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.

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

Results are presented reporting on the martensite domain variant selection and stress-induced martensite morphology in [001]-oriented superelastic Co49Ni21Ga30 shape memory alloy (SMA) single crystals under tensile load. In situ neutron diffraction, as well as in situ optical- and confocal laser scanning microscopy were conducted focusing on three differently treated samples, i.e. in the as-grown, solution-annealed and aged condition. An aging treatment performed at 350 °C promotes the precipitation of nanoprecipitates. These second phase precipitates contribute to an increase of the number of habit plane interfaces, while reducing lamellar martensite plate thickness compared to the as-grown and solution-annealed (precipitate free) samples. During tensile loading, all samples show a stress-induced formation of martensite, characterized by one single domain variant (“detwinned”) and one set of parallel habit planes in a shear band. The results clearly show that γ’ nanoprecipitates do not necessarily promote multi-variant interaction during tensile loading. Thus, reduced recoverability in Co-Ni-Ga SMAs upon aging cannot be solely attributed to this kind of interaction as has been proposed in literature so far. © 2022

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 present paper focuses on the analysis of functional fatigue properties in 〈001〉-oriented single crystalline Fe-Ni-Co-Al-Ta shape memory alloys. Superelastic cycling experiments up to 4.5% at different temperatures were conducted and revealed excellent cyclic stability at lower testing temperatures. Transmission electron microscopy observations shed light on the influence of precipitation and dislocation activity on functional stability. © 2021

High entropy shape memory alloys (HESMAs) represent a relatively young class of functional materials. They show a reversible martensitic phase transformation which allows to exploit shape memory effects at relatively high temperatures. HESMAs represent ordered complex solid-solutions. Their high temperature phase is of B2 type, and various elements (e.g. Ni, Cu, Ti, Zr, Hf) occupy sites in specific sub-lattices. In the present work, we study the processing and the functional properties of HESMAs. We study effects of chemical complexity on solidification microstructures and martensitic transformations. Binary, ternary, quaternary, quinary and senary model alloys were investigated using advanced microstructural and thermal characterization methods. The results show that element partitioning during solidification results in a redistribution of individual alloy elements in dendritic/interdendritic regions. Surprisingly, the atomic ratios of the two groups of elements which occupy the Ni- (first group: Ni, Cu and Pd) and Ti-sub-lattice (second group: Ti, Zr, Hf) are maintained. This allows the material to form martensite throughout its heterogeneous microstructure. The effect of chemical complexity/composition on martensite start temperatures, MS, is discussed on the basis of valence electron concentrations, cV. Some of the alloys fall into MS(cV)-regimes which are uncommon for classical Ni-Ti-based shape memory alloys. In the present work, a new HESMA of type NiCuPdTiZrHf was identified which has the potential to provide maximum shape memory strains close to 15%. © 2020

This study concentrates on several factors which govern the nanoscale plasticity of in situ compressed dislocation-free Ni3 Al nanocubes: cube size, aspect ratio and the presence of grooves. The yield strength of dislocation-free Ni3 Al nanocubes exhibits an apparent size dependence. The size dependence is strong when cubes are smaller than 300 nm. Compared with the strength of bulk Ni3 Al single crystals, the strength of nanocubes is two orders of magnitude higher, which clearly demonstrates that there is a size effect. Nanocube plasticity strongly depends on the alignment and the shape of the cubes. Deformed aligned nanocubes either display only a few localized deformation events (slip lines) or were homogenously compressed into flats due to multiple slip dislocation-mediated plasticity. For an aligned cube, crack initiation at the intersection of a slip line with a groove in the cube surface was observed. In case of a double cube, crack initiation occurs at surface irregularities, while subsequent crack propagation occurs along one or more slip planes. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.

High entropy shape memory alloys (HE-SMAs) show reversible martensitic phase transformations at elevated temperatures. HE-SMAs were derived from binary NiTi, to which the elements Cu, Pd, Zr and Hf are added. They represent ordered complex solid solutions. Their high temperature phase is of B2 type, where the added elements occupy sites in the Ni-(Cu, Pd) and Ti-sub-lattices (Zr, Hf). In the present study, advanced microstructural and thermal characterization methods were used to study the effects of the additional alloy elements on microstructures and phase transformations. The ratios of Ni-equivalent (Ni, Cu, Pd) and Ti-equivalent (Ti, Zr, Hf) elements in HE-SMAs were varied to establish systems that correspond to stoichiometric, under- and over-stoichiometric binary alloys. It is shown that basic microstructural features of cast and heat-treated HE-SMAs are inherited from the nine binary X–Y subsystems (X: Ni, Cu, Pd; Y: Ti, Zr, Hf). The phase transition temperatures that characterize the martensitic forward and reverse transformations depend on the concentrations of all alloy elements. The data obtained demonstrate how martensite start temperatures are affected by deviations from the composition of an ideal stoichiometric B2 phase. The findings are discussed in the light of previous work on the concentration dependence of SMA transformation temperatures, and directions for the development of new shape memory alloy compositions are proposed. © 2020 The Authors

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

Ti–Ta alloys represent candidate materials for high-temperature shape-memory alloys (HTSMAs). They outperform several other types of HTSMAs in terms of cost, ductility, and cold workability. However, Ti–Ta alloys are characterized by a relatively fast microstructural degradation during exposure to elevated temperatures, which gives rise to functional fatigue. In the present study, we investigate how isothermal aging affects the martensitic transformation behavior and microstructures in Ti70Ta30 HTSMAs. Ti–Ta sheets with fully recrystallized grain structures were obtained from a processing route involving arc melting, heat treatments, and rolling. The final Ti–Ta sheets were subjected to an extensive aging heat treatment program. Differential scanning calorimetry and various microstructural characterization techniques such as scanning electron microscopy, transmission electron microscopy, conventional X-ray, and synchrotron diffraction were used for the characterization of resulting material states. We identify different types of microstructural evolution processes and their effects on the martensitic and reverse transformation. Based on these results, an isothermal time temperature transformation (TTT) diagram for Ti70Ta30 was established. This TTT plot rationalizes the dominating microstructural evolution processes and related kinetics. In the present work, we also discuss possible options to slow down microstructural and functional degradation in Ti–Ta HTSMAs. © 2018, ASM International.

