High-temperature microstructure evolution of an advanced intermetallic nano-lamellar γ-TiAl-based alloy and associated diffusion processes

Nano-lamellar advanced γ-TiAl based alloys doped with small amounts of C and Si are being developed to improve the creep resistance in order to increase the performances of this kind of alloys applied in the low-pressure turbine of aircraft engines. In order to extend the service temperature up to 1073 K or even above, the control of the microstructure stability is key. In this work, a complete study of the microstructure evolution during high-temperature exposure up to 1153 K has been approached through different electron microscopy techniques including HRTEM and HRSTEM with microanalysis. The nucleation and growth of the ordered βo precipitates and the ζ silicides inside the α2 lamellae has been carefully characterized and new orientation relationships and the misfit between all crystalline lattices has been determined, as well as the chemical concentration of the different atomic species on each phase. The electron microscopy study shows that βo and ζ precipitates inside α2 prevents or retards the dissolution of the α2 lamellae and its final disintegration in favor of the γ lamellae. This phenomenon has been discussed in terms of the phase coherence and diffusion processes. These important results allow conclude that the coarsening of the γ lamellae is delayed because of the βo and ζ precipitation, allowing to explain the observed enhancement of the creep resistance in this γ-TiAl based alloy exhibiting a nano-lamellar microstructure.This work was supported by the Spanish MINECO through the project CONSOLIDER-INGENIO 2010 CSD2009–00013 and further Networks MAT2016–81720-Red Imagine and Red2018–102609T, as well as by the Consolidated Research Group, GIU-21/024, from the University of the Basque Country (UPV/EHU). This work made use of the FEI-TITAN at the SGIKER facilities from the UPV/EHU

Universal Scaling Law for the Size Effect on Superelasticity at the Nanoscale Promotes the Use of Shape‐Memory Alloys in Stretchable Devices

Shape-memory alloys (SMAs) are the most stretchable metallic materials thanks to their superelastic behavior associated with the stress-induced martensitic transformation. This property makes SMAs of potential interest for flexible and wearable electronic technologies, provided that their properties will be retained at small scale. Nanocompression experiments on Cu-Al-Be SMA single crystals demonstrate that micro- and nanopillars, between 2 mu m and 260 nm in diameter, exhibit a reproducible superelastic behavior fully recoverable up to 8% strain, even at the nanoscale. Additionally, these micro-/nanopillars exhibit a size effect on the critical stress for superelasticity, which dramatically increases for pillars smaller than approximate to 1 mu m in diameter, scaling with a power law of exponent n = -2. The observed size effect agrees with a theoretical model of homogeneous nucleation of martensite at small scale and the universality of this scaling power law for Cu-based SMAs is proposed. These results open new directions for using SMAs as stretchable conductors and actuating devices in flexible and wearable technologies.This work was supported by the Spanish Ministry of Economy and Competitiveness, MINECO, projects MAT2017-84069P and CONSOLIDER-INGENIO 2010 CSD2009-00013, as well as by the ELKARTEK-ACTIMAT project from the Industry Department of the Basque Government, and GIU-17/071 from the University of the Basque Country, UPV/EHU. This work made use of the FIB facilities of the SGIKER from the UPV/EHU. V.F. also acknowledges the Post-Doctoral Mobility Grant from the CONICET of Argentina, and J.F.G.-C. acknowledges the Post-Doctoral Grant (ESPDOC18/37) from the UPV/EHU

Thermal Stability of Cu-Al-Ni Shape Memory Alloy Thin Films Obtained by Nanometer Multilayer Deposition

Cu-Al-Ni is a high-temperature shape memory alloy (HTSMA) with exceptional thermomechanical properties, making it an ideal active material for engineering new technologies able to operate at temperatures up to 200 °C. Recent studies revealed that these alloys exhibit a robust superelastic behavior at the nanometer scale, making them excellent candidates for developing a new generation of micro-/nano-electromechanical systems (MEMS/NEMS). The very large-scale integration (VLSI) technologies used in microelectronics are based on thin films. In the present work, 1 μm thickness thin films of 84.1Cu-12.4 Al-3.5Ni (wt.%) were obtained by solid-state diffusion from a multilayer system deposited on SiNx (200 nm)/Si substrates by e-beam evaporation. With the aim of evaluating the thermal stability of such HTSMA thin films, heating experiments were performed in situ inside the transmission electron microscope to identify the temperature at which the material was decomposed by precipitation. Their microstructure, compositional analysis, and phase identification were characterized by scanning and transmission electron microscopy equipped with energy dispersive X-ray spectrometers. The nucleation and growth of two stable phases, Cu-Al-rich alpha phase and Ni-Al-rich intermetallic, were identified during in situ heating TEM experiments between 280 and 450 °C. These findings show that the used production method produces an HTSMA with high thermal stability and paves the road for developing high-temperature MEMS/NEMS using shape memory and superelastic technologies.This research was funded by the Spanish Ministry of Science and Innovation, project PID2021-122160NB-I00, and the GIU-21/024 from the University of the Basque Country, UPV/EHU. This work made use of the TEM and SEM facilities of the Electron Microscopy and Microanalysis of Materials SGIKER of the UPV/EHU, as well as the FIB facilities of EML at NanoGune

