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Advances

in Magnetic
Shape Memory
Materials

Edited by
V.A. Chernenko

Advances in Magnetic Shape


Memory Materials

Special topic volume with invited peer reviewed papers only.

Edited by:

V.A. Chernenko

Copyright 2011 Trans Tech Publications Ltd, Switzerland


All rights reserved. No part of the contents of this publication may be reproduced or
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Volume 684 of
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Preface
Magnetic shape memory materials (MSMMs) comprise ferromagnetic alloys, such as
the off-stoichiometric Heusler X2YZ compounds (X is 3d-metal, Y is usually Mn but
could be some other 3d-metal or rare-earth element, Z is one of the elements from groups
III or IV of the periodic table), Fe3Pt, and Fe-Pd, which exhibit a thermoelastic
martensitic transformation (MT). The martensitic state formed as a result of MT can
possess either a similar saturation magnetization value as the initial austenitic cubic phase,
or else a sharply reduced magnetic moment, depending on the type of MSMM. In the first
case, the combined influence of the martensitic twin structure and magnetism gives rise
to the phenomenon of giant magnetostrain in the martensitic phase; on the other hand, a
magnetic field-induced MT is associated with giant functional properties such as the
magnetocaloric effect and magnetoresistance, in the second type of MSMMs. All
aforementioned MSMMs have received an enormous attention during the last decade,
whereby the related research activity is one of fast and vibrant growth in the area of smart
materials.
This second Special Topic book follows the success of the first one edited and
published by TTP in 2008. It intends to communicate the latest progress and research
advances in the theory and R&D of MSMMs.
This volume comprises a collection of fifteen invited peer-reviewed papers, each
detailing a particular aspect in the fundamental and/or applied investigation of MSMMs
and related phenomena. The comprehensive overview provided by these contributions
reflects strikingly the diverse facets of this materials science field. The papers show how
research is continuing to evolve and address new challenges, and are a corpus of up-todate information on the ongoing studies of MSMMs.
It is hoped that the present book will be useful to physicists and materials scientists,
both specialists and graduate students and enable future technological breakthroughs in
engineering.
This volume is the result of the hard work and remarkable cooperation of
distinguished experts in the field, to whom I wish to express my deepest gratitude.

V.A. Chernenko

Table of Contents
Preface
Composition-Dependent Basics of Smart Heusler Materials from First- Principles
Calculations
P. Entel, A. Dannenberg, M. Siewert, H.C. Herper, M.E. Gruner, V.D. Buchelnikov and V.A.
Chernenko
Magnetic Anisotropy of Ferromagnetic Martensites
V.A. L'vov and V.A. Chernenko
Entropy Changes in Ferromagnetic Shape Memory Alloys
E. Cesari, D. Salas and S. Kustov
Stress-Temperature Phase Diagram of Ni2MnGa and Structural Relations between its
Constituent Phases
T. Fukuda, T. Terai, H. Maeda and T. Kakeshita
Neutron Diffraction Studies of Magnetic Shape Memory Alloys
J.M. Barandiarn, J. Gutirrez, P. Lzpita and J. Feuchtwanger
Influence of Long-Range Atomic Order on the Structural and Magnetic Properties of NiMn-Ga Ferromagnetic Shape Memory Alloys
V. Snchez-Alarcos, J.I. Prez-Landazbal and V. Recarte
Crystal Structures of Modulated Martensitic Phases of FSM Heusler Alloys
L. Righi, F. Albertini, S. Fabbrici and A. Paoluzi
Magnetic Microstructure Analysis of Ferromagnetic Shape Memory Alloys and Related
Compounds
Y. Murakami, R. Kainuma, D. Shindo and A. Tonomura
Polycrystalline Ni-Mn-Ga as a Potential Material for Magnetically Driven Actuators
M. Ptschke, S. Roth, U. Gaitzsch, C. Hrrich, A. Bhm and L. Schultz
Metamagnetic Shape Memory Effect and Magnetic Properties of Ni-Mn Based Heusler
Alloys
R. Kainuma, W. Ito, R.Y. Umetsu, V.V. Khovaylo and T. Kanomata
Reverse Magnetostructural Transitions by Co and In Doping NiMnGa Alloys: Structural,
Magnetic, and Magnetoelastic Properties
F. Albertini, S. Fabbrici, A. Paoluzi, J. Kamarad, Z. Arnold, L. Righi, M. Solzi, G. Porcari, C.
Pernechele, D. Serrate and P. Algarabel
Magnetic Phase Diagram of the Ferromagnetic Shape Memory Alloys Ni2MnGa1-xCux
K. Endo, T. Kanomata, A. Kimura, M. Kataoka, H. Nishihara, R.Y. Umetsu, K. Obara, T.
Shishido, M. Nagasako, R. Kainuma and K.R.A. Ziebeck
Effects of Surface Pinning, Locking and Adaption of Twins on the Performance of Magnetic
Shape-Memory Alloys
M. Chmielus and P. Mllner
Long-Term Cyclic Loading of 10M Ni-Mn-Ga Alloys
I. Aaltio, O. Sderberg, Y.L. Ge and S.P. Hannula
Surface Study of Ni2MnGa(100)
S.W. D'Souza, R.S. Dhaka, A. Rai, M. Maniraj, J. Nayak, S. Singh, D.L. Schlagel, T.A. Lograsso,
A. Chakrabarti and S.R. Barman

