretical strength were determined. The slip trace patterns after microindentation were imaged in a microscope. A novel slip trace analysis was developed and the underlying deformation mechanisms identified. The analysis shows that under both (001) and (1-10) indentations, the activated slip system for the BCC alloys is {112} for the FCC alloys the activated slip plane is {111}. These results were confirmed with finite element simulations using a slip-based crystal-plasticity model. Finally, the effects of heterogeneous pop-in mechanisms are discussed in the context of incipient plasticity in the four different alloys. © 2014 Elsevier B.V.

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.

Ni-free austenitic steels alloyed with Cr and Mn are an alternative to conventional Ni-containing steels. Nitrogen alloying of these steel grades is beneficial for several reasons such as increased strength and corrosion resistance. Low solubility in liquid and δ-ferrite restricts the maximal N-content that can be achieved via conventional metallurgy. Higher contents can be alloyed by powder-metallurgical (PM) production via gas–solid interaction. The performance of sintered parts is determined by appropriate sintering parameters. Three major PM-processing routes, hot isostatic pressing, supersolidus liquid phase sintering (SLPS), and solid-state sintering, were performed to study the influence of PM-processing route and N-content on densification, fracture, and mechanical properties. Sintering routes are designed with the assistance of thermodynamic calculations, differential thermal analysis, and residual gas analysis. Fracture surfaces were studied by X-ray photoelectron spectroscopy, secondary electron microscopy, and energy dispersive X-ray spectroscopy. Tensile tests and X-ray diffraction were performed to study mechanical properties and austenite stability. This study demonstrates that SLPS process reaches high densification of the high-Mn-containing powder material while the desired N-contents were successfully alloyed via gas–solid interaction. Produced specimens show tensile strengths >1000 MPa combined with strain to fracture of 60 pct and thus overcome the other tested production routes as well as conventional stainless austenitic or martensitic grades. © 2014, The Author(s).

Sputter deposition of 50 nm thick NiO films on p+-n-Si and subsequent treatment in an Fe-containing electrolyte yielded highly transparent photoanodes capable of water oxidation (OER) in alkaline media (1 M KOH) with high efficiency and stability. The Fe treatment of NiO thin films enabled Si-based photoanode assemblies to obtain a current density of 10 mA/cm2 (requirement for >10% efficient devices) at 1.15 V versus RHE (reversible hydrogen electrode) under red-light (38.6 mW/cm2) irradiation. Thus, the photoanodes were harvesting ∼80 mV of free energy (voltage), which places them among the best-performing Si-based photoanodes in alkaline media. The stability was proven by chronoamperometry at 1.3 V versus RHE for 300 h. Furthermore, measurements with electrochemical quartz crystal microbalances coupled with ICP-MS showed minor corrosion under dark operation. Extrapolation of the corrosion rate showed stability for more than 2000 days of continuous operation. Therefore, protection by Fe-treated NiO films is a promising strategy to achieve highly efficient and stable photoanodes. © 2014 American Chemical Society.

Nickel Titanium (NiTi) alloys possess special mechanical properties and good biocompatibility hence used as base material for the production of vascular stents. Normally, vascular stents are machined from NiTi tubes, using laser cutting processes. Braiding is a promising alternative for the machining of certain NiTi stents. However, a surface finish treatment, such as electropolishing of the braided stents, is still required in order to achieve a medical-grade surface finish. The thermally-grown oxide resulting from the shape-setting heat treatment, following the braiding must be removed. Moreover, electropolishing is required to achieve optimum corrosion resistance. Therefore, the aim of this study is to find suitable parameters for the effective electropolishing of NiTi textile stents. Electropolishing of a device with such a complex geometry is challenging, hence a custom-designed electrolytic cell was constructed and used in this study. We examined the stent surfaces before and after electropolishing, using scanning electron microscopy (SEM) and confocal laser scanning microscopy (CLSM). Potentiodynamic tests were performed in NaCl 0.9% solution for as-received and electropolished samples. The results from the present study indicate an improvement in surface quality of the braided stents after electropolishing. Potentiodynamic tests revealed that electropolishing improves the corrosion resistance of the NiTi stents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

The influence of redox dynamics of a Ni/MgAl oxide catalyst for dry reforming of methane (DRM) at high temperature was studied to correlate structural stability with catalytic activity and coking propensity. Structural aging of the catalyst was simulated by repeated temperature-programmed reduction/oxidation (TPR/TPO) cycles. Despite a very high Ni loading of 55.4 wt.%, small Ni nanoparticles of 11 nm were obtained from a hydrotalcite-like precursor with a homogeneous distribution. Redox cycling gradually changed the interaction of the active Ni phase with the oxide support resulting in a crystalline Ni/MgAl2O4-type catalyst. After cycling the average particle size increased from 11 to 21 nm - while still a large fraction of small particles was present - bringing about a decrease in Ni surface area of 72%. Interestingly, the redox dynamics and its strong structural and chemical consequences were found to have only a moderate influence on the activity in DRM at 900 °C, but lead to a stable attenuation of carbon formation due to a lower fraction of graphitic carbon after DRM in a fixed-bed reactor. Supplementary DRM experiments in a thermobalance revealed that coke formation as a continuous process until a carbon limit is reached and confirmed a higher coking rate for the cycled catalyst. © 2014 Published by Elsevier B.V.

