Robert Niemann

Metamagnetic transitions and magnetocaloric effect in epitaxial Ni–Co–Mn–In films

Due to their large strains and multifunctionality, magnetic shape memory alloys are of particular interest for microsystems. Here epitaxially grown metamagnetic Ni–Co–Mn–In films on MgO (001) are analyzed which exhibit a magnetically induced austenite transition. This opens the way to use Ni–Co–Mn–In films in microactuators combining high stroke with high forces. Additionally these films exhibit an inverse magnetocaloric effect with an entropy change of 8.8 J kg−1 K−1 in 9 T at 353 K. The high surface-to-volume fraction of films promises a fast heat exchange, which is beneficial for efficient magnetic cooling.

Magnetically induced martensite transition in freestanding epitaxial Ni–Mn–Ga films

The martensitic transformation in freestanding Ni–Mn–Ga films obtained by epitaxial growth on NaCl (001) is analyzed. A temperature-magnetic field phase diagram reveals that the martensitic phase, exhibiting a higher magnetization compared to austenite, is favored by an external field. A shift of martensite temperature of dT/dH=0.36 K/T is observed, in good agreement with the value expected from a Clausius–Clapeyron equation. The practicality and energy input for actuation using magnetically induced martensitic transition is compared with a magnetically induced reorientation of martensitic variants.

Inapplicability of the Maxwell relation for the quantification of caloric effects in anisotropic ferroic materials

Giant caloric effects were reported in elasto-, electro- and magnetocaloric materials near phase transformations. Commonly, their entropy change is indirectly evaluated by a Maxwell relation. Additionally to the well-known spurious “colossal” results near first-order phase transitions and limitations in the presence of magnetic domains, we report the fundamental failure of this approach for materials that show structural reorientations in external fields. We analyze exemplarily the magnetic shape memory alloy Ni-Mn-Ga. Application of a magnetic field causes magnetically induced reorientation of the crystal structure in the martensite phase. This results in a spurious inverse magnetocaloric effect that disappears when the measurement procedure is repeated. This failure is universal as the vector character of the applied field is not considered in the common scalar evaluation of a Maxwell relation.

Reducing the nucleation barrier in magnetocaloric Heusler alloys by nanoindentation

Magnetocaloric materials are promising as solid state refrigerants for more efficient and environmentally friendly cooling devices. The highest effects have been observed in materials that exhibit a first-order phase transition. These transformations proceed by nucleation and growth which lead to a hysteresis. Such irreversible processes are undesired since they heat up the material and reduce the efficiency of any cooling application. In this article, we demonstrate an approach to decrease the hysteresis by locally changing the nucleation barrier. We created artificial nucleation sites and analyzed the nucleation and growth processes in their proximity. We use Ni-Mn-Ga, a shape memory alloy that exhibits a martensitic transformation. Epitaxial films serve as a model system, but their high surface-to-volume ratio also allows for a fast heat transfer which is beneficial for a magnetocaloric regenerator geometry. Nanoindentation is used to create a well-defined defect. We quantify the austenite phase fracti...

Field-temperature phase diagrams of freestanding and substrate-constrained epitaxial Ni-Mn-Ga-Co films for magnetocaloric applications

Ferroic cooling processes that rely on field-induced first-order transformations of solid materials are a promising step towards a more energy-efficient refrigeration technology. In particular, thin films are discussed for their fast heat transfer and possible applications in microsystems. Substrate-constrained films are not useful since their substrates act as a heat sink. In this article, we examine a substrate-constrained and a freestanding epitaxial film of magnetocaloric Ni-Mn-Ga-Co. We compare phase diagrams and entropy changes obtained by magnetic field and temperature scans, which differ. We observe an asymmetry of the hysteresis between heating and cooling branch, which vanishes at high magnetic fields. These effects are discussed with respect to the vector character of a magnetic field, which acts differently on the nucleation and growth processes compared to the scalar character of the temperature.