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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.1

Composition-Dependent Basics of Smart Heusler Materials from FirstPrinciples Calculations


P. Entel1,a, A. Dannenberg1,b, M. Siewert1,c, H. C. Herper1,d, M. E. Gruner1,e,
V. D. Buchelnikov2,f and V. A. Chernenko3,4,g
1

Faculty of Physics and CeNIDE, D-47048 Duisburg, Germany,

Physics Department, Chelyabinsk State University, Chelyabinsk 454001, Russia

Dpto. de Electricidad y Electronica, Universidad del Pais Vasco, E-48080 Bilbao, Spain
4

Ikerbasque, Basque Foundation for Science, E-48011 Bilbao, Spain

entel@thp.uni-duisburg.de, bantje@thp.uni-duisburg.de, cmario@thp.uni-duisburg.de,


d
heike@thp.uni-duisburg.de, eme@thp.uni-dusiburg.de, fbuche@csu.ru,
g
vladimir.chernenko@gmail.com

Key words: Smart materials, Intermetallic Heusler alloys, First-principles calculations.

Abstract. The structural and magnetic order are the decisive elements which vastly determine the
properties of smart ternary intermetallics such as X2YZ Heusler alloys. Here, X and Y are transition
metal elements and Z is an element from the III-V group. In order to give a precise prescription of
the possibilities to optimize the magnetic shape memory and magnetocaloric effects of these alloys,
we use density functional theory calculations. In particular, we outline how one may find new
intermetallics which show higher Curie and martensite transformation temperatures when compared
with the prototypical magnetic shape-memory alloy Ni2MnGa. Higher operation temperatures are
needed for technological applications at elevated temperatures.
Introduction
The interplay of magnetism and structure in magnetoelastic materials gives rise to novel effects
such as the magnetic-shape memory effect (MSME) which is observed in the martensitic state of
magnetic shape-memory alloys (MSMA), and the magnetocaloric effect (MCE) at temperatures
near the magnetostructural phase transition. The MSMA are mostly ferromagnetic intermetallic
Heusler alloys, although Fe-Ni, Fe-Pd and Fe-Pt may display similar effects. The colossal
magnetoresistance (CMR) in the manganites not discussed in this paper, is another effect where the
mutual influence of magnetism and structure is the underlying principle that governs most of the
physical properties and is relevant when trying to optimize various functionalities for large-scale
technological applications [1-5]. Another intriguing magnetism-structure-based effect is related to
the magnetic intermetallics which have manganese as one of the constituting transition metal
elements. In such alloys we may find strong competition of diverse magnetic ordering tendencies
such as ferromagnetism and antiferromagnetism leading to a decrease of ferromagnetic order below
the martensite transformation temperature which may stabilize a spin-glass phase causing the Curie
temperature to drop to zero in some of the materials. The strong mixing of ferromagnetic and
antiferromagnetic interactions is also responsible for the exchange bias effect (EBE) which is
another effect of technological importance. In this contribution we summarize our todays basic
knowledge of smart Heusler alloys already in use or of interest for future exploitation of MSME [68] and MCE [9, 10]. The EBE displayed by some of the magnetic Heusler intermetallics, has so far
not been used in actual devices. Concerning magnetic refrigerators not involving the magnetic
intermetallic Heusler alloys but other families of magnetic materials, see [11, 12].
The interest in the MSMA arises from the fact that because of the large magnetomechanical
coupling in the modulated 5M and 7M martensites [3] their twin variants can be reoriented and