The current investigation proposes a novel method for simultaneous assessment of the electrochemical and structural fatigue properties of nickel-titanium shape memory alloy (NiTi SMA) wires. The design and layout of an in situ electrochemical cell in a custom-made bending rotation fatigue (BRF) test rig is presented. This newly designed test rig allows performing a wide spectrum of experiments for studying the influence of fatigue on corrosion and vice versa. This can be achieved by performing ex situ andor in situ measurements. The versatility of the combined electrochemicalmechanical test rig is demonstrated by studying the electrochemical behavior of NiTi SMA wires in 0.9 NaCl electrolyte under load. The ex situ measurements allow addressing various issues, for example, the influence of pre-fatigue on the localized corrosion resistance, or the influence of hydrogen on fatigue life. Ex situ experiments showed that a pre-fatigued wire is more susceptible to localized corrosion. The synergetic effect can be concluded from the polarization studies and specifically from an in situ study of the open circuit potential (OCP) transients, which sensitively react to the elementary repassivation events related to the local failure of the oxide layer. It can also be used as an indicator for identifying the onset of the fatigue failure. © 2013 American Institute of Physics.

In patented and cold-drawn pearlitic steel wires dissociation of cementite occurs during mechanical deformation. In this study the influence of the carbon decomposition on the diffusion of nickel in ferrite is investigated by means of atom probe tomography. In the temperature range 423-523 K we observed a much smaller activation energy of Ni diffusion than for self-diffusion in body-centered cubic iron, indicating an increased vacancy density owing to enhanced formation of vacancy-carbon complexes. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy allows a detailed analysis of surface attached molecules, including their secondary structure, orientation, and interaction with small molecules in the case of proteins. Here, we present a universal immobilization technique on germanium for all oligo-histidine-tagged proteins. For this purpose, new triethoxysilane derivates were developed: we synthesized a linker-silane with a succinimidyl ester as amine-reactive headgroup and a matrix-silane with an unreactive ethylene glycol group. A new methodology for the attachment of triethoxysilanes on germanium was established, and the surface was characterized by ATR-FTIR and X-ray photoelectron spectroscopy. In the next step, the succinimidyl ester was reacted with aminonitrilotriacetic acid. Subsequently, Ni2+ was coordinated to form Ni-nitrilotriacetic acid for His-tag binding. The capability of the functionalized surface was demonstrated by experiments using the small GTPase Ras and photosystem I (PS I). The native binding of the proteins was proven by difference spectroscopy, which probes protein function. The function of Ras as molecular switch was demonstrated by a beryllium trifluoride anion titration assay, which allows observation of the "on" and "off" switching of Ras at atomic resolution. Furthermore, the activity of immobilized PS I was proven by light-induced difference spectroscopy. Subsequent treatment with imidazole removes attached proteins, enabling repeated binding. This universal technique allows specific attachment of His-tagged proteins and a detailed study of their function at the atomic level using FTIR difference spectroscopy. © 2013 American Chemical Society.

In the present contribution several advanced electron microscopy techniques are employed in order to describe chemical and structural features of the nano- and microstructure of a Ni45.5Ti45.5Nb9 alloy. A line-up of Nb-rich nano-precipitates is found in the Ni-Ti-rich austenite of as-cast material. Concentration changes of the matrix after annealing are correlated with changes in the transformation temperatures. The formation of rows and plates of larger Nb-rich precipitates and particles is described. The interaction of a twinned martensite plate with a Nb-rich nano-precipitate is discussed and the substitution of Nb atoms on the Ti-sublattice in the matrix is confirmed. © (2013) Trans Tech Publications, Switzerland.

Different heats of the nickel-base Alloy 617B are tested under in-phase and out-of-phase thermo-mechanical fatigue (TMF) conditions at temperatures between 50 and 900 °C. During one of the TMF tests the growth of microcracks is observed using the replica technique. After the tests, some of the specimens are inspected by scanning electron microscopy in order to analyse the prevailing damage mechanisms compared with those observed in isothermal low-cycle fatigue (LCF) tests. In addition, a Chaboche-type model and a fracture-mechanics-based lifetime model are employed to describe the cyclic viscoplastic deformation and fatigue lifetime. The Chaboche model adjusted to isothermal data is found to reasonably predict the cyclic viscoplastic behaviour of thermo-mechanically loaded specimens. Lifetime data of TMF tests fall into a common scatter band with LCF tests at temperatures above 400 °C if the test results are analysed based on the introduced lifetime model.

The application of high nearly hydrostatic pressures at elevated temperatures on the LEK94 single crystal (SX) nickel-based superalloy directly affects its microstructure. This is due to a combination of the effect of pressure on the Gibbs free energy, on the diffusion coefficients of the alloying elements, on the internal coherent stresses, and on the porosity distribution. The last effect depends at least on the first three. Therefore, based on the theoretical influences of the pressure, the main objective of this work is to understand, by means of an experimental work, the effect of high pressure at elevated temperature during annealing on the evolution of the phases morphology, and porosity of the high-temperature material LEK94. Specifically, pressures up to 4 GPa, temperatures up to 1180 C, and holding times up to 100 h were investigated. The main findings are that, porosity can be considerably reduced without affecting significantly the γ/γ′ microstructure by high pressure annealing and the verification that increasing the external pressure stabilizes the γ′-phase. © 2012 Springer Science+Business Media, LLC.