The structure and chemistry of the orthorhombic O′ phase after quenching of a Ti-23 at.%Nb-2 at.%O was measured using aberration-corrected transmission electron microscopy and atom probe tomography. The nanosized O′ phase, formed in the vicinity of ω, is enriched with oxygen and slightly depleted in Nb. Upon annealing, ω dissolves and the O′ phase develops in β up to 350 °C, above which temperature it transforms to colonies of fine α phase. Another needle-like form of α with lower Nb content is thought to nucleate from Nb-lean regions related to spinodal decomposition of β. © 2019 Elsevier Ltd

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

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

The microalloying of low-alloyed steels with Nb can improve the strength-to-toughness balance. Such an effect of Nb is usually ascribed to the refinement of the grain structure occurring in the austenite regime during hot forming. In the present work, we report that Nb enhances the impact toughness of a low-alloyed Cr–Mo steel by a mechanism which has not been appreciated so far. The lower impact toughness in the Nb-free Cr–Mo steel is due to segregation of Mo to boundaries, which facilitates the formation of fine Mo-rich ξ-phase carbides lining up along the boundaries. This further promotes the nucleation and propagation of microcracks. The addition of Nb leads to the formation of Mo-enriched NbC particles. The interfaces between these particles and the matrix supply new preferential sites for precipitation of Mo-rich ξ-phase carbides upon subsequent tempering. In this way, Nb additions result in a decrease of Mo segregation to boundaries, significantly reducing the precipitation of ξ-phase carbides on grain boundaries, thus leading to improved impact toughness. In addition to the classical microstructural explanation (grain size effect), this chemical role of Nb sheds new light on the design strategies of advanced low-alloyed steels with optimized strength-to-toughness ratios. © 2019, Springer Science+Business Media, LLC, part of Springer Nature.

Due to their ability to provide a shape memory effect at elevated temperatures, high-temperature shape memory alloys (HT-SMAs) came into focus of academia and industry in the last decades. Ternary and quaternary Ni–Ti-based HT-SMAs have been in focus of a large number of studies so far. Ti–Ta HT-SMAs feature attractive shape memory properties along with significantly higher ductility and lower costs for alloying elements compared to conventional Ni–Ti-based HT-SMAs, which qualifies them as promising candidate alloys for high-temperature applications. Unfortunately, precipitation of undesired phases, e.g., the ω-phase, leads to significant functional degradation upon cyclic loading in binary Ti–Ta. Therefore, additions of ternary elements, such as Al, which suppress the ω-phase formation, are important. In the present study, the influence of different heating–cooling rates on the cyclic functional properties of a Ti–20Ta–5Al HT-SMA is investigated. Transmission electron microscopy as well as in situ synchrotron analysis revealed unexpected degradation mechanisms in the novel alloy studied. Elementary microstructural mechanisms leading to a degradation of the functional properties were identified, and the ramifications with respect to application of Ti–Ta–Al HT-SMAs are discussed. © 2019, ASM International.

In the present work, the influence of oxidation on the martensitic transformation in Ti–Ta high-temperature shape memory alloys is investigated. Thermogravimetric analysis in combination with microstructural investigations by scanning electron microscopy and transmission electron microscopy were performed after oxidation at 850 °C and at temperatures in the application regime of 450 °C and 330 °C for 100 h, respectively. At 850 °C, internal oxidation results in the formation of a mixed layered scale of TiO2 and β-Ta2O5, associated with decomposition into Ta-rich bcc β-phase and Ti-rich hexagonal α-phase in the alloy. This leads to a suppression of the martensitic phase transformation. In addition, energy dispersive X-ray analysis suggests an oxygen stabilization of the α-phase. At 450 °C, a slow decomposition into Ta-rich β-phase and Ti-rich α-phase is observed. After oxidation at 330 °C, the austenitic matrix shows strong precipitation of the ω-phase that suppresses the martensitic transformation on cooling. © 2019, ASM International.

The structural characterization of the various phases that occur in Ti–Ta-based high-temperature shape-memory alloys is complicated by the presence of many competing phases as a function of composition. In this study, we resolve apparent inconsistencies between experimental data and theoretical calculations by suggesting that phase separation and segregation of undesired phases are not negligible in these alloys, and that finite temperature effects should be taken into account in the modeling of these materials. Specifically, we propose that the formation of the ω phase at low Ta content and of the σ phase at high Ta content implies a difference between the nominal alloy composition and the actual composition of the martensitic and austenitic phases. In addition, we show that temperature affects strongly the calculated values of the order parameters of the martensitic transformation occurring in Ti–Ta. © 2018, ASM International.

The plasma spray-physical vapor deposition technique (PS-PVD) is used to deposit various types of ceramic coatings. Due to the low operating pressure and high enthalpy transfer to the feedstock, deposition from the vapor phase is very effective. The particular process conditions allow for the deposition of columnar microstructures when applying thermal barrier coatings (TBCs). These coatings show a high strain tolerance similar to those obtained by electron beam-physical vapor deposition (EB-PVD). But compared to EB-PVD, PS-PVD allows significantly reducing process time and costs. The application-related properties of PS-PVD TBCs have been investigated in earlier work, where the high potential of the process was described and where the good resistance to thermo-mechanical loading conditions was reported. But until now, the elementary mechanisms which govern the material deposition have not been fully understood and it is not clear, how the columnar structure is built up. Shadowing effects and diffusion processes are assumed to contribute to the formation of columnar microstructures in classical PVD processing routes. For such structures, crystallographic textures are characteristic. For PS-PVD, however, no crystallographic textures could initially be found using X-ray diffraction. In this work a more detailed TEM investigations and further XRD measurements of the columnar PS-PVD microstructure were performed. The smallest build units of the columnar TBC structure are referred to as sub-columns. The observed semi-single crystal structure of individual sub-columns was analyzed by means of diffraction experiments. The absence of texture in PS-PVD coatings is confirmed and elementary nucleation and growth mechanisms are discussed. © 2018, Springer Science+Business Media, LLC, part of Springer Nature.