Advances in Magnetic Shape Memory Materials

redistributed by an external magnetic field giving rise to magnetic field-induced (MFI) strain effects
in a single crystal of Ni2MnGa [13, 14] which has meanwhile reached 10% in a magnetic field of
less than 1 T [15]. This has initiated many experimental and theoretical investigations [3,4, 6-8, 10,
16-20].
Very early, OHandley modeled magnetization processes and MFI strain effects suggesting that
depending on the magnetocrystalline anisotropy (MCA) energy relative to the Zeeman energy the
magnetization mechanism is either caused by twin boundary motion in case of strong anisotropy or
by magnetization rotation in case of weak anisotropy [21]. A magnetoelastic model of
ferromagnetic martensite was also developed in [22]. It is now generally accepted that the
mechanism of MFI strain in the MSMA involves transitions between the variants of the modulated
tetragonal martensite phase where the magnetically easy axis is the shortest c axis. By applying
stress or a magnetic field, the martensite twin variant may be transformed to one of the orthogonally
aligned neighbor variants. However, this reconstruction of martensitic domains is only possible
when their twin boundaries are mobile enough, i.e. when the martensite transformation is a
thermoelastic one. This leads to the appearance of adaptive martensite [23] which in case of
Ni2MnGa is responsible for the adaptive modulation of the lattice planes down to the atomic scale
[24].
Regarding twin boundary motion, a few attempts were made to obtain the associated energy barriers
using ab initio supercell calulations [25, 26]. In spite of this work, details of the twin boundary
motion on the atomic scale are not available, neither experimentally nor theoretically. Theory is to
some extent hampered because of the lack of appropriate, i.e. accurate enough model potentials
which would allow the simulation of moving twins under stress or magnetic field using molecular
dynamics tools for a sufficiently large number of atoms.
Since the Curie temperature of Ni-Mn-Ga alloys is not so high (TC 365 K) and since, moreover,
actuator devices require single crystals, technological applications are, apart from devices of
prototype nature, still missing. In addition, the Ni-Mn-Ga material is rather brittle. So, there is a
serious demand for replacing Ni2MnGa by other magnetic shape-memory materials which would
allow higher operational temperatures and, if possible, would allow the use of polycrystals.
Regarding the use of magnetic Heusler intermetallics in magnetic refrigeration, different obstacles
appear. The most serious one is that in order to achieve a reasonable entropy and temperature
change over the magnetic phase transition, one uses, e.g., alloys of Ni2+xMn1-xGa with 0.18 < x <
0.27 where the merging of magnetic and structural phase transition enhances the adiabatic
temperature change that can be achieved to a few Kelvin at high magnetic field which is not really
sufficient. The MCE has recently been calculated using a combination of ab initio methods and
model Hamiltonians [27]. The results show clearly that it is difficult to optimize the MCE because
of the many parameters involved [28].
In summary, the properties of the magnetoelastic materials arise from the strong interplay of
magnetic and structural degrees of freedom which also determines the electronic structure of the
materials. It is therefore mandatory to gain an understanding of the origin of the structural
(martensitic) instability and the change of magnetic ordering tendencies upon small compositional
changes as well as the formation of highly mobile twins down to the nanoscale. Furthermore, it is
not clear, whether the atomic modulation of the martensitic structure is needed to achieve the
MSME. It is also not clear whether the modulation itself is a consequence of the adaptive nature of
martensite or arises naturally from minimization of the elastic energy or from stacking faults,
dislocations and vacancy formation while passing from austenite to the martensite structure. In the
following we will discuss some of these questions by, first, explaining the magnetic order and,
second, to what extent they are related to the crystalline or disordered structures and what is their
relationship to the phase diagram of the MSMA. Finally, we will briefly outline how to improve the
MSMA, i.e. how to control the Curie and martensite transformation temperatures.