Nickel pincer complexes of the type [2,6-(R2PO) 2C6H3]NiH (R = tBu, 1a; R = iPr, 1b; R = cPe, 1c) react with BH3·THF to produce borohydride complexes [2,6-(R2PO)2C 6H3]Ni(η2-BH4) (2a-c), as confirmed by NMR and IR spectroscopy, X-ray crystallography, and elemental analysis. The reactions are irreversible at room temperature but reversible at 60 C. Compound 1a exchanges its hydrogen on the nickel with the borane hydrogen of 9-BBN or HBcat, but does not form any observable adduct. The less bulky hydride complexes 1b and 1c, however, yield nickel dihydridoborate complexes reversibly at room temperature when mixed with 9-BBN and HBcat. The dihydridoborate ligand in these complexes adopts an η2- coordination mode, as suggested by IR spectroscopy and X-ray crystallography. Under the catalytic influence of 1a-c, reduction of CO2 leads to the methoxide level when 9-BBN or HBcat is employed as the reducing agent. The best catalyst, 1a, involves bulky substituents on the phosphorus donor atoms. Catalytic reactions involving 1b and 1c are less efficient because of the formation of dihydridoborate complexes as the dormant species as well as partial decomposition of the catalysts by the boranes. © 2012 American Chemical Society.

A promising approach to improving the performance of iron-phosphate FePO4 cathode materials for Li-ion batteries is to partly or fully substitute Fe with other metals. Here, we use high-throughput density-functional theory (DFT) calculations to investigate binary mixtures of metal atoms M and M′ in (Li)MyM'1-yPO4 olivine phosphates. We determine the formation energy for various stoichiometries of different binary combinations of metals for the cases of full lithiation and delithiation. Systematic screening of all combinations of Fe and Mn with elements of the 3d transition-metal (TM) series allows us to identify trends with average band filling and atomic size. We also included compounds that verify the observed relations or that were discussed as cathode materials, particularly Ni-Co, V-Cu and V-Ni, as well as combinations with 4d TMs (Fe-Zr, Fe-Mo, Fe-Ag) and with Mg (Fe-Mg and Ni-Mg). Based on our DFT calculations for each compound, we estimate the volume change during intercalation, the intercalation voltage, the energy density and the thermal stability with respect to reaction with oxygen. Our calculations indicate that the energy density of the binary TM phosphates increases with average band filling while the thermal stability of the compounds decreases. © 2013 IOP Publishing Ltd.

Nick of time: The nickel cyanomethyl complex 1 catalyzes the room temperature coupling of aldehydes with acetonitrile under base-free conditions. The catalytic system is long-lived and remarkably efficient with high turnover numbers (TONs) and turnover frequencies (TOFs) achieved. The mild reaction conditions allow a wide variety of aldehydes, including base-sensitive ones, to catalytically react with acetonitrile. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nickel-Titanium shape memory alloys (NiTi-SMA) are of biomedical interest due to their unusual range of pure elastic deformability and their elastic modulus, which is closer to that of bone than any other metallic or ceramic material. Newly developed porous NiTi, produced by Selective Laser Melting (SLM), is currently under investigation as a potential carrier material for human mesenchymal stem cells (hMSC). SLM enables the production of highly complex and tailor-made implants for patients on the basis of CT data. Such implants could be used for the reconstruction of the skull, face, or pelvis. hMSC are a promising cell type for regenerative medicine and tissue engineering due to their ability to support the regeneration of critical size bone defects. Loading porous SLM-NiTi implants with autologous hMSC may enhance bone growth and healing for critical bone defects. The purpose of this study was to assess whether porous SLM-NiTi is a suitable carrier for hMSC. Specimens of varying porosity and surface structure were fabricated via SLM. hMSC were cultured for 8 days on NiTi specimens, and cell viability was analyzed using two-color fluorescence staining. Viable cells were detected on all specimens after 8 days of cell culture. Cell morphology and surface topography were analyzed by scanning electron microscopy (SEM). Cell morphology and surface topology were dependent on the orientation of the specimens during SLM production. The Nickel ion release can be reduced significantly by aligned laser processing conditions. The presented results clearly attest that both dense SLM-NiTi and porous SLM-NiTi are suitable carriers for hMSC. Nevertheless, before carrying out in vivo studies, some work on optimization of the manufacturing process and post-processing is required. © 2012 Elsevier B.V.

A thickness dependent exchange bias in the low temperature martensitic state of epitaxial Ni-Mn-Sn thin films is found. The effect can be retained down to very small thicknesses. For a Ni50Mn32Sn18 thin film, which does not undergo a martensitic transformation, no exchange bias is observed. Our results suggest that a significant interplay between ferromagnetic and antiferromagnetic regions, which is the origin for exchange bias, is only present in the martensite. The finding is supported by ab initio calculations showing that the antiferromagnetic order is stabilized in the phase. © 2013 Author(s).

Processing of Nickel-Titanium shape memory alloys (NiTi) is by no means easy because all processing steps can strongly affect the properties of the material. Hence, near-net-shaping technologies are very attractive for processing NiTi due to reduction of the processing route. Additive Manufacturing (AM) provides especially promising alternatives to conventional processing because it offers unparalleled freedom of design. In the last 5 years AM of NiTi received little attention from academics and researchers and, therefore, is far from being established for processing NiTi today. This work is to highlight the current state of the art of using the AM technique Selective Laser Melting (SLM) for processing high quality NiTi parts. For this reason, fundamentals for SLM processing of NiTi are described. It is shown in detail that a careful control of process parameters is of great importance. Furthermore, this work characterizes structural and functional properties like shape recovery, referring to the shape memory effect in Ti-rich SLM NiTi, or pseudoelasticy in Ni-rich SLM NiTi. It is shown that both types of shape memory effects can be adjusted in SLM NiTi by the choice of the raw material and processing strategy. By comparing the properties of SLM NiTi to those of conventionally processed NiTi, this work clearly shows that SLM is an attractive manufacturing method for production of high quality NiTi parts. Copyright © 2013 by ASME.