The strength and toughness of low alloyed ferritic/bainitic steels depend on their microstructure, which evolves during thermo-mechanical treatments along the processing chain. Chromium-molybdenum steel microstructures are complex. Therefore, only a limited number of attempts have been made to fully characterize carbide populations in such steels. In the present work, analytical transmission electron microscopy is employed to study the microstructure of a low alloyed chromium-molybdenum steel, which features ferritic (F, mainly α-iron and niobium-carbides) and bainitic (B, α-phase, dislocation, grain/subgrain boundaries, various MxCy carbides) regions. The crystal structure and chemical nature of more than 200 carbides are determined and their distributions in the two microstructural regions are analyzed. The present work shows how particles can be identified in an effective manner and how the microstructural findings can be interpreted on the basis of thermodynamic calculations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Steels belong to one of the best established materials, however, the mechanisms of various phase transformations down to the nano length scale are still not fully clear. In this work, high-resolution transmission electron microscopy is combined with atomistic simulations to study the nanoscale carbide precipitation in a Fe–Cr–C alloy. We identify a cooperative growth mechanism that connects host lattice reconstruction and interstitial segregation at the growing interface front, which leads to a preferential growth of cementite (Fe3C) nanoprecipitates along a particular direction. This insight significantly improves our understanding of the mechanisms of nanoscale precipitation in interstitial alloys, and paves the way for engineering nanostructures to enhance the mechanical performance of alloys. © 2018, The Author(s).

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).

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.

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 investigate monocrystalline InAs nanowires (NWs) which are grown catalyst assisted by molecular beam epitaxy (MBE) and create the catalyst by focused ion beam (FIB) implanted Au spots. With this combination of methods an aspect ratio, i.e. the length to width ratio, of the grown NWs up to 300 was achieved. To control the morphology and crystalline structure of the NWs, the growth parameters like temperature, flux ratios and implantation fluence are varied and optimized. Furthermore, the influence of the used molecular arsenic species, in particular the As2 to As4 ratio, is investigated and adjusted. In addition to the high aspect ratio, this optimization results in the growth of monocrystalline InAs NWs with a negligible number of stacking faults. Single NWs were placed site-controlled by FIB implantation, which supplements the working field of area growth. © 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.

It is demonstrated that amorphous cobalt boride (Co2B) prepared by the chemical reduction of CoCl2 using NaBH4 is an exceptionally efficient electrocatalyst for the oxygen evolution reaction (OER) in alkaline electrolytes and is simultaneously active for catalyzing the hydrogen evolution reaction (HER). The catalyst achieves a current density of 10 mA cm(-2) at 1.61 V on an inert support and at 1.59 V when impregnated with nitrogen-doped graphene. Stable performance is maintained at 10 mA cm(-2) for at least 60 h. The optimized catalyst, Co2B annealed at 500 degrees C (Co2B-500) evolves oxygen more efficiently than RuO2 and IrO2, and its performance matches the best cobalt-based catalysts reported to date. Co2B is irreversibly oxidized at OER conditions to form a CoOOH surface layer. The active form of the catalyst is therefore represented as CoOOH/Co2B. EXAFS observations indicate that boron induces lattice strain in the crystal structure of the metal, which potentially diminishes the thermodynamic and kinetic barrier of the hydroxylation reaction, formation of the OOH* intermediate, a key limiting step in the OER.

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.

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.

Ti-Ta alloys are attractive materials for applications in actuators as well as biomedical implants. When fabricated as thin films, these alloys can potentially be employed as microactuators, components for micro-implantable devices and coatings on surgical implants. In this study, Ti100-xTa x (x = 21, 30) nanocolumnar thin films are fabricated by glancing angle deposition (GLAD) at room temperature using Ti73Ta27 and Ta sputter targets. Crystal structure, morphology and microstructure of the nanostructured thin films are systematically investigated by XRD, SEM and TEM, respectively. Nanocolumns of ∼150-160 nm in width are oriented perpendicular to the substrate for both Ti79Ta21 and Ti70Ta30 compositions. The disordered α″ martensite phase with orthorhombic structure is formed in room temperature as-deposited thin films. The columns are found to be elongated small single crystals which are aligned perpendicular to the and planes of α″ martensite, indicating that the films' growth orientation is mainly dominated by these crystallographic planes. Laser pre-patterned substrates are utilized to obtain periodic nanocolumnar arrays. The differences in seed pattern, and inter-seed distances lead to growth of multi-level porous nanostructures. Using a unique sputter deposition geometry consisting of Ti73Ta27 and Ta sputter sources, a nanocolumnar Ti-Ta materials library was fabricated on a static substrate by a co-deposition process (combinatorial-GLAD approach). In this library, a composition spread developed between Ti72.8Ta27.2 and Ti64.4Ta35.6, as confirmed by high-throughput EDX analysis. The morphology over the materials library varies from well-isolated nanocolumns to fan-like nanocolumnar structures. The influence of two sputter sources is investigated by studying the resulting column angle on the materials library. The presented nanostructuring methods including the use of the GLAD technique along with pre-patterning and a combinatorial materials library fabrication strategy offer a promising technological approach for investigating Ti-Ta thin films for a range of applications. The proposed approaches can be similarly implemented for other materials systems which can benefit from the formation of a nanocolumnar morphology. © 2016 IOP Publishing Ltd.