V.A. Chernenko

Reconstruction of the Electronic Density of States due to the Martensitic Transformation


A series of intermetallics crystallizes in the zinc-blende and Heusler crystal structures which consist
of four interpenetrating fcc lattices. The site occupancy of full (X2YZ) and half (XYZ) Heusler
alloys, i.e. distribution of the three elements X, Y and Z over the four fcc lattices denoted by A-D,
is shown in Fig. 1 (adapted from [30, 31]). Here, X and Y are transition metal elements while Z is
usually a covalently bonding element from the III-V group [30, 31]. With respect to the magnetic
properties of Heusler alloys of type X2MnZ, specific roles have been assigned to the elements
whereby X determines the lattice parameter while the (sp)-orbitals from Z mediate the magnetic
Mn-Mn interactions. There is strong interrelation of composition (X2YZ), chemical (L21) and
magnetic order. One of the most investigated system is Cu2MnAl which has become known as the
prototype Heusler alloy (see [30] and references therein). The half-metal full Heusler alloys like
Co2MnGe are of particular interest since the semiconducting gap is related to competing crystalfield effects: The X and (Mn, Ge) atoms are subject to octahedral and tetrahedral crystal fields,
respectively. As a result part of the antibonding d-electronic states of X2 (eu and t1u) and Mn are
mutually orthogonal to each other which may for appropriate valence electron concentration (e/a)
lead to an energy gap in the minority-spin channel of the cubic (L21) phase [32-34]. Half-metallicity
may also occur in cubic half-Heusler compounds such as NiMnSb with C1b structure. This was
predicted by de Groot et al. on the basis of ab initio calculations [35]. The half-metallic state may
gradually vanish due to disorder or non-quasiparticle effects [36].

Fig. 1: Left: The prototypical magnetic shape memory Heusler compound Ni2MnGa in the L21
structure (consisting of four interpenetrating fcc sublattices labeled A, B, C and D) with unit cell of
space group Fm3m (O5h). Sites B and D have point symmetry m3m (octahedral site) and sites A and
C have point symmetry 43m (tetrahedral site), see [30, 31]. Note that the whole crystal has
tetrahedral symmetry Td which is a subgroup of Oh. Preferential disorder type is B2 with
interchange of Y and Z. A half-metal state may appear for appropriate valence electron
concentration e/a when the Fermi level EF falls into the gap between crystal-field split antibonding
eu and t1u states. This gap is caused by the octahedral crystal field acting on the X2-3d states which
are orthogonal to the Mn-3d states as in case of Co2MnGe, for details see [33]. Ni2MnGa has one
more valence electron per formula unit compared to Co2MnGe: This shifts EF to higher energies
and pushes the semiconducting gap region below EF [37]. Right: A series of ordered structures can
be formed from the four fcc sublattices A-D such as L21 (D filled as B), A2 (all lattices identically
filled corresponding to complete disorder resulting in a bcc-like lattice with Im3m symmetry), B2
(C filled as A and D filled as B, resulting in a CsCl-like lattice of Im3m symmetry), B32 (B filled as
A and D filled as C), D03 (A, C, and D identically filled), C1 (D filled as B, C void), C1b (C void),
inverse Heusler structure (XY)XZ (B and C filled with X, D filled with Y and A filled with Z [38,
39]), quarternary Heusler alloys of type X1X2YZ and X2Y1Y2Z are discussed in [30, 31] and [40]).
For a discussion of L21-B2-A2 type disorder and ordering models (13 models of X2YZ and 42
models of XYZ) see [41].

Advances in Magnetic Shape Memory Materials

Those ferromagnetic Heusler alloys for which the Fermi energy falls into the semiconducting gap in
the minority-spin channel exhibit 100% spin polarization at EF. Therefore, these systems are of
interest for magnetoresistance devices, in particular, in view of their usually quite high Curie
temperatures and large magnetic moments per formula unit [42].