Inelastic neutron scattering measurements on Ba(Fe0.963Ni 0.037)2As2 manifest a neutron spin resonance in the superconducting state with anisotropic dispersion within the Fe layer. Whereas the resonance is sharply peaked at the antiferromagnetic (AFM) wave vector QAFM along the orthorhombic a axis, the resonance disperses upwards away from QAFM along the b axis. In contrast to the downward dispersing resonance and hourglass shape of the spin excitations in superconducting cuprates, the resonance in electron-doped BaFe 2As2 compounds possesses a magnonlike upwards dispersion. © 2013 American Physical Society.

High configurational entropies have been hypothesized to stabilize solid solutions in equiatomic, multi-element alloys which have attracted much attention recently as "high-entropy" alloys with potentially interesting properties. To evaluate the usefulness of configurational entropy as a predictor of single-phase (solid solution) stability, we prepared five new equiatomic, quinary alloys by replacing individual elements one at a time in a CoCrFeMnNi alloy that was previously shown to be single-phase [1]. An implicit assumption here is that, if any one element is replaced by another, while keeping the total number of elements constant, the configurational entropy of the alloy is unchanged; therefore, the new alloys should also be single-phase. Additionally, the substitute elements that we chose, Ti for Co, Mo or V for Cr, V for Fe, and Cu for Ni, had the same room temperature crystal structure and comparable size/electronegativity as the elements being replaced to maximize solid solubility consistent with the Hume-Rothery rules. For comparison, the base CoCrFeMnNi alloy was also prepared. After three-day anneals at elevated temperatures, multiple phases were observed in all but the base CoCrFeMnNi alloy, suggesting that, by itself, configurational entropy is generally not able to override the competing driving forces that also govern phase stability. Thermodynamic analyses were carried out for each of the constituent binaries in the investigated alloys (Co-Cr, Fe-Ni, Mo-Mn, etc.). Our experimental results combined with the thermodynamic analyses suggest that, in general, enthalpy and non-configurational entropy have greater influences on phase stability in equiatomic, multi-component alloys. Only when the alloy microstructure is a single-phase, approximately ideal solid solution does the contribution of configurational entropy to the total Gibbs free energy become dominant. Thus, high configurational entropy provides a way to rationalize, after the fact, why a solid solution forms (if it forms), but it is not a useful a priori predictor of which of the so-called high-entropy alloys will form thermodynamically stable single-phase solid solutions.

We have studied a nanocrystalline AlCrCuFeNiZn high-entropy alloy synthesized by ball milling followed by hot compaction at 600 C for 15 min at 650 MPa. X-ray diffraction reveals that the mechanically alloyed powder consists of a solid-solution body-centered cubic (bcc) matrix containing 12 vol.% face-centered cubic (fcc) phase. After hot compaction, it consists of 60 vol.% bcc and 40 vol.% fcc. Composition analysis by atom probe tomography shows that the material is not a homogeneous fcc-bcc solid solution but instead a composite of bcc structured Ni-Al-, Cr-Fe- and Fe-Cr-based regions and of fcc Cu-Zn-based regions. The Cu-Zn-rich phase has 30 at.% Zn α-brass composition. It segregates predominantly along grain boundaries thereby stabilizing the nanocrystalline microstructure and preventing grain growth. The Cr- and Fe-rich bcc regions were presumably formed by spinodal decomposition of a Cr-Fe phase that was inherited from the hot compacted state. The Ni-Al phase remains stable even after hot compaction and forms the dominant bcc matrix phase. The crystallite sizes are in the range of 20-30 nm as determined by transmission electron microscopy. The hot compacted alloy exhibited very high hardness of 870 ± 10 HV. The results reveal that phase decomposition rather than homogeneous mixing is prevalent in this alloy. Hence, our current observations fail to justify the present high-entropy alloy design concept. Therefore, a strategy guided more by structure and thermodynamics for designing high-entropy alloys is encouraged as a pathway towards exploiting the solid-solution and stability idea inherent in this concept. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A study of the morphological and chemical stability of shape-selected octahedral Pt0.5Ni0.5 nanoparticles (NPs) supported on highly oriented pyrolytic graphite (HOPG) is presented. Ex situ atomic force microscopy (AFM) and in situ X-ray photoelectron spectroscopy (XPS) measurements were used to monitor the mobility of Pt0.5Ni0.5 NPs and to study long-range atomic segregation and alloy formation phenomena under vacuum, H2, and O2 environments. The chemical state of the NPs was found to play a pivotal role in their surface composition after different thermal treatments. In particular, for these ex situ synthesized NPs, Ni segregation to the NP surface was observed in all environments as long as PtOx species were present. In the presence of oxygen, an enhanced Ni surface segregation was observed at all temperatures. In contrast, in hydrogen and vacuum, the Ni outward segregation occurs only at low temperature (< 200-270 C), while PtOx species are still present. At higher temperatures, the reduction of the Pt oxide species results in Pt diffusion toward the NP surface and the formation of a Ni-Pt alloy. A consistent correlation between the NP surface composition and its electrocatalytic CO oxidation activity was established. © 2013 American Chemical Society.