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

Preparing a stable suspension is a main step towards the electrophoretically depositing of homogeneous and dense composite coatings on NiTi for its biomedical application. In the present study, different composite suspensions of hydroxyapatite, silicon and multi-walled carbon nano-tubes were prepared using n-butanol and triethanolamine as media and dispersing agent, respectively. Multi-walled carbon nanotubes were first functionalized in the nitric acid vapor for 15 h at 175 °C, and then mixed into suspensions. Thermal desorption spectroscopy profiles indicate the formation of functional groups on multi-walled carbon nano-tubes. An excellent suspension stability can be achieved for different amounts of triethanolamine. The amount of triethanolamine can be increased by adding a second component to a stable hydroxyapatite suspension due to an electrostatic interaction between components in suspension. The stability of composite suspension is less than that of the hydroxyapatite suspension, due to density differences, which under the gravitational force promote the demixing. The scanning electron microscopy images of the coatings surface show that more dense coatings are developed on NiTi substrate using electrophoretic deposition and sintering at 850 °C in the simultaneous presence of silicon and multi-walled carbon nanotubes in the hydroxyapatite coatings. The atomic force microscopy results of the coatings surface represent that composite coatings of hydroxyapatite-20 wt.% silicon and hydroxyapatite-20 wt.% silicon-1 wt.% multi-walled carbon nano-tubes with low zeta potential have rougher surfaces. © 2016 Elsevier B.V. All rights reserved.

In this work, the microstructures of superalloy specimens produced using selective electron beam melting additive manufacturing were characterized. The materials were produced using a CMSX-4 powder. Two selective electron beam melting processing strategies, which result in higher and lower effective cooling rates, are described. Orientation imaging microscopy, scanning transmission electron microscopy and conventional high resolution transmission electron microscopy are used to investigate the microstructures. Our results suggest that selective electron beam melting processing results in near equilibrium microstructures, as far as γ′ volume fractions, the formation of small amounts of TCP phases and the partitioning behavior of the alloy elements are concerned. As expected, higher cooling rates result in smaller dendrite spacings, which are two orders of magnitude smaller than observed during conventional single crystal casting. During processing, columnar grains grow in <100> directions, which are rotated with respect to each other. There are coarse γ/γ′ microstructures in high angle boundary regions. Dislocation networks form low angle boundaries. A striking feature of the as processed selective electron beam melting specimens is their high dislocation density. From a fundamental point of view, this opens new possibilities for the investigation of elementary dislocation processes which accompany solidification. © 2016 by the authors; licensee MDPI, Basel, Switzerland.

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.

Titanium-tantalum shape memory alloys (SMAs) are promising candidates for actuator applications at elevated temperatures. They may even succeed in substituting ternary nickel-titanium high temperature SMAs, which are either extremely expensive or difficult to form. However, titanium-tantalum alloys show rapid functional and structural degradation under cyclic thermo-mechanical loading. The current work reveals that degradation is not only governed by the evolution of the ω-phase. Dislocation processes and chemical decomposition of the matrix at grain boundaries also play a major role. © 2015 The Author(s).

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.

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.

Alloys based on the titanium-tantalum system are considered for application as high-temperature shape memory alloys due to their martensite start temperatures, which can surpass 200 °C. In the present work we study the evolution of microstructure and the influence of creep on the phase transformation behavior of a Ti70Ta30 (at.%) high-temperature shape memory alloy. Creep tests were performed in a temperature range from 470 to 530 °C at stresses between 90 and 150 MPa. The activation energy for creep was found to be 307 kJ mol-1 and the stress exponent n was determined as 3.7. Scanning and transmission electron microscopy investigations were carried out to characterize the microstructure before and after creep. It was found that the microstructural evolution during creep suppresses subsequent martensitic phase transformations. © Carl Hanser Verlag GmbH & Co. KG.

Ti-Ta based alloys are an interesting class of high-temperature shape memory materials. When fabricated as thin films, they can be used as high-temperature micro-actuators with operation temperatures exceeding 100 °C. In this study, microstructure, shape memory effect and thermal cycling stability of room-temperature sputter deposited Ti<inf>67</inf>Ta<inf>33</inf> thin films are investigated. A disordered α martensite (orthorhombic) phase is formed in the as-deposited Ti<inf>67</inf>Ta<inf>33</inf> films. The films show a columnar morphology with the columns being oriented perpendicular to the substrate surface. They are approximately 200 nm in width. XRD texture analysis reveals a martensite fiber texture with {120} and {102} fiber axes. The XRD results are confirmed by TEM analysis, which also shows columnar grains with long axes perpendicular to the {120} and {102} planes of α martensite. The shape memory effect is analyzed in the temperature range of -10 to 240 °C using the cantilever deflection method, with special emphasis placed on cyclic stability. Ti<inf>67</inf>Ta<inf>33</inf> thin films undergo a forward martensitic transformation at M<inf>s</inf> ≈ 165 °C, with a stress relaxation of approximately 33 MPa during the transformation. The actuation response of the film actuators degrades significantly during thermal cycling. TEM analysis shows that this degradation is related to the formation of nanoscale ω precipitates (5-13 nm) which form above the austenite finish temperature. These precipitates suppress the martensitic transformation, as they act as obstacles for the growth of martensite variants. Ti-Ta thin films can be used as high-temperature micro-actuators. In this study, microstructure, shape memory effect, and functional stability of room-temperature sputter deposited Ti<inf>67</inf>Ta<inf>33</inf> thin films are systematically investigated. The actuation response of the film actuators degrades significantly during thermal cycling. This degradation is related to the formation of nanoscale ω precipitates (5-13 nm) which form above the austenite finish temperature. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

This study focuses on the functional stability of [0 0 1]-oriented Fe 41Ni28Co17Al11.5Ta2.5 (at.%) single crystals. It is shown that functional degradation of aged FeNiCoAlTa, containing fine dispersed γ′-particles ∼5-8 nm in diameter is caused by the interaction of different martensite variants under cyclic loading in tension. Superelastic cycling experiments up to 4.5% total strain resulted in the accumulation of permanent strain mainly caused by the formation of retained martensite. In situ observations were conducted in order to evaluate the local strain evolution and martensite variant interactions on the meso- and microscale. Optical microscopy and transmission electron microscopy observations revealed various differently oriented martensite variants which were retained upon 100 superelastic cycles. In addition, fine martensitic structures remaining in the vicinity of the γ′ precipitates were found after mechanical cycling, which are shown to be important for cyclic degradation in Fe-based shape memory alloys. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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.