Fig. 2: Electronic density of states of (a) L21 Fe2MnSi, (b) L21 Co2MnGe, (c) L21 Co2FeSi, (d) L21
Ni2MnGa, (e) 5M Ni2MnGa, and (f) L10 Ni2MnGa. Lattice constants, c/a ratios, and magnetic
moments are those of the relaxed structures. All calculations were performed with the VASP [43]
(PBE-potentials included Mn-p and Ge-d in case of (b) and Ni-p, Mn-p and Ga-d in case of (d), for
the 5M structure, PW91 potentials were used not including Mn-p and Ga-d). Curie and Nel
temperatures for (a) were taken from [44], Curie temperatures in (b-d) were taken from [45-47],
respectively. Compare also [42] for further Curie temperatures of various Heusler compounds.
Note that half-metallic Co2FeSi has the highest Curie temperature and magnetic moment of all
ferromagnetic Heusler alloys. Fe2MnSi displays ferromagnetism and antiferromagnetism and seems
to be on the edge of a martensitic transformation at 339 K for stoichiometric compositions [44]. The
prototypical MSMA Ni2MnGa has one electron more per formula unit than Co2MnGe which shifts
EF to the upper edge of the semiconducting gap. This is responsible for the martensitic instability
since the system can lower its energy due to the band-Jahn-Teller effect [48].
Because of the semiconducting gap at EF in the minority-spin channel, the cubic half-metallic full
Heusler compounds do not undergo a martensitic transformation with decreasing temperature in
contrast to the MSMA, although the MSMA may show signatures of a semiconducting gap at
several energies in the minority-spin states. Since this feature is very important and vastly
determines the stability and physical properties of the diverse martensites of MSMA at low
temperatures, we have assembled in Fig. 2 the electronic density of states (DOS) curves of three
ferromagnetic half-metals, Fe2MnSi, Co2MnGe and Co2FeSi, all in the L21 structure, in comparison
to metallic Ni2MnGa (L21) and its 5M and L10 martensites. This comparison shows nicely the
change of the DOS with change of e/a, which may be understood by using a rigid band-like model

V.A. Chernenko

to explain the shift of EF with increasing e/a. Figure 2 also shows the reconstruction of the DOS of
Ni2MnGa when the system undergoes a martensitic transformation. As mentioned before, because
of the large MFI strain effects in Ni2MnGa, this system is considered as the prototypical MSMA
[7].
In case of atomic disorder, the half-metallic character is lost because the gap becomes partially
filled with one-electron states. Besides disorder, also non-quasi-particle effects may lead to
vanishing half-metallicity. These additional many-particle states which fill the gap may arise from
virtual spin-flip processes interacting with a bath of spin waves [36] (see also results of variational
cluster approximation with ab initio parameters to the multiorbital Hubbard model of NiMnSb
[49]).

Fig. 3: Supercell structure of Co9Fe4Si3 with Co colored yellow, Fe blue and Si in magenta (left)
and element-resolved and total DOS (right). Substitutional disorder leads to a partial filling of the
minority-spin gap in Fig. 2(c) which causes the Fermi energy to coincide with a high DOS peak
originating from Co-eg states (which does not yet destabilize the cubic structure). The total
magnetic moment is 23.14 B per 16-atom supercell (i.e. 5.79 B/f.u. if one counts four atoms per
formula unit). This means that disorder has led to slightly increased magnetic moments (mostly Fe).

Fig. 4: Variation of the total energy with respect to the energy of the cubic phase (c/a = 1) of
tetragonal distorted Co-Fe-Si. There is a clear trend of the alloy system to develop a structural
instability with increasing concentration of Si.