Nb-rich precipitates in the matrix of as-cast and annealed Ni45.5Ti45.5Nb9alloys are investigated by scanning and scanning transmission electron microscopy, including slice-and-view and geometric phase analysis (GPA). The Nb-rich bcc nano-precipitates in the as-cast alloy have a 10% lattice parameter difference with the B2 matrix and reveal compensating interface dislocations. The 3D reconstruction of the configuration of small Nb-rich precipitates in the annealed alloy reveals a wall-like distribution of precipitates, which may increase the thermal hysteresis of the material. © (2013) Trans Tech Publications, Switzerland.

In the present work, modulated four- and five-layered orthorhombic, seven-layered monoclinic (4O, 10M and 14M) and unmodulated double tetragonal (L10) martensites are characterized in Heusler Ni-Mn-Sn alloys using X-ray diffraction, high-resolution transmission electron microscopy, electron diffraction techniques and thermal analysis. All modulated layered martensites exhibit twins and stacking faults, while the L10 martensite shows fewer structural defects. The substitution of Sn with Mn in Ni 50Mn37+xSn13-x (x = 0, 2, 4) enhances the martensitic transition temperatures, while the transition temperatures decrease with increasing Mn content for constant Sn levels in Ni50-yMn37+ySn13 (y = 0, 2, 4). The compositional dependence of the martensitic transition temperatures is mainly attributed to the valence electron concentration (e/a) and the unit-cell volume of the high-temperature phase. With increasing transition temperatures (or e/a), the resultant martensitic crystal structure evolves in a sequence of 4O → 10M → 14M → L10 in bulk Ni-Mn-Sn alloys. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A NiAl-Mo eutectic having a nominal composition of Ni-45Al-10Mo was directionally solidified in a floating-zone furnace at two different growth rates, 20 and 80 mm/h. At the slower growth rate, the Mo fibers in the composite are well-aligned with the growth direction, whereas at the higher growth rate cellular microstructures are observed. Creep testing at 900°C showed that the minimum creep rate is much higher for cellular than for well-aligned structures. In the cellular case a "soft" cell boundary consisting primarily of binary NiAl surrounding "hard" eutectic cell interiors seems to facilitate cell boundary sliding and therefore results in low creep strength. A microstructure-based composite model is used to explain the effects of fiber alignment on creep resistance. © 2013 Elsevier Ltd. All rights reserved.

A setup for optically monitoring the agglomerate growth of multiwalled carbon nanotubes (MWCNTs) by catalytic chemical vapor deposition on single Co-Mn-Al-Mg oxide catalyst particles with ethene as carbon precursor has been developed. Ethene concentrations and temperatures were varied between 5. -75. Vol.% and 550-770. °C, respectively. It could be shown that the agglomerate growth is rapid and the final diameter is reached after a few ten seconds to about 3. min depending on the reaction conditions. The average enlargement factor of the agglomerates over all experiments was found to be 6.5. ±. 1.2 compared to the original diameter of the catalyst particle. The growth rate is enhanced by both, reaction temperature and ethene concentration. Hence it is concluded that the agglomerate growth rate is associated with the reaction rate of MWCNT synthesis. Short time experiments and analysis of the resulting agglomerates have confirmed an earlier proposed growth mechanism. © 2013 Elsevier B.V.

Tight-binding models derived from density functional theory potentially provide a systematic approach to the development of accurate and transferable models of multicomponent systems. We introduce a systematic methodology for environmental tight binding in which both the overlap and environmental contributions to the electronic structure are included. The parameters of the model are determined directly from ab initio considerations, thus providing a formal conceptual link to density functional approaches. In order to test the validity of the approach, the model is applied to small clusters of Ni and Co, whose electronic structure is largely determined by the interplay of tightly bound d-valent states and the disperse s-states. We numerically illustrate that it is essential to include environmental contributions in the tight-binding approach in order to reliably reproduce the electronic structure of such clusters. © 2013 IOP Publishing Ltd.

Martensitic transformations are generally classified into two groups, namely athermal and isothermal, according to their kinetics. In case of athermal transformations, the amount of the product phase only depends on temperature, and not on time. However, much debate rises about this issue due to unexpected experimental observations of isothermal effects in typically athermal transformations. Considering that the wide applications of Heusler Ni-Mn based materials are based on martensitic transformations, it is of importance to clarify the nature of their martensitic transformation. In this paper, we made an effort to study isothermal effects in a Ni-Mn-Sn alloy using differential scanning calorimetry (DSC). It is proposed that the martensitic transformation of Ni-Mn based materials is athermal in nature although a time-depending effect is observed through DSC interrupted measurements. © 2013 Elsevier Ltd. All rights reserved.

