Magnetism of nanotwinned martensite in magnetic shape memory alloys.

Heusler-type magnetic shape memory alloys (MSMAs) exhibit a martensitic transformation (MT) accompanied by a complex magnetic reordering, strongly affected by an intricate martensitic microstructure. The hierarchic twin structure of martensite, formed as a result of minimization of elastic energy down to atomic scale, is under intensive study nowadays. On the other hand, the much more sophisticated problem of the relationship between nanoscale twin structure and the magnetism in MSMAs has being tackled only recently. It will be shown in this topical review that the nanotwin structure affects not only the basic magnetic parameters of MSMAs, but also can change qualitatively its magnetic nature and related magnetodynamic and magnetoresistance properties. This will be primarily illustrated, both theoretically and experimentally, on the prototype Ni-Mn-Ga and Ni(Co)-Mn-Sn MSMAs in the form of epitaxial thin films, but the conclusions are also valid for other Heusler-type MSMAs, both in the form of thin films, ribbons and bulk single crystals and polycrystals. The following new and remarkable phenomena will be highlighted. (i) A strong ferromagnetic exchange coupling is observed between the submicron twin components in Ni-Mn-Ga ferromagnetic martensite. It results in the modification of the average magnetic anisotropy and the formation of a non-collinear magnetic structure, whereby a negative magnetoresistance appears in a wide temperature range. (ii) Weak antiferromagnetic coupling occurs between the ferromagnetically ordered twin components in Ni(Co)-Mn-Sn martensite. This coupling enabled to explain the exchange bias and magnetic resonance spectra in the same terms as for artificial antiferromagnetically coupled multilayered structures.

Negative Magnetoresistance in Nanotwinned NiMnGa Epitaxial Films.

Magnetic shape memory alloys are under intensive investigation due to their unusual physical properties, such as magnetic shape memory effect, magnetic field induced superelasticity, direct and inverse magnetocaloric effect etc., promising for novel applications. One of the intriguing properties of these materials in a single phase state is a giant magnetoresistance. Here we report the remarkable results about the magnetoresistive properties of epitaxial films of Ni52.3Mn26.8Ga20.9 magnetic shape memory alloy in the temperature range of 100-370 K, well below the martensitic transformation temperature. It was found that the formation of non-collinear magnetic structure due to a nanotwinning of the film results in electron scattering on such a structure and noticeable negative magnetoresistance in the entire investigated temperature range.

Polarized Neutron Study of Ni-Mn-Ga Alloys: Site-Specific Spin Density Affected by Martensitic Transformation.

Polarized neutron scattering has been used to obtain the magnetic moment at specific crystallographic sites of the austenitic and martensitic phases of two nonstoichiometric Ni-Mn-Ga single crystals with close composition. These alloys have been chosen because they exhibit different structures in the paramagnetic state and inverse positions of the respective martensitic transformation and Curie temperature. The diffraction analysis revealed a remarkable result: Despite the similar alloy composition, the magnetic moments of Mn are quite different for the two alloys at the same crystallographic position. Furthermore, such a difference enabled us to assess that the exchange coupling between Mn atoms switches from ferro- to antiferromagnetic at a distance between 2.92 and 3.32 Å in the martensite. These results are of great importance to guide first principles calculations that, up to now, have not been contrasted with experiments at the atomic level.

High-yield fabrication of 60 nm Permalloy nanodiscs in well-defined magnetic vortex state for biomedical applications.

Permalloy disc structures in magnetic vortex state constitute a promising new type of magnetic nanoparticles for biomedical applications. They present high saturation magnetisation and lack of remanence, which ease the remote manipulation of the particles by magnetic fields and avoid the problem of agglomeration, respectively. Importantly, they are also endowed with the capability of low-frequency magneto-mechanical actuation. This effect has already been shown to produce cancer cell destruction using functionalized discs, about 1 µm in diameter, attached to the cell membrane. Here, Permalloy nanodiscs down to 60 nm in diameter are obtained by hole-mask colloidal lithography, which is proved to be a cost-effective method for the uniform patterning of large substrate areas, with a high production yield of nanostructures. The characterisation of the magnetic behaviour of the nanodiscs, complemented with micromagnetic simulations, confirms that they present a very well defined magnetic vortex configuration, unprecedented, to our knowledge, for nanostructures of this size prepared by a high-yield method. The successful detachment of the gold-covered nanodiscs from the substrate is also demonstrated by the use of sacrificial layers.

Magnetic field and atomic order effect on the martensitic transformation of a metamagnetic alloy.

The martensitic transformation (MT) of metamagnetic shape memory alloys is very sensitive to the applied magnetic field and atomic order. We analyze the alloy Ni50Mn34.5In15.5 in magnetic fields up to 13 T. The alloy has been prepared both in an ordered state by slow cooling, and in a disordered state by rapid quenching. In both cases the dependence of the martensitic transition temperature on the field is highly nonlinear. Such departure from linearity is due to a decrease of the entropy change at the transition, ΔS, with the applied field. This can be explained by the ordering effect of the magnetic field on the frustrated magnetic structure of the alloy in the martensitic phase. Compliance with a recent model, relying on the strong magnetoelastic interactions in these compounds, is very satisfactory.