Advances in Magnetic Shape Memory Materials

We have investigated the strong effect of disorder in case of Co-Fe-Si alloys by using a cubic
supercell of 16 atoms with the compositions listed in Table I: Co8Fe5Si3, Co9Fe4Si3, Co9Fe3Si4 and
Co8Fe3Si5. Figure 3 shows the cubic supercell of 16 atoms used in the calculation of Co9Fe4Si3 as
well as the resulting DOS: The Fermi energy coincides now with the DOS peak of the Co-eg state
which is split from the high DOS region of Co and Fe right above EF, compare the DOS in Fig. 2(c)
and Fig. 3. This situation may lead to a martensitic instability as in case of Ni2MnGa with energy
minima at c/a < 1 and c/a > 1, which makes this system a new potential MSMA candidate, see Fig.
4. This is an interesting point since it shows that one may use some of the spintronics Heusler alloys
with their advantageous high Curie temperatures as potential MSMA candidates provided the alloys
become martensitic when varying the valence electron concentration.
Magnetic Correlations in X2YZ Heusler Alloys
The magnetic correlations in Heusler alloys were discussed in the literature by analyzing Curie
temperatures and hyperfine fields showing that the itinerant electrons of s- and d-character can be
studied quite independently [50]. For Y = Mn, neutron scattering experiments show that all the
magnetic moment (~ 4) resides on the Mn atom. The s-like electron from the X atom from the
latter part of the transition element series and the (sp)-electrons from the non-transition element Z
seem not to disturb the localized nature of the magnetic moments of the Mn atoms too much,
although the degree of s-d hybridization will ultimately determine the absolute value of magnetic
moment per formula unit. Hence, the magnetic behavior of the Heusler alloys is governed by three
types of interactions: (i) the magnetic Jsd interaction between the localized d- and itinerant s-like
electrons (this includes Coulomb exchange and hybridization), (ii) the magnetic Jdd exchange
interaction resulting from the interaction between localized and itinerant d-like electrons, (iii) a
superexchange-like interaction through the Z-(sp) electrons.
Although the concentration of itinerant d-like electrons is small in the Heusler alloys, it was
postulated that Jdd is by far the largest interaction which determines the Curie temperature TC. See
[50] for an analysis of the hyperfine field values at X and Z sites of a series of Heusler alloys which
shows that, quite unusually, the (sp)-electrons from Z contribute very little to the s-like conduction
electron polarization. It was furthermore observed that Jdd but not Jsd is responsible for the
ferromagnetic alignment in Heusler alloys. However, recent work by aolu et al. and by other
groups attributes more importance to the indirect exchange mediated mechanism by the Z-(sp)
electrons [51].
A first theoretical study of exchange interactions Jij and Curie temperatures TC of X2MnZ based on
ab initio calculations was undertaken by Kbler et al. [52] who showed that the microscopic origin
of magnetism in the Heusler alloys can be understood by comparing the relative stability of
ferromagnetic and antiferromagnetic configurations of the spin moments. Whereas the X-atoms
serve primarily to determine the lattice constants, the Z-atoms mediate the interactions between the
Mn-atoms. The localized character of magnetism results from the exclusion of minority spin
electrons from the Mn-3d shell. They argue that a Heisenberg model may be used to describe the
interaction between the localized magnetic moments of Mn and that a sign change of Jij results from
a competition of the intra-atomic magnetic energy and that the inter-atomic Z-atom mediated
covalent interaction between the Mn-d states is responsible for antiferromagnetism. The magnetic
character depends thus on the occupation of the p-d hybrid states. Although this hybridization
delocalizes the Mn-d states (which supports the picture in [50]), it also shows the essential role of
the (sp)-electrons from Z in forming the magnetic state (which contradicts the picture in [50]).
The magnetic exchange interaction parameters Jij can be calculated on an ab initio basis and may be
inserted into Monte Carlo codes to yield reliable Curie or Nel temperatures. They can therefore be
used to check the conjectures in [50] associated with the importance of the different contributions to