Stereo transmission electron microscopy (TEM) provides a 3D impression of the microstructure in a thin TEM foil. It allows to perform depth and TEM foil thickness measurements and to decide whether a microstructural feature lies inside of a thin foil or on its surface. It allows appreciating the true three-dimensional nature of dislocation configurations. In the present study we first review some basic elements of classical stereo TEM. We then show how the method can be extended by working in the scanning transmission electron microscope (STEM) mode of a modern analytical 200. kV TEM equipped with a field emission gun (FEG TEM) and a high angle annular dark field (HAADF) detector. We combine two micrographs of a stereo pair into one anaglyph. When viewed with special colored glasses the anaglyph provides a direct and realistic 3D impression of the microstructure. Three examples are provided which demonstrate the potential of this extended stereo TEM technique: a single crystal Ni-base superalloy, a 9% Chromium tempered martensite ferritic steel and a NiTi shape memory alloy. We consider the effect of camera length, show how foil thicknesses can be measured, and discuss the depth of focus and surface effects. © 2012 Elsevier B.V.

A new nickel bis(phosphinite) pincer complex [2,6-(R 2PO) 2C 6H 3]NiCl (L RNiCl, R = cyclopentyl) has been prepared in one pot from resorcinol, ClP(C 5H 9) 2, NiCl 2, and 4-dimethylaminopyridine. The reaction of this pincer compound with LiAlH 4 produces a nickel hydride complex, which is capable of reducing CO 2 rapidly at room temperature to give a nickel formate complex. X-ray structures of two related nickel formate complexes L RNiOCHO (R = cyclopentyl and isopropyl) have shown an "in plane" conformation of the formato group with respect to the coordination plane. The stoichiometric reaction of nickel formate complexes L RNiOCHO (R = cyclopentyl, isopropyl, and tert-butyl) with catecholborane has suggested that the reaction is favored by a bulky R group. L RNiOCHO (R = tert-butyl) does not react with PhSiH 3 at room temperature; however, it reacts with 9-borabicyclo[3.3.1]nonane and pinacolborane to generate a methanol derivative and a boryl formate species, respectively. The catalytic reduction of CO 2 with catecholborane is more effectively catalyzed by a more sterically hindered nickel pincer hydride complex with bulky R groups on the phosphorus donor atoms. The nickel pincer hydride complexes are inactive catalysts for the hydrosilylation of CO 2 with PhSiH 3. © 2011 Elsevier Ltd. All rights reserved.

The current investigation aims at studying the passivity behaviour of NiTi shape memory alloys with different levels of secondary phase titanium carbide (TiC) particles in an electrolyte of 0.9% sodium chloride at 37 °C. The influence of carbides and thermo-mechanical treatment/cold working on the passivity breakdown is highlighted. The polarisation studies on the as-cast and cold worked NiTi with high (0.05 wt%) and low (0.005 wt%) carbon levels show a significant difference in oxide stability. The alloy with extremely low carbon content shows a higher breakdown potential. Higher carbon levels result in higher density of larger TiC and these carbide/matrix interfaces are more susceptible to pitting. The qualitative behaviour of passive layer formed at 0.5 V on the cold worked NiTi alloy with different carbon levels was ascertained by electrochemical impedance spectroscopy (EIS). The oxide on the NiTi alloy with high (0.05 wt%) carbon levels showed lower resistance and poor stability at this condition. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Processing of Nickel-Titanium (NiTi) shape memory alloys (SMAs) is challenging because smallest compositional variances and all types of microstructural features strongly affect the elementary processes of the martensitic transformation and thus the functional properties of the material. Against this background, powder metallurgical near net shape methods are attractive for the production of NiTi components. Especially additive manufacturing technologies (AM) seem to provide high potential, although they have received only little attention for processing NiTi so far. This work is the first to report on pseudoelastic properties of additive manufactured Ni-rich NiTi. We show how to establish pseudoelasticity in NiTi samples prepared by the additive manufacturing technique Selective Laser Melting (SLM). Therefore, we analyze phase transformation behavior, mechanical characteristics and functional properties of our materials subjected to different heat treatments. The obtained results are compared to the behavior of conventional NiTi. The presented results clearly indicate that SLM provides a promising processing route for the fabrication of high quality NiTi parts. Copyright © 2012 by ASME.

For reducing the porosity of single crystal (SX) nickel-based superalloys, Hot Isostatic Pressing (HIP) is used. High pressures of about 100-170 MPa lead to local deformation, which close the pores. However, since HIP also requires high temperatures (1000-12007deg;C) it has a pronounced effect on the microstructure and the local distribution of elements. This contribution analyses the effect of different HIP treatments on both the microstructure and the segregation of the SX superalloy LEK94 in the as-precipitation-hardened state. In addition, the effects of rapid or slow cooling are analyzed. To distinguish the effect of pressure from those of temperature, the HIPed samples are compared with specimens annealed at atmospheric pressure. © (2011) Trans Tech Publications, Switzerland.

Nickel-titanium shape memory alloys (NiTi-SMAs) exhibit mechanical and chemical properties which make them attractive candidate materials for various types of biomedical applications. However, the high nickel content of NiTi-SMAs may result in adverse tissue reactions, especially when they are considered for load-bearing implants. It is generally assumed that a protective titanium oxide layer separates the metallic alloy from its environment and that this explains the good biocompatibility of NiTi. Cyclic loading may result in failure of the protective oxide layer. The scientific objective of this work was to find out whether cyclic dynamic strain, in a range relevant for orthopedic implants, diminishes the biocompatibility of NiTi-SMAs. In order to analyze the biocompatibility of NiTi-SMA surfaces subjected to cyclic loading, NiTi-SMA tensile specimens were preloaded with mesenchymal stem cells, transferred to a sterile cell culture system and fixed to the pull rods of a tensile testing machine. Eighty-six thousand and four hundred strain cycles at 2% pseudoelastic strain were performed for a period of 24 h or 7 days. Cytokines (IL-6, IL-8 and VEGF) and nickel ion release were determined within the cell culture medium. Adherent cells on the tensile specimens were stained with calcein-AM and propidium iodide to determine cell viability. Dynamic loading of the tensile specimens did not influence the viability of adherent human mesenchymal stem cells (hMSCs) after 24 h or 7 days compared with the non-strained control. Dynamic cycles of loading and unloading did not affect nickel ion release from the tensile specimens. The release of IL-6 from hMSCs cultured under dynamic conditions was significantly higher after mechanical load (873 pg ml -1) compared with static conditions (323 pg ml-1). The present work demonstrates that a new type of mechanical in vitro cell culture experiment can provide information which previously could only be obtained in large animal experiments. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