Optimization of the magnetoelectric response of poly(vinylidene fluoride)/epoxy/Vitrovac laminates.

The effect of the bonding layer type and piezoelectric layer thickness on the magnetoelectric (ME) response of layered poly(vinylidene fluoride) (PVDF)/epoxy/Vitrovac composites is reported. Three distinct epoxy types were tested, commercially known as M-Bond, Devcon, and Stycast. The main differences among them are their different mechanical characteristics, in particular the value of the Young modulus, and the coupling with the polymer and Vitrovac (Fe39Ni39Mo4Si6B12) layers of the laminate. The laminated composites prepared with M-Bond epoxy exhibit the highest ME coupling. Experimental results also show that the ME response increases with increasing PVDF thickness, the highest ME response of 53 V·cm(-1)·Oe(-1) being obtained for a 110 µm thick PVDF/M-Bond epoxy/Vitrovac laminate. The behavior of the ME laminates with increasing temperatures up to 90 °C shows a decrease of more than 80% in the ME response of the laminate, explained by the deteriorated coupling between the different layers. A two-dimensional numerical model of the ME laminate composite based on the finite element method was used to evaluate the experimental results. A comparison between numerical and experimental data allows us to select the appropriate epoxy and to optimize the piezoelectric PVDF layer width to maximize the induced magnetoelectric voltage. The obtained results show the critical role of the bonding layer and piezoelectric layer thickness in the ME performance of laminate composites.

High performance magnetoimpedance in FeNi/Ti nanostructured multilayers with opened magnetic flux.

Magnetic [FeNi (170 nm)/Ti (6 nm)]3/Cu (L(cu) = 250 or 500 nm)/[Ti (6 nm)/FeNi (170 nm)]3 multilayers were designed with focus on high frequency applications. They were deposited onto glass or a microfluidic system compatible flexible Ciclo Olefin Copolymer substrate and comparatively tested. A maximum sensitivity for the total impedance of 110%/Oe was obtained for a driving current frequency of 30 MHz for [FeNi/Ti]3/Cu (L(cu) = 500 nm)/[Ti/FeNi]3 multilayers deposited onto a glass substrate and 45%/Oe for a driving current frequency of 65 MHz for the same multilayers deposited onto the flexible polymer substrate, a very promising result for applications. The possibility of using flexible substrate/[FeNi/Ti],/Cu/[Ti/FeNi]3 multilayers as MI pressure-sensitive elements was also demonstrated.

Transformation behavior of Ni-Mn-Ga in the low-temperature limit.

The magnetic, magnetocaloric and thermal characteristics have been studied in a Ni(50.3)Mn(20.8)Ga(27.6)V(1.3) ferromagnetic shape memory alloy (FSMA) transforming martensitically at around 40 K. The alloy shows first a transformation from austenite to an intermediate phase and then a partial transformation to an orthorhombic martensite, all the phases being ferromagnetically ordered. The thermomagnetization dependences enabled observation of the magnetocaloric effect in the vicinity of the martensitic transformation (MT). The Debye temperature and the density of states at the Fermi level are equal to θ(D) = (276 ± 4) K and 1.3 states/atom eV , respectively, and scarcely dependent on the magnetic field. The MT exhibited by Ni-Mn-Ga FSMAs at very low temperatures is distinctive in the sense that it is accompanied by a hardly detectable entropy change as a sign of a small driving force. The enhanced stability of the cubic phase and the low driving force of the MT stem from the reduced density of states near the Fermi level.

XAS and XMCD study of the influence of annealing on the atomic ordering and magnetism in an NiMnGa alloy.

The proper annealing of Ni(51)Mn(28)Ga(21) ribbon alloy gives rise to an increase of the saturation magnetization and of the magnetic order T(C) (up to 20 K) and martensitic transition T(M) (up to 10 K) temperatures. The combined x-ray absorption spectroscopy (XAS) and x-ray magnetic circular dichroism (XMCD) studies indicate that the annealing treatment drives the alloy to a more ordered structure without significantly affecting the local structure in terms of interatomic distances and bonding geometry. By contrast, the annealing strongly affects the near-edge absorption at the Mn K-edge while no effect is observed at either the Ni or Ga K-edge. These results suggest that annealing leads to a modification of the electronic structure of the Mn atoms while that of Ni and Ga atoms remains unvaried. However, strong XMCD signals are detected at both Ni and Ga K-edges whose amplitude increases after annealing. These results point out that despite the change of the magnetic properties of the system being mainly associated with the modification of the electronic properties of the Mn atoms, both Ni and Ga may play a non-negligible role through the polarization of the conduction band.