V.A. Chernenko

the Jij. The information about the change of the Jij with distance between pairs of atoms i and j and
how this alters with composition may also be used to complete the magnetic characterization of
X2YZ Heusler alloys.
The exchange constants of Heusler compounds of the generic pseudo-binary series Ni2Mn1+x(Ga,
In, Sn, Sb)1-x have been evaluated either by using the so called frozen-magnon approach [51] (for
details of the method see [53]) or alternatively in our group by using Lichtensteins approach within
the KKR formalism [54, 55]. The two methods yield comparable results.
Using the frozen magnon approach by aolu et al. [51] the intra- and inter-sublattice exchange
parameters and mean-field Curie temperatures of the prototypical MSMA series Ni2MnZ (Z = Ga,
In, Sn, Sb) were calculated with the augmented spherical wave (ASW) method [56] in the atomic
sphere approximation (ASA) [57] with exchange-correlation potential in the generalized gradient
approximation (GGA) of Perdew and Wang 1992 [58]. The authors describe the inter-atomic
exchange interaction in terms of the Heisenberg model

where , denote different sublattices and i = Ri, j = Rj are the corresponding lattice vectors within

the sublattices (, ), ei is the unit vector in direction of the magnetic moment at site (, i)
(henceforth we drop the sublattice indices). The exchange parameters Jij were calculated from the
frozen magnon energies (see [51] for details). There are a few important observations: (i)
Throughout the alloy series Ni2MnZ (Z = Ga, In, Sn, Sb) the variation of the Mn magnetic moment
is small whereas the moments of Ni and the Z atoms vary strongly. This has been attributed to the
different number of (sp)-electrons of (Ga, In) and (Sn, Sb), respectively. (ii) While for Ni2Mn(Ga,
In) the ferromagnetic inter-sublattice Mn-Ni exchange interaction is by far much larger than the
intra-sublattice Mn-Mn exchange interaction, this relation changes when considering Ni2Mn(Sn,
Sb), for Ni2MnSb the Mn-Mn exchange is now by a factor of three larger than the Mn-Ni
interaction. (iii) The Mn-Mn interactions in Ni2Mn(Ga, In) are all positive up to the fourth nearest
neighbor shell, for further distances a sign change occurs (6th nearest neighbor shell), for still
further distances between the Mn atoms the exchange parameters become very small. In Ni2MnSn
the Jij are positive up the third nearest neighbor shell and become strongly negative for the fourth
shell. For Ni2MnSb the interactions become very small after the second Mn-shell.
The points (i-iii) have been discussed in [51] in conjunction with the variation of spin waves or
frozen magnon energies as a function of the q-vector along the [110] direction. It was furthermore
noticed that in order to obtain reliable TC values, both type of interactions, Mn-Mn and Mn-Ni, are
important and have to be taken into account when calculating TC. It was also noted that because of
the large separation of the Mn atoms and the local moment behavior in the Ni2MnZ alloys, the
exchange coupling is indirect and mediated by the (sp)-conduction electrons from the Z-atoms. The
important role of conduction electrons in mediating the exchange interactions in the Mn-based
Heusler compound has further been discussed by the same authors in [59] suggesting that the local
moment formation on the Mn atoms may be discussed in terms of Andersons (sd)-impurity model
generalized to a lattice of magnetic impurities [60]. The localized magnetic moments may then be
coupled by the conduction electron-mediated exchange in terms of the Rudermann-Kittel-KasuyaYosida (RKKY) type of interaction [61-63]. As a consequence of the hybridization of localized
magnetic and conduction electron states in the Anderson model, fourth-order perturbation theory
gives rise to two terms, the ferromagnetically based RKKY-type of interaction and the Anderson
type of antiferromagnetically based superexchange interaction [62, 63]. Both are simultaneously

Advances in Magnetic Shape Memory Materials

present and must be taken into account. A recent application of this model-type of approach to halfHeusler (Cu, Pd)MnZ and full- Heusler (Cu, Pd)2MnZ alloys has been presented in [59].
We would however like to point out that the DOS of the (sp)-electrons is very small in a substantial
range of energies around EF (compare Fig. 2) and that in the exchange mediated interaction
delocalized d-electrons from Mn and Ni may play a non-negligible role, which supports to some
extent the view in [50]. So an angular momentum decomposition of the Jij is needed in order to
clarify the final picture, which interactions are mainly responsible for the local moment formation
on the Mn atoms and the resulting ferromagnetic or antiferromagnetic order (this calculation is
under way).
We have calculated the Jij by using the alternative method based on Lichtenstein approach [55] for
small rotations of the spin moments with frozen potentials, which expresses the exchange
parameters in terms of Korringa-Kohn-Rostoker (KKR) Greens functions and corresponding tmatrix elements and scattering-path operator for the disordered alloys as