CO2 hydrogenation to short-chain hydrocarbons was investigated over iron catalysts supported on oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) and on silica, which were synthesized by the dry impregnation method using ammonium ferric citrate as precursor. The reduction of the calcined catalysts was examined in detail using temperature-programmed reduction in H2 and in situ X-ray absorption near-edge structure (XANES) analysis. The XANES results revealed that the mixture of hematite and magnetite was gradually transformed into wustite and metallic iron during heating in H2. Iron oxide nanoparticles supported on nitrogen-functionalized CNTs were easier to reduce compared to those on oxygen-functionalized CNTs indicating a promoting effect of the nitrogen functional groups. The interaction between iron oxide and silica was found to be much stronger inhibiting the reduction to metallic iron. As a result, the catalytic activity of iron nanoparticles supported on CNTs in CO2 hydrogenation at 360 °C, 25 bar and a H2:CO 2 ratio of 3 was almost twofold higher compared with iron supported on silica. CO2 was converted into C1-C5 hydrocarbons with CO and methane as major products over all catalysts. The Fe/NCNT catalyst achieved the highest olefin selectivity of 11% in the hydrocarbons range of C2-C5. In contrast, mostly paraffins were formed over the Fe/SiO2 catalyst. © 2014 Elsevier B.V.

In the present work we perform a detailed investigation of ingot metallurgy processing routes of Ti-30Ta, a shape memory alloy with a good potential for applications at higher temperatures. There is currently considerable interest in high temperature shape memory alloys, both in industry (automotive and aerospace applications) and in academia. By means of scanning electron microscopy, we provide recommendations on the number of remelting cycles in the vacuum arc melting process, and on annealing temperatures/times in order to obtain chemical homogeneity. It is also shown that this is required to obtain well defined differential scanning calorimeter charts, which facilitates characterization and investigations of martensitic transformation in this alloy. Areas in need of further work are identified. Copyright © 2014 Carl Hanser Verlag GmbH & Co. KG.

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.

Co-Re-based alloys have been introduced as a novel metallic system that possesses a wide exploitable composition range and high melting temperatures. The poor oxidation resistance of the binary system can be improved by alloying chromium. However, adding chromium also leads to the occurrence of the sigma phase of type Cr2Re3. In the present study, we investigate the evolution of the sigma phase during creep and aging at 1100 C for three selected alloys based on the ternary composition Co-17Re-23Cr (at.%). In all alloys, sigma phase populates the grain boundaries of the hexagonally close-packed (HCP) matrix phase in a blocky morphology. Additionally, a fine dispersion of lamellar sigma phase in the grain interiors has formed during the initial processing or forms during thermal exposure. This precipitation takes place by a cellular reaction that transforms a supersaturated HCP phase into alternating lamellae of a near-equilibrium HCP phase and the sigma phase. The process therefore has the character of a discontinuous precipitation. Using orientation imaging microscopy, we observe an orientation relationship between the lamellae, which describes the basal plane of the HCP phase to form a coherent interface with the base layer of atoms of the tetragonal sigma phase. After long-term thermal exposure to 1100 C, overaging of the lamellar structure results in spheroidization of the sigma lamellae and subsequent Ostwald ripening. © 2013 Elsevier Ltd. All rights reserved.

This paper focuses on the investigation of the ageing behaviour of silver nanoparticle containing polytetrafluoroethylene thin films during exposure to phosphate buffer solution (pH = 7.5). In order to investigate the effect of the electrical connection between the silver nanoparticles via a conductive substrate, two kinds of composite films were compared. One model where the nanoparticles are directly deposited on an inert conducting substrate and then covered by an ultra-thin polytetrafluoroethylene like film. In the second case a polytetrafluoroethylene/silver nanoparticle/polytetrafluoroethylene sandwich film was prepared on the same substrate to prevent electrical connection of the silver nanoparticles. Degradation was followed in-situ by means of the combination of ultraviolet-visible spectroscopy and electrochemical impedance spectroscopy. In the case of electrically connected nanoparticles electrochemical Ostwald ripening took place, while this process was not observed for the insulated nanoparticles. The electrochemical impedance spectroscopy studies allowed for the parallel study of the correlated loss of barrier properties. Transmission electron microscopy images of both composite films confirmed the results obtained by means of the in situ electrochemical ultraviolet-visible studies. © 2014 Elsevier B.V.

In this study the thermal cycling behavior of differently aged [1 0 0]-oriented Fe-28Ni-17Co-11.5Al-2.5Ta (at.%) shape memory single crystals was investigated. The strain-temperature response determined from thermal cycling experiments revealed a strong dependency on the precipitate morphology, which was adjusted by aging heat treatments. Specifically, a high precipitate density in the microstructure leads to small phase transformation-induced strains and low stresses necessary for activation of the martensitic phase transformation. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Isothermal low cycle fatigue tests are carried out on the nickel-base Alloy 617B in the solution-annealed, stabilized and long-term aged conditions at temperatures between room temperature and 900 C. In addition, fatigue microcrack growth is measured using the replica technique. Transmission electron microscopy studies suggest that the observed differences in cyclic hardening between the different heat treatments result from the precipitation of fine carbides. Scanning electron microscope observations indicate a change in fracture mode for the solution-annealed and long-term aged material with temperature. The Chaboche model is able to describe the time and temperature dependent cyclic plasticity of the three material conditions. The measured lifetimes and crack growth rates can be described using a fracture mechanics based lifetime model. However, the data for room temperature and for temperatures above 400 C fall into two different scatter bands due to differences in crack growth rates. © 2013 Elsevier Ltd. All rights reserved.