Growth of sputter-deposited metamagnetic epitaxial Ni-Co-Mn-In films

Metamagnetic thin films represent a promising geometry for more efficient magnetocaloric cooling applications due to a fast heat transfer. Here, we identify suitable growth conditions to obtain epitaxial Ni-Mn-In-Co films with a metamagnetic transition in vicinity of room temperature. We show that both increased substrate temperature and target aging result in loss of indium. This can be attributed to evaporation and preferential sputtering, respectively. We present a model that treats the effect of target aging and temperature dependence of evaporation on the film composition independently and enables predictions of the film composition as a function of initial target composition, target age, and deposition temperature. Furthermore, our analysis reveals that a sufficient degree of chemical B2 order is required for a transformation, in addition to an appropriate film composition.

Geometry of adaptive martensite in Ni-Mn-based Heusler alloys

Abstract Modulated martensites play an important role in magnetic shape memory alloys, because all functional properties are closely connected to the twin microstructure and the phase boundary. The nature of the modulated martensites is still unclear. One approach is the concept of adaptive martensite, which regards all modulated phases as nanotwinned microstructures. In this article, we use the Ni-Mn-based shape memory alloys as an example to show the geometric rationale behind this concept using analytic equations based on the phenomenological theory of martensite. This could enhance discussions about the implications of the adaptive martensite by showing the exact relations between the various unit cells used to describe the structure. We use the concept to discuss the compatibility at the habit plane, the nature of high-order twin boundaries and the dependence of the lattice constants on the different types of modulation.

Nucleation and growth of hierarchical martensite in epitaxial shape memory films

Abstract Shape memory alloys often show a complex hierarchical morphology in the martensitic state. To understand the formation of this twin-within-twins microstructure, we examine epitaxial Ni-Mn-Ga films as a model system. In-situ scanning electron microscopy experiments show beautiful complex twinning patterns with a number of different mesoscopic and macroscopic twin boundaries between already twinned regions. We explain the appearance and geometry of these patterns by constructing an internally twinned martensitic nucleus, which can take the shape of a diamond or a parallelogram, within the basic phenomenological theory of martensite. These nucleus contains already the seeds of different possible mesoscopic twin boundaries. Nucleation and growth of these nuclei determines the creation of the hierarchical space-filling martensitic microstructure. This is in contrast to previous approaches to explain a hierarchical martensitic microstructure. This new picture of creation and anisotropic, well-oriented growth of twinned martensitic nuclei explains the morphology and exact geometrical features of our experimentally observed twins-within-twins microstructure on the meso- and macroscopic scale.

Epitaxial Ni-Mn-Ga-Co thin films on PMN-PT substrates for multicaloric applications

Multicaloric stacks consisting of a magnetocaloric film on a piezoelectric substrate promise improved caloric properties as the transition temperature can be controlled by both magnetic and electric fields. We present epitaxially grown magnetocaloric Ni-Mn-Ga-Co thin films on ferroelectric Pb(Mg1/3Nb2/3)0.72Ti0.28O3 substrates. Structure and microstructure of two samples, being in the austenitic and martensitic state at room temperature, are investigated by X-ray diffraction in two- and four-circle geometry and by atomic force microscopy. In addition, high temperature magnetometry was performed on the latter sample. The combination of these methods allows separating the influence of epitaxial growth and martensitic transformation. A preferential alignment of twin boundaries is observed already in the as-deposited state, which indicates the presence of prestress, without applying an electric field to the substrate. A temperature-magnetic field phase diagram is presented, which demonstrates the inverse magn...

Modulations in martensitic Heusler alloys originate from nanotwin ordering

Heusler alloys exhibiting magnetic and martensitic transitions enable applications like magnetocaloric refrigeration and actuation based on the magnetic shape memory effect. Their outstanding functional properties depend on low hysteresis losses and low actuation fields. These are only achieved if the atomic positions deviate from a tetragonal lattice by periodic displacements. The origin of the so-called modulated structures is the subject of much controversy: They are either explained by phonon softening or adaptive nanotwinning. Here we used large-scale density functional theory calculations on the Ni2MnGa prototype system to demonstrate interaction energy between twin boundaries. Minimizing the interaction energy resulted in the experimentally observed ordered modulations at the atomic scale, it explained that a/b twin boundaries are stacking faults at the mesoscale, and contributed to the macroscopic hysteresis losses. Furthermore, we found that phonon softening paves the transformation path towards the nanotwinned martensite state. This unified both opposing concepts to explain modulated martensite.