In the present study, we investigate the fatigue behavior of Nickel Titanium (NiTi) microstents at 22°C (room temperature) and 37°C up to 30×10 6 load cycles. We briefly describe our test procedure, which applies displacement-controlled pull-pull fatigue cycling between displacements corresponding to apparent strains of 5 and 7.5%. The response of the microstents to mechanical loading indicates cyclic softening during 30×10 4 cycles. Subsequently, the maximum load remains constant throughout the remainder of the test. We use transmission electron microscopy (TEM) to clarify the microstructural reasons for cyclic softening. A focused ion beam (FIB) technique is used to take out thin foil specimens from critical microstent locations. Our TEM results show that the dislocation density increases during cycling. We also find that microstructural regions with stabilized stress-induced B19 martensite can be detected. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alloy 690 based 'nuclear waste vitrification furnace' components degrade prematurely due to molten glass-alloy interactions at high temperatures and thereby increase the volume of metallic nuclear waste. In order to reduce the waste inventory, compositionally graded Ni-YSZ (Y 2O 3 stabilized ZrO 2) composite coating has been developed on Alloy 690 using Pulsed Laser Deposition technique. Five different thin-films starting with Ni80YSZ20 (Ni 80wt%+YSZ 20wt%), through Ni60YSZ40 (Ni 60wt%+YSZ 40wt%), Ni40YSZ60 (Ni 40wt%+YSZ 60wt%), Ni20YSZ80 (Ni 20wt%+YSZ 80wt%) and Ni0YSZ100 (Ni 0wt%+YSZ 100wt%), were deposited successively on Alloy 690 coupons. Detailed analyses of the thin-films identify them as homogeneous, uniform, pore free and crystalline in nature. A comparative study of coated and uncoated Alloy 690 coupons, exposed to sodium borosilicate melt at 1000°C for 1-6h suggests that the graded composite coating could substantially reduced the chemical interactions between Alloy 690 and borosilicate melt. © 2011 Elsevier B.V.

Nickel hydride with a diphosphinite-based ligand catalyzes the highly efficient reduction of CO2 with catecholborane, and the hydrolysis of the resulting methoxyboryl species produces CH3OH in good yield. The mechanism involves a nickel formate, formaldehyde, and a nickel methoxide as different reduced stages for CO2. The reaction may also be catalyzed by an air-stable nickel formate. © 2010 American Chemical Society.

Magnetron sputtered Ni thin films on both oxidised Si (100) and α-Al2O3 (0001) substrates of thickness 150-1000 nm were tested thermomechanically with a wafer curvature system, as well as in situ in a transmission electron microscope. The films on oxidised Si have a {111}-textured columnar microstructure with a mean grain size similar to the film thickness. On (0001) α-Al2O3 a near single crystal epitaxy with two growth variants is achieved leading to a significantly larger grain size. The thermomechanical testing was analysed in terms of the room temperature/high temperature flow stresses in the films and the observed thermoelastic slopes. It was found that the room temperature flow stresses increased with decreasing film thickness until a plateau of ∼1100 MPa was reached for films thinner than 400 nm. This plateau is attributed to the present experiments exerting insufficient thermal strain to induce yielding in these thinner films. At 500 °C the compressive flow stresses of the films show a competition between dislocation and diffusion mediated plasticity. A size effect is also observed in the thermoelastic slopes of the films, with thinner films coming closer to the slope predicted by mismatch in thermal expansion coefficients. It is put forward here that this is due to a highly inhomogeneous stress distribution in the films arising from the grain size distribution. © 2010 Springer Science+Business Media, LLC.

Nanoactuators made from nanoparticulate NiTi shape memory alloy show potential in the mechanical stimulation of bone tissue formation from stem cells. We demonstrate the fabrication of Ni, Ti, and NiTi shape memory alloy nanoparticles and their biocompatibility to human adipose-derived stem cells. The stoichiometry and phase transformation property of the bulk alloy is preserved during attrition by femtosecond laser ablation in liquid, giving access to colloidal nanoactuators. No adverse effect on cell growth and attachment is observed in proliferation assay and environmental electron scanning microscopy, making this material attractive for mechanical stimulation of stem cells.

