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Self‐Patterning of Multifunctional Heusler Membranes by Dewetting
Ni-Mn-based Heusler alloys are an emerging class of materials which enable actuation by (magnetic) shape memory effects, magnetocaloric cooling, and thermomagnetic energy harvesting. Multifunctional materials have a particular advantage for miniaturization since their functionality is already built within the material. However, often complex microtechnological processing is required to bring these materials into shape. Here, self-organized formation of single crystalline membranes having arrays of rectangular holes with high aspect ratio is demonstrated. Dewetting avoids the need for complicated processing and allows to prepare freestanding Ni–Mn–Ga–Co membranes. These membranes are martensitic and magnetic, and their functional properties are not disturbed by self-patterning. Feature sizes of these membranes can be tailored by film thickness and heat treatment, and the tendencies can be explained with dewetting. As an outlook, the advantages of these multifunctional membranes for magnetocaloric and thermomagnetic microsystems are sketched. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH
Solving the puzzle of hierarchical martensitic microstructures in NiTi by (111)-oriented epitaxial films
The martensitic microstructure decides on the functional properties of shape memory alloys. However, for the most commonly used alloy, NiTi, it is still unclear how its microstructure is built up because the analysis is hampered by grain boundaries of polycrystalline samples. Here, we eliminate grain boundaries by using epitaxially grown films in (111)B2 orientation. By combining scale-bridging microscopy with integral inverse pole figures, we solve the puzzle of the hierarchical martensitic microstructure. We identify two martensite clusters as building blocks and three kinds of twin boundaries. Nesting them at different length scales explains why habit plane variants with ⟨011⟩B19' twin boundaries and {942} habit planes are dominant; but also some incompatible interfaces occur. Though the observed hierarchical microstructure agrees with the phenomenological theory of martensite, the transformation path decides which microstructure forms. The combination of local and global measurements with theory allows solving the scale bridging 3D puzzle of the martensitic microstructure in NiTi exemplarily for epitaxial films.
Influencing Martensitic Transition in Epitaxial Ni-Mn-Ga-Co Films with Large Angle Grain Boundaries
Magnetocaloric materials based on field-induced first order transformations such as Ni-Mn-Ga-Co are promising for more environmentally friendly cooling. Due to the underlying martensitic transformation, a large hysteresis can occur, which in turn reduces the efficiency of a cooling cycle. Here, we analyse the influence of the film microstructure on the thermal hysteresis and focus especially on large angle grain boundaries. We control the microstructure and grain boundary density by depositing films with local epitaxy on different substrates: Single crystalline MgO(0 0 1), MgO(1 1 0) and Al2O3(0 0 0 1). By combining local electron backscatter diffraction (EBSD) and global texture measurements with thermomagnetic measurements, we correlate a smaller hysteresis with the presence of grain boundaries. In films with grain boundaries, the hysteresis is decreased by about 30% compared to single crystalline films. Nevertheless, a large grain boundary density leads to a broadened transition. To explain this behaviour, we discuss the influence of grain boundaries on the martensitic transformation. While grain boundaries act as nucleation sites, they also lead to different strains in the material, which gives rise to various transition temperatures inside one film. We can show that a thoughtful design of the grain boundary microstructure is an important step to optimize the hysteresis.
What is the speed limit of martensitic transformations?
Structural martensitic transformations enable various applications, which range from high stroke actuation and sensing to energy efficient magnetocaloric refrigeration and thermomagnetic energy harvesting. All these emerging applications benefit from a fast transformation, but up to now their speed limit has not been explored. Here, we demonstrate that a thermoelastic martensite to austenite transformation can be completed within 10 ns. We heat epitaxial Ni-Mn-Ga films with a nanosecond laser pulse and use synchrotron diffraction to probe the influence of initial temperature and overheating on transformation rate and ratio. We demonstrate that an increase in thermal energy drives this transformation faster. Though the observed speed limit of 2.5 × 1027 (Js)1 per unit cell leaves plenty of room for further acceleration of applications, our analysis reveals that the practical limit will be the energy required for switching. Thus, martensitic transformations obey similar speed limits as in microelectronics, as expressed by the Margolus–Levitin theorem.
How to grow single-crystalline and epitaxial NiTi films in (100)- and (111)-orientation
Understanding the martensitic microstructure in nickel-titanium (NiTi) thin films helps to optimize their properties for applications in microsystems. Epitaxial and single-crystalline films can serve as model systems to understand the microstructure, as well as to exploit the anisotropic mechanical properties of NiTi. Here, we analyze the growth of NiTi on single-crystalline MgO(100) and Al2O3(0001) substrates and optimize film and buffer deposition conditions to achieve epitaxial films in (100)- and (111)-orientation. On MgO(100), we compare the transformation behavior and crystal quality of (100)-oriented NiTi films on different buffer layers. We demonstrate that a vanadium buffer layer helps to decrease the low-angle grain boundary density in the NiTi film, which inhibits undesired growth twins and leads to higher transformation temperatures. On Al2O3(0001), we analyze the orientation of a chromium buffer layer and find that it grows (111)-oriented only in a narrow temperature range around 500 ∘C. By depositing the Cr buffer below the NiTi film, we can prepare (111)-oriented, epitaxial films with transformation temperatures above room temperature. Transmission electron microscopy confirms a martensitic microstructure with Guinier Preston-zone precipitates at room temperature. We identify the deposition conditions to approach the ideal single crystalline state, which is beneficial for the analysis of the martensitic microstructure and anisotropic mechanical properties in different film orientations.