Stress-assisted atomic diffusion in metastable austenite D03 phase of Cu-Al-Be shape memory alloys

Cu-Al-based shape memory alloys are firm candidates to be used up to 473 K. The main limiting aspect is the activation of diffusion processes in the metastable austenite phase, which drive the alloy decomposition. In the present work the study of short-distance diffusion processes has been approached by internal friction. A relaxation peak has been found in the metastable beta (D0(3)) phase of a Cu-Al-Be shape memory alloy, around 500 K (at 1 Hz), with an activation energy of E-a = 138 +/- 0.05 eV. An atomic mechanism of elastic dipoles Antisite-Vacancy reorientation, involving stress-assisted short distance Cu-atoms diffusion, has been proposed. (C) 2016 Elsevier B.V.This work was supported by the European H2020 Project REACT, Grant No 640241, and the Spanish Ministry MINECO projects, MAT2012-36421 and CONSOLIDER-INGENIO 2010 CSD2009-00013, as well as by the Consolidated Research Group IT-1090-16 from the Education Department and the project ELKARTEK ACTIMAT, KK-2015/0000094, from the Industry Department of the Basque Government

High temperature internal friction in a Ti–46Al–1Mo–0.2Si intermetallic, comparison with creep behaviour

Advanced gamma-TiAl based intermetallics Mo-bearing have been developed to obtain the fine-grained microstructure required for superplastic deformation to be used during further processing. In the present work we have studied an alloy of Ti-46.8Al-1Mo-0.2Si (at%) with two different microstructures, ascast material with a coarse grain size above 300 mu m, and the hot extruded material exhibiting a grain size smaller than 20 mu m. We have used a mechanical spectrometer especially developed for high temperature internal friction measurements to study the defect mobility processes taking place at high temperature. The internal friction spectra at different frequencies has been studied and analyzed up to 1360 K in order to characterize the relaxation processes appearing in this temperature range. A relaxation peak, with a maximum in between 900 K and 1080 K, depending on the oscillating frequency, has been attributed to Ti-atoms diffusion by the stress-induced reorientation of Al-V-Ti-Al elastic dipoles. The high temperature background in both microstructural states, as-cast and extruded, has been analyzed, measuring the apparent activation parameters, in particular the apparent energies of E-cast(IF) = 4.4 +/- 0.05 eV and E-ext(IF) = 4.75 +/- 0.05 eV respectively. These results have been compared to those obtained on the same materials by creep deformation. We may conclude that the activation parameters obtained by internal friction analysis, are consistent with the ones measured by creep. Furthermore, the analysis of the high temperature background allows establish the difference on creep resistance for both microstructural states. (c) 2015 Acta Materialia Inc. Published by Elsevier Ltd.This work was supported by the Spanish MICINN project CONSOLIDER-INGENIO 2010 CSD2009-00013, as well as by the Consolidated Research Group IT-10-310 from the Education Department and the project ETORTEK ACTIMAT from the Industry Department of the Basque Governmen

Strain Relaxation in Cu-Al-Ni Shape Memory Alloys Studied by in Situ Neutron Diffraction Experiments