Here, the atomic disorder is averaged out by using the coherent potential approximation (CPA)
which amounts to the replacement of each of the Greens functions by the corresponding CPA
Greens function. Nonlocal CPA corrections may become important in Heusler alloys which exhibit
strong atomic short-range order (SRO) effects. But so far, we have only calculated the Jij by using
the single-site CPA.
In the calculation we have used the Munich SPR-KKR package [56]. Our results (see also [27, 6466]) for the stoichiometric and cases of Ni2Mn1+x(Ga, In, Sn, Sb)1-x are displayed in Fig. 5. They
agree well with those obtained by the frozen-magnon approach to Ni2MnZ (Z = Ga, In, Sn, Sb) [51]
apart from small differences.
Since Ni2MnGa is the only Heusler system which shows a martensitic instability at stoichiometric
composition (with a martensitic transformation temperature around 200 K), we compare in Fig. 5
the corresponding exchange parameters of stoichiometric composition with those from supercell
calculations which allow to simulate the influence of disorder (although, strictly speaking, the
chosen supercells still correspond to stoichiometric compositions). In specific the Jij have been
evaluated for Ni8Mn6(Ga, In, Sn, Sb)2 superstructures corresponding to e/a = 8 for the Ga-based
system with MS = 585 K, e/a = 8 for the In-based alloy with MS = 400 K, e/a = 8.125 for the Snbased system with MS = 350 K, and e/a = 8.25 for the Sb-based alloy system with MS = 325 K,
respectively. Here, the martensitic transformation temperatures MS have been taken from the
experimental phase diagram displayed in Fig. 10. It is evident from Fig. 5 that strong
antiferromagnetic Mn-Mn exchange interactions emerge between those Mn atoms which have
become nearest neighbors (marked as Mn1 and Mn2 in Fig. 5). The nearest neighbor Mn-Mn
distance in stoichiometric Ni2MnGa is a0(2/2) = 4.1 while for Mn1-Mn2 in Ni8Mn6Ga2 it reduces
to a0/2 = 2.9 . The latter value lies in the range for which elemental fcc/bcc Mn is at the onset of
antiferromagnetic behavior: The respective E(rWS) curves exhibit an energy minimum at rWS = 2.716
a.u. (antiferromagnetic fcc Mn) and 2.799 a.u. (antiferromagnetic bcc Mn) which correspond to
nearest neighbor distances of 2.599 and 2.566 , respectively [67]. This means that
antiferromagnetism in the disordered Ni-Mn-Z alloys is induced by direct Mn-Mn interactions and
is not caused by (sp)-mediated superexchange. For the fcc structure of NiMn the Mn-Mn distance in
the Mn layers reduces further to 2.56 .

V.A. Chernenko

Fig. 5: (a-d) shows the magnetic exchange parameters of stoichiometric Ni2MnZ (Z = Ga, In, Sn,
Sb) compounds as a function of the distance between the atoms with Mn at the origin in each plot.
Lichtensteins formula [54] and the SPR-KKR method [55] were used in the calculations. The
results compare well with frozen-magnon calculations in [51]. A crossover can be observed with
respect to the relative magnitude of Mn-Ni and Mn-Mn interactions from the Ga- to the Sb-based
systems. In (e-h) we show the change of the Jij for the alloy series Ni8Mn6(Ga, In, Sn, Sb)2. Each
system in (e-h) is on the edge of a martensitic transformation, compare the experimental phase
diagram in Fig. 10(b) for the corresponding martensite transformation temperatures. Mn1 denotes
manganese on the regular Mn-sublattice and Mn2 has replaced Ga, In, Sn or Sb.

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It has been shown elsewhere that besides disorder also tetragonal distortions will induce
antiferromangetic correlations [27]. For example, in Ni2MnGa there is a change from ferromagnetic
to antiferromagnetic