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 high-temperature and low-stress creep (1293 K, 160 MPa) of the single-crystal Ni-based superalloy LEK 94 is investigated, comparing the tensile creep behavior of miniature creep specimens in [0 0 1] and [1 1 0] directions. In the early stages of creep, the [0 0 1]-direction loading shows higher minimum creep rates, because a greater number of microscopic crystallographic slip systems are activated, the dislocation networks at γ/γ′ interfaces accommodate lattice misfit better, and γ channels are wider. After the creep rate minimum, creep rates increase more strongly as a function of strain for [1 1 0] tensile loading. This may be related to the nature of rafting during [1 1 0] tensile creep, which results in a more open topology of the γ channels. It may also be related to more frequent γ′ cutting events compared with [1 0 0] tensile creep. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

We use a nanoindenter with a Berkovich tip to study local mechanical properties of two polycrystalline intermetallics with a B2 crystal structure, NiAl and NiTi. We use orientation imaging scanning electron microscopy to select a relevant number of grains with appropriate sizes and surface normals parallel to 〈0 0 1〉, 〈1 0 1〉 and 〈1 1 1〉. As a striking new result, we find a strong crystallographic orientation dependence for NiTi. This anisotropy is less pronounced in the case of NiAl. For NiTi, the indentation force required to impose a specific indentation depth is highest for indentation experiments performed in the 〈0 0 1〉 direction and lowest along the 〈1 1 1〉 direction. We consider transmission electron microscopy results from cross-sections below the indents and use molecular dynamics simulations and resolved shear stress calculations to discuss how this difference can be accounted for in terms of elementary deformation and transformation processes, related to dislocation plasticity (NiAl and NiTi), and in terms of the stress-induced formation and growth of martensite (NiTi). Our results show that the crystallographic anisotropy during nanoindentation of NiTi is governed by the orientation dependence of the martensitic transformation; dislocation plasticity appears to be less important. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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

The influence of silicon on the oxidation behaviour of Co- Re- Cr-alloys has been studied at 1 000 °C and 1 100 °C. Consideration was given to the synergetic effects between chromium and silicon with respect to the development of a protective Cr 2O 3 layer. The Si addition to the Co- Re-alloys produces a significant decrease in the evaporation rate of Re oxides. Moreover, the beneficial influence in the transient oxidation period results in a rapid formation of Cr2O3 scale. While the addition of 1 and 2 at.% Si to the ternary Co-17Re-23Cr alloy was insufficient to form a continuous Cr2O3 scale, the addition of 3 at.% silicon caused a change in the oxidation mode resulting in the formation of a nearly continuous Cr 2O 3 scale. On the oxide/alloy interface of the alloy Co-17Re-30Cr-2Si, a continuous and dense Cr 2O 3 scale was observed, which remained stable after 100 h exposure protecting the metallic substrate. © 2012 Carl Hanser Verlag GmbH & Co. KG.

During repeatedly imposed thermally induced martensitic transformations in Ti-Ni shape memory alloys, the martensite start temperature M s decreases. This has been rationalized on the basis of a scenario where an increasing dislocation density makes it more and more difficult for martensite to form. However, it is not clear why dislocations which form because they accommodate the growth of martensite during the first cooling cycle should act as obstacles during subsequent transformation cycles. In the present work we use diffraction contrast transmission electron microscopy to monitor the formation of unique leaf-like dislocation substructures which form as the martensite start temperature decreases during thermal cycling. We interpret our microstructural results on the basis of a microstructural scenario where dislocations play different roles with respect to the propagation of a big martensite needle in one transformation cycle and the nucleation and growth of new martensite needles in the following cycles. As a consequence, chestnut-leaf-like dislocation arrays spread out in different crystallographic directions. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Dislocation densities are investigated in a short-fiber-reinforced Al-11 wt.% Zn-0.2 wt.% Mg metal matrix composite (MMC) with a special focus on regions near the fiber-matrix interfaces. Clear microstructural evidence is provided for the formation of work-hardened zones (WHZs) around fibers during creep using transmission electron microscopy (TEM). The dislocation densities in the WHZs are higher after creep than after squeeze casting, where the plastic strains associated with the thermal stresses that build up during solidification also result in an increased dislocation density close to fibers. The effect of heating and cooling on the dislocation substructure is also considered. The results are discussed in light of previous findings and provide microstructural evidence for the presence of WHZs as predicted by the Dlouhy model of MMC creep. © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

NiTi shape memory alloys can be used as micro actuators and small scale pseudoelastic components. Therefore there is a need to characterize their mechanical properties on the micro scale. In several previous studies, such tests (nanoindentation, pillar compression) were performed for different NiTi alloys. However, no consistent results concerning the coupling between plastic deformation and martensitic transformation were obtained. Moreover it is unclear whether the material's response to loading on the micro scale reflects its large scale mechanical anisotropy. In this study, we investigate a binary, solution annealed precipitate free NiTi alloy and compress small pillars in <0. 0. 1>-, <1. 0. 1>- and <1. 1. 1>-directions. Mechanical results are analyzed in the light of SEM and post-mortem TEM investigations. We identify deformation mechanisms and show that there is deformation anisotropy. We show that micro pillar testing yields results which are in good qualitative agreement with previous work from macroscopic investigations. © 2012 Elsevier B.V.