In situ neutron diffraction is used to study the strain relaxation on a single crystal and other powdered Cu-Al-Ni shape memory alloys (SMAs) around martensitic transformation temperatures. This work is focused on the analysis of the strain evolution along the temperature memory effect appearing in these alloys after partial thermal transformations. A careful study of the influence of partial cycling on the neutron diffraction spectra in the martensitic phase is presented. Two different effects are observed, the d-spacing position shift and the narrowing of various diffraction peaks, along uncompleted transformation cycles during the thermal reverse martensitic transformation. These changes are associated with the relaxation of the mechanical stresses elastically stored around the martensitic variants, due to the different self-accommodating conditions after uncompleted transformations. The evolution of the stresses is measured through the strain relaxation, which is accessible by neutron diffraction. The observed effects and the measured strain relaxations are in agreement with the predictions of the model proposed to explain this behavior in previous calorimetric studies. In addition, the thermal expansion coefficients of both martensite and austenite phases were measured. The neutron experiments have allowed a complete description of the strains during martensitic transformation, and the obtained conclusions can be extrapolated to other SMA systems. (c) 2019 Author(s).This work was supported by the Spanish Ministry of Economy and Competitiveness (No. MINECO MAT2017-84069-P), as well as by the Consolidated Research Group (No. IT-1090-16) and the ELKARTEK-ACTIMAT project from the Education and Industry Departments of the Basque Government. The University of the Basque Country (UPV/EHU) also supported this work with the Research Group GIU17/071. This work has benefited from the use of NPDF at the Lujan Center at Los Alamos Neutron Science Center, funded by the Department of Energy (DOE) Office of Basic Energy Sciences. Los Alamos National Laboratory is operated by Los Alamos National Security LLC, under DOE Contract No. DE-AC52-06NA25396. The upgrade of NPDF was funded by the National Science Foundation (NSF) through Grant No. DMR 00-76488

The Influence of Thermal History on the Multistage Transformation of NiTi Shape-Memory Alloys

The multistage martensitic phase transformation of a polycrystalline NiTi shape-memory alloy (50.3 at. %Ni-49.7 at. % Ti) has been studied by means of calorimetric measurements. After a conventional thermal treatment followed by successive thermal cycles, the initial two-step forward transformation splits into four-overlapping stages. However, the reverse martensitic transformation maintains the initial two-step sequence, usually assigned to the B19'-> R -> B2 transformation. The correlation between the forward and reverse steps has been established by means of selected thermal cycles together with an estimation of their enthalpy and thermal hysteresis. These results have also provided information about the storage of the elastic strain energy and the frictional works associated with the variants' nucleation. Moreover, the study around the forward transformation temperature range by means of uncompleted thermal cycles undoubtedly shows the presence of temperature memory effects in both stages.This work has been supported by the Spanish Ministry of Economy and Competitiveness, MINECO, CONSOLIDER-INGENIO 2010 CSD2009-00013, as well as by the Consolidated Research Group IT-1090-16 and the ELKARTEK-ACTIMAT project from the Education and Industry Departments of the Basque Government. The University of the Basque Country has also supported this work with the Research Group grant: UPV/EHU GIU17/071. The authors appreciate the cooperation of J. Rodriguez-Aseguinolaza in the thermal treatments of the samples

Designing for Shape Memory in Additive Manufacturing of Cu–Al–Ni Shape Memory Alloy Processed by Laser Powder Bed Fusion

Shape memory alloys (SMAs) are functional materials that are being applied in practically all industries, from aerospace to biomedical sectors, and at present the scientific and technologic communities are looking to gain the advantages offered by the new processing technologies of additive manufacturing (AM). However, the use of AM to produce functional materials, like SMAs, constitutes a real challenge due to the particularly well controlled microstructure required to exhibit the functional property of shape memory. In the present work, the design of the complete AM processing route, from powder atomization to laser powder bed fusion for AM and hot isostatic pressing (HIP), is approached for Cu–Al–Ni SMAs. The microstructure of the different processing states is characterized in relationship with the processing parameters. The thermal martensitic transformation, responsible for the functional properties, is analyzed in a comparative way for each one of the different processed samples. The present results demonstrate that a final post–processing thermal treatment to control the microstructure is crucial to obtain the expected functional properties. Finally, it is demonstrated that using the designed processing route of laser powder bed fusion followed by a post–processing HIP and a final specific thermal treatment, a satisfactory shape memory behavior can be obtained in Cu–Al–Ni SMAs, paving the road for further applications.This research was supported by the Industry Department of the Basque Government through the ELKARTEK–CEMAP (KK–2020/00047) project, as well as from the GIU–17/071 from the University of the Basque Country UPV/EHU. Financial support was also received from the Spanish Ministry of Economy and Competitiveness, MINECO, through the project MAT2017-84069P. This work made use of the facilities from the Electronic Microscopy and Material Microanalysis Service of the SGIKER from the UPV/EHU. M.P.-C. acknowledges the pre–doctoral grant (PRE_2019_2_0268) from the Education Department of the Basque Country. J.F.G.-C. thanks the post–doctoral grant (ESPDOC18/37) from the UPV/EHU