The effects of thermal annealing at 1000°C in air on the microstructure and the mechanical properties (Young's modulus and hardness) of thermal barrier coatings consisting of a 4mol% Y2O3 partially stabilized ZrO2 top coat and a NiCoCrAlY bond coat, deposited by electron beam physical vapour deposition on nickel-based superalloy IN 625, have been investigated using X-ray diffraction, Raman spectroscopy, scanning electron microscopy (SEM), image analysis and nanoindentation. During annealing, the ceramic top coat undergoes sintering and recrystallization. These processes lead to stress relaxation, an increase of the intra-columnar porosity and the number of large pores as measured by image analysis of SEM micrographs. An increase of the grain size of the γ-phase in the bond coat, accompanied by changes in the morphology of γ-grains with annealing time, is also observed. Correlations between these microstructural changes in the top coat and the bond coat and their mechanical properties are established and discussed. © 2010 Elsevier B.V.

An in situ tensile rig is proposed, which allows performing electrochemical (repassivation) experiments during dynamic mechanical testing of wires. Utilizing the basic components of a conventional tensile tester, a custom-made minitensile rig was designed and fabricated. The maximal force that can be measured by the force sensor is 80 N, with a sensitivity of 0.5 mV/V. The maximum travel range of the crosshead induced by the motor is 10 mm with a minimum step size of 0.5 nm. The functionality of the tensile test rig was validated by investigating Cu and shape memory NiTi wires. Wires of lengths between 40 and 50 mm with varying gauge lengths can be tested. An interface between wire and electrochemical setup (noncontact) with a smart arrangement of electrodes facilitated the electrochemical measurements during tensile loading. Preliminary results on the repassivation behavior of Al wire are reported. © 2010 American Institute of Physics.

A new layered ammonium nickel(II) diphosphate, (NH4) 2[Ni3(P2O7)2(H 2O)2], has been synthesized ionothermally in the ionic liquid 1-butyl-3-methyl imidazolium bromide and characterized by powder X-ray diffraction, elemental analysis, scaning electron microscopy, thermogravimetry etc. The results of the characterization show that the crystal adopts the monoclinic space group P21/a with the lattice constants a = 9.23529(2) Å, b = 7.98489(2) Å, c = 9.40772(2) Å, β = 100.2608(2)° and Z = 2. Its structure consists of chains of cis- and trans-edge-sharing [NiO6]-octahedra linked via [P2O 7] units to form layers of [Ni3(P2O 7)2(H2O)2]2- in the ab plane. Adjacent layers are separated in the c-direction by ammonium ions. © 2010 Elsevier B.V. All rights reserved.

This paper focuses on the modelling of primary, secondary and tertiary creep of nickel-base single crystal superalloys at high temperatures. In particular, we propose an extension of the Cailletaud single crystal plasticity model [Méric L, Poubanne P, Cailletaud G. Single crystal modeling for structural calculations: part I-model presentation. Transactions of the ASME 1991;133:162-170] to include tertiary creep. This is achieved by introducing an additional evolution equation for a scalar damage variable per slip system. In addition, a methodology for the calibration of the material parameters of the model to fit the results from experiments has been implemented. The parameter identification rests upon a two-membered evolution strategy. The comparison with uniaxial and multiaxial test data shows a good agreement between model and experiment. The structural simulations have been performed by means of a special element technology which enables efficient and accurate finite element computations. © 2009 Elsevier Ltd. All rights reserved.

A modelling approach is presented for the prediction of microstructure evolution during directional solidification of nickel-based superalloys. A phase-field model is coupled to CALPHAD thermodynamic and kinetic (diffusion) databases, so that a multicomponent alloy representative of those used in industrial practice can be handled. Dendritic growth and the formation of interdendritic phases in an isothermal (2-D) cross-section are simulated for a range of solidification parameters. The sensitivity of the model to changes in the solidification input parameters is investigated. It is demonstrated that the predicted patterns of microsegregation obtained from the simulations compare well to the experimental ones; moreover, an experimentally observed change in the solidification sequence is correctly predicted. The extension of the model to 3-D simulations is demonstrated. Simulations of the homogenization of the as-cast structure during heat treatment are presented. © 2009 Acta Materialia Inc.

Nickel PCP-pincer hydride complexes catalyze chemoselective hydrosilylation of C=O bonds of aldehydes and ketones in the presence of other functional groups. The mechanism involves C=O insertion into a nickel-hydrogen bond, followed by cleavage of the newly formed Ni-O bond with a silane. © 2009 American Chemical Society.

Electropolishing of NiTiCu shape memory alloy was performed in methanolic sulfuric acid as a surface processing method. The current investigation, using a rotating disk electrode, aims at identifying appropriate electropolishing conditions for this alloy based on understanding the underlying mechanism. The influence of temperature, rotation rate, and sulfuric acid concentration (3 or 5 M H2 S O4) was quantified. Electropolishing in methanolic 5 M H2 S O4 is solely mass-transport-controlled, while a mixed control is found for the methanolic 3 M H2 S O4. This behavior is different from that of the binary NiTi alloy. From the electrochemical perspective, a methanolic 5 M H2 S O4 solution is more suitable for electropolishing NiTiCu. The activation energy for electrodissolution is 21.5 kJ mol-1. © 2008 The Electrochemical Society.

This paper reviews our current research activities on developing new multiphase metallic materials for structural applications with a temperature capability beyond 1,200°C. Two promising material systems have been chosen: first, alloys in the system Mo-Si-B which have demonstrated potential due to their high melting point of around 2,000°C and due to the formation of a protecting borosilicate glass layer on the surface at temperatures exceeding 900°C; and second, novel Co-Re-based alloys which have been chosen as a model system for complete miscibility between the elements cobalt and rhenium, offering the possibility of continuous increases of the melting point of the alloy through rhenium additions. © TMS 2009.