The stress-induced B2-B19′ transformation in aged 51 at.% NiTi was investigated using in situ straining transmission electron microscopy (TEM). Increased applied strain along [1 1 0] B2 transforms B2 into plates containing B19′ variants that are related by a (1 1 0) B2 compound twin plane. This atypical twin plane is explained by relaxing the invariant plane constraint in the crystallographic theory of martensite (CTM) to an invariant line constraint. The relaxation is rationalized from the thin foil geometry. The relaxed CTM approach, coupled with conditions to maximize transformation strain along the loading axis and minimize elastic energy, predicts the observed twin interface, diffraction patterns, and interface with the B2 austenite. These results demonstrate subtleties in interpreting thin foil TEM results regarding martensitic transformations, and translating those results to bulk response. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A directionally solidified NiAl-Mo eutectic and an NiAl intermetallic, having respective nominal compositions Ni-45.5Al-9Mo and Ni-45.2Al (at.%), were loaded in compression at 1073 and 1173 K. Formidable strengthening by regularly distributed Mo fibres (average diameter 600 nm, volume fraction 14%) was observed. The fibres can support compression stresses transferred from the plastically deforming matrix up to a critical stress of the order of 2.5 GPa, at which point they yield. Microstructural evidence is provided for the dislocation-mediated stress transfer from the NiAl to the Mo phase. © 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.

Hardness and Young's moduli values for TixNi90-xCu10 (37at.%< x< 67at.%) thin films from a continuous composition spread type materials library, annealed at 500°C for 1h, were determined at room temperature (martensitic state) and 80°C (austenitic state) using high-throughput nanoindentation experiments. These values are found to increase as the compositions deviate from Ti contents close to 50at.%. The increases in hardness is correlated to the presence of Ti-rich and (Ni,Cu)-rich precipitates resulting in precipitate hardening and grain size refinement (Hall-Petch effect). The increase of the Young's moduli is rationalized by considering the significantly higher Young's moduli of the different precipitate phases and applying the rule of mixtures. The contributions of the precipitate phases and the matrix to the combined Young's modulus were estimated by evaluating the load-displacement curves in detail. The obtained results are in good agreement with the Young's moduli determined from thin film curvature measurements [R. Zarnetta et al., Smart Mater. Struct. 19 (2010) 65032]. Thus, the experimental restrictions for nanoindentation experiments at elevated temperatures are concluded to not adversely affect the validity of the results. © 2011 Elsevier B.V.

The effect of a superimposed stress on the coarsening of interacting Ni 4Ti 3 particles is studied using the multi-phase field method. It is found that the thickness/diameter ratio of a Ni 4Ti 3 particle in a (1 1 1) B2 plane increases with an increasing [1 1 1] B2 stress component. The particle shape can change from a disk to a sphere with increasing applied stress. It is also found that diffusional and mechanical interactions between two Ni 4Ti 3 particles can promote the nucleation of new particles. This provides an explanation for the autocatalytic nature of nucleation reported previously. Compressive stresses along [1 1 1] B2 increase the volume fraction and growth velocity of the Ni 4Ti 3 particles of the (1 1 1) B2 plane. Misoriented particles disappear during particle growth. The simulation results are discussed in the light of previous experimental results. © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The melting point of a novel Co-17Re-23Cr alloy (numbers given in at.%) could be increased by 250 °C as compared to established Ni-based superalloys, by optimising the content of Re. Samples were produced by vacuum arc-melting in order to evaluate the creep behaviour at temperatures beyond 1100 °C and for microstructural analysis. Three alloys (the Co-17Re-23Cr-based material, and the carbide strengthened alloys Co-17Re-23Cr-2.6C and Co-17Re-23Cr-2.6C-1.2Ta) were investigated. Creep properties, especially the minimum creep rate and the Larson-Miller plots, were compared. The Co-17Re-23Cr-2.6C-1.2Ta alloy has a higher minimum creep rate than Co-17Re-23Cr at 1200 °C but it has a lower minimum creep rate than Co-17Re-23Cr at 1100 °C. TaC coarsening, detected via transmission electron microscope (TEM) measurements may explain this effect. The overall creep behaviour of Co-17Re-23Cr-2.6C at 1200 °C is better than that of Co-17Re-23Cr-2.6C-1.2Ta, but worse than that of Co-17Re-23Cr.Microstructural investigations by scanning electron microscopy and TEM reveal a hexagonal closed-packed (hcp) matrix and σ-phases. The microhardness of the σ-phase was about 1570. HV (load: 1. g) and around 800. HV for the matrix. Pores and cracks occur along the brittle σ-phases and grain boundaries in the Co-Re-Cr alloys. A Norton exponent n in between 1.4 and 3.0 points to grain boundary dominated creep mechanisms. © 2010 Elsevier B.V.

Thermal cycling of NiTi shape memory alloys is associated with functional fatigue: the characteristic phase transformation temperatures decrease with increasing number of cycles, and the transformation behavior changes from a single- to a two-stage martensitic transformation involving the intermediate R-phase. These effects are usually attributed to a gradual increase of dislocation density associated with micro-plasticity during repeated cycling through the transformation range. Here, these changes are shown to increase at a higher maximum temperature (in the fully austenitic state) during differential scanning calorimetric cycling of a Ni-rich alloy. Additional thermal cycling experiments without repeated phase transformations, and post-mortem microstructural observations by transmission electron microscopy, demonstrate that a relevant portion of functional fatigue is due to the formation of nano-scale Ni-rich precipitates of type Ni4Ti3 even at temperatures relatively close to the austenite finish temperature. These results show that both dislocation generation during the diffusion-less phase transformation, and diffusion-controlled nucleation and growth of Ni4Ti3 precipitates, can interact and contribute to the evolution of functional properties during thermal cycling of Ni-rich NiTi. © 2010 Elsevier Ltd. All rights reserved.