Superelastic damping at nanoscale in ternary and quaternary Cu-based shape memory alloys

Superelasticity is a characteristic thermomechanical property in shape memory alloys (SMA), which is due to a reversible stress-induced martensitic transformation. Nano-compression experiments made possible the study of this property in Cu-Al-Ni SMA micropillars, showing an outstanding ultra-high mechanical damping capacity reproducible for thousands of cycles and reliable over the years. This scenario motivated the present work, where a comparative study of the damping capacity on four copper-based SMA: Cu-Al-Ni, Cu-Al-Be, Cu-Al-Ni-Be and Cu-Al-Ni-Ga is approached. For this purpose, [001] oriented single crystal micropillars of comparable dimensions (around 1 mu m in diameter) were milled by focused ion beam technique. All micropillars were cycled up to two hundred superelastic cycles, exhibiting a remarkable reproducibility. The damping capacity was evaluated through the dimensionless loss factor eta, calculated for each superelastic cycle, representing the dissipated energy per cycle and unit of volume. The calculated loss factor was averaged between three micro-pillars of each alloy, obtaining the following results: Cu-Al-Ni eta = 0.20 +/- 0.01; Cu-Al-Be eta = 0.100 +/- 0.006; Cu-Al-Ni-Be eta = 0.072 +/- 0.004 and Cu-Al-Ni-Ga eta = 0.042 +/- 0.002. These four alloys exhibit an intrinsic superelastic damping capacity and offer a wide loss factor band, which constitutes a reference for engineering, since this kind of micro/nano structures can potentially be integrated not only as sensors and actuators but also as dampers in the design of MEMS to improve their reliability. In addition, the study of the dependence of the superelastic loss factor on the diameter of the pillar was approached in the Cu-Al-Ni-Ga alloy, and here we demonstrate that there is a size effect on damping at the nanoscale.This research was supported by the Spanish Ministry of Economy and Competitiveness, MINECO, projects MAT2017-84069P and CONSOLIDER-INGENIO 2010 CSD2009-00013, as well as by the ELKARTEK-CEMAP project from the Industry Department of the Basque Government, and GIU-17/071 from the University of the Basque Country UPV/EHU, Spain. This work made use of the FIB and ICP facilities of the SGIKER from the UPV/EHU. The author V.F. acknowledges the Post-Doctoral Mobility Grant from the CONICET of Argentina, and J.F.G.-C. also acknowledges the Post-Doctoral Grant (ESPDOC18/37) from the UPV/EHU

Additive Manufacturing of Fe-Mn-Si-Based Shape Memory Alloys: State of the Art, Challenges and Opportunities

Additive manufacturing (AM) constitutes the new paradigm in materials processing and its use on metals and alloys opens new unforeseen possibilities, but is facing several challenges regarding the design of the microstructure, which is particularly awkward in the case of functional materials, like shape memory alloys (SMA), as they require a robust microstructure to withstand the constraints appearing during their shape change. In the present work, the attention is focused on the AM of the important Fe-Mn-Si-based SMA family, which is attracting a great technological interest in many industrial sectors. Initially, an overview on the design concepts of this SMA family is offered, with special emphasis to the problems arising during AM. Then, such concepts are considered in order to experimentally develop the AM production of the Fe-20Mn-6Si-9Cr-5Ni (wt%) SMA through laser powder bed fusion (LPBF). The complete methodology is approached, from the gas atomization of powders to the LPBF production and the final thermal treatments to functionalize the SMA. The microstructure is characterized by scanning and transmission electron microscopy after each step of the processing route. The reversibility of the ε martensitic transformation and its evolution on cycling are studied by internal friction and electron microscopy. An outstanding 14% of fully reversible thermal transformation of ε martensite is obtained. The present results show that, in spite of the still remaining challenges, AM by LPBF offers a good approach to produce this family of Fe-Mn-Si-based SMA, opening new opportunities for its applications.This research was supported by the Industry Department of the Basque Government through the ELKARTEK-MINERVA (KK-2022/000082) project, and also from the GIU-021/24 from the University of the Basque Country UPV/EHU. This work made use of the electron microscopes installed at the General Service of Electron Microscopy of Materials, of the SGIKER—UPV/EHU, and the Zeiss at LORTEK technology center. Lucía Del-Río acknowledges the Pre-Doctoral grant (PRE_2022_1_0109) from the Education Department of the Basque Government