A novel electrochemical method to prepare platinum shells around carbon-supported metal nanoparticles (Ru and Au) by pulsed electrodeposition from solutions containing Pt ions is presented. Shell formation is confirmed by characteristic changes in the cyclic voltammograms, and is further evidenced by monitoring particle growth by transmission electron microscopy as well as by energy-dispersive analysis of X rays (EDX). Scanning electrochemical microscopy and EDX measurements indicate a selective Pt deposition on the metal/carbon catalyst, but not on the glassy carbon substrate. The thus prepared carbon-supported core-shell nanoparticles are investigated with regard to their activity in electrocatalytic oxygen reduction, which demonstrates the applicability of these materials in electrocatalysis or sensors. © 2010 Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim.

The size, morphology and configuration of Ni4Ti3 precipitates in a single-crystal Ni-Ti alloy have been investigated by two-dimensional transmission electron microscopy-based image analysis and three-dimensional reconstruction from slice-and-view images obtained in a focused ion beam/scanning electron microscopy (FIB/SEM) dual-beam system. Average distances between the precipitates measured along the compression direction correlate well between both techniques, while particle shape and configuration data is best obtained from FIB/SEM. Precipitates form pockets of B2 of 0.54 μm in the compression direction and 1 μm perpendicular to the compression direction. © 2009 Acta Materialia Inc.

We document the evolution of dislocation densities in tempered martensite ferritic steels during long-term aging and creep. Scanning transmission electron microscopy in combination with a high-angle annular dark-field detector is used to study dislocations in a 12% Cr steel. During aging, the dislocation density quickly decreases by a factor 2 and then remains constant. Long-term creep results in an initial decrease by a factor 10, and after this sharp drop, the dislocation density continues to decrease. © 2009 Acta Materialia Inc.

The influence of microstructure on the stress-strain behavior of an Ni-rich NiTi shape memory alloy is examined. Specimens cut from a large-diameter bar of Ni50.7Ti49.3 shape memory alloy were analyzed in two states: (i) annealed and (ii) annealed and aged. The annealed state shows a fully austenitic structure with no precipitates and no distortions caused by residual stresses. The annealed and aged state has coherent Ni 4Ti3 particles precipitated in the proximity of the austenite grain boundaries. The size of the precipitates increases moving away from the grain boundaries toward the grain interiors. The evolution of the two states in the stress-strain-temperature space has been analyzed using tensile specimens with special geometry. Due to the complex effects of the coherent precipitates, the specimens in the aged state exhibited lower stress plateaus in the tensile loading-unloading curves, which enabled the occurrence of transformation pseudoelasticity from room temperature to 333 K. © 2010 Carl Hanser Verlag.

High-precision data on phase transformation temperatures in NiTi, including numerical expressions for the effect of Ni on MS, MF, AS, AF and T0, are obtained, and the reasons for the large experimental scatter observed in previous studies are discussed. Clear experimental evidence is provided confirming the predictions of Tang et al. 1999 [19] regarding deviations from a linear relation between the thermodynamic equilibrium temperature and Ni concentration. In addition to affecting the phase transition temperatures, increasing Ni contents are found to decrease the width of thermal hysteresis and the heat of transformation. These findings are rationalized on the basis of the crystallographic data of Prokoshkin et al. 2004 [68] and the theory of Ball and James [25]. The results show that it is important to document carefully the details of the arc-melting procedure used to make shape memory alloys and that, if the effects of processing are properly accounted for, precise values for the Ni concentration of the NiTi matrix can be obtained. © 2010 Acta Materialia Inc.

Multifunctional nanocomposites consisting of at least one ferromagnetic phase (e.g. FeCo) and one protective, wear resistant phase (e.g. TiN) are of interest for applications as sensors or actuators in harsh environments. This paper reports on the fabrication and characterization of nanocomposite thin films, prepared from FeCo/Ti metallic precursor multilayer composition spreads using a combinatorial sputter-deposition system. After deposition, the composition spread was annealed in nitrogen (5 × 10 5 Pa pressure) at 850 °C for 1.5 h, leading to preferential nitriding of Ti to TiN, thus forming the protective phase. Automated energy dispersive X-ray analysis, Auger electron spectroscopy, X-ray diffraction measurements, transmission electron microscopy (TEM) and vibrating sample magnetometry were used for the characterization of the as deposited and nitrided composition spreads. As an unexpected result, the appearance of a Heusler phase (Co 2FeSi) in the nanocomposite was observed by TEM. After N 2 annealing, the nanocomposites show reduced saturation magnetization values μ 0M S between 0.5 and 0.95 T and improved coercive field values μ 0H c between 4 and 13.8 mT, dependent on the TiN content. © 2010 Elsevier B.V. All rights reserved.

In situ and post-mortem diffraction contrast transmission electron microscopy (TEM) was used to study the multiplication of dislocations during a thermal martensitic forward and reverse transformation in a NiTi shape memory alloy single crystal. An analysis of the elongated dislocation loops which formed during the transformation was performed. It is proposed that the stress field of an approaching martensite needle activates an in-grown dislocation segment and generates characteristic narrow and elongated dislocation loops which expand on {1 1 0}B2 planes parallel to {0 0 1}B19′ compound twin planes. The findings are compared with TEM results reported in the literature for NiTi and other shape memory alloys. It is suggested that the type of dislocation multiplication mechanism documented in the present study is generic and that it can account for the increase in dislocation densities during thermal and stress-induced martensitic transformations in other shape memory alloys. © 2010.

The main strengthening precipitates of aluminum alloy 2198-T8, which are of the T1 phase, dissolve during friction stir welding, sending many Li atoms into solid solution. The stir zone precipitates are characterized using high-resolution transmission electron microscopy, energy dispersive spectroscopy, and selected area diffraction techniques to begin answering questions about the microstructural evolution and the relationship between microstructure and mechanical properties in friction stir welding of the next generation of lightweight Li-containing Al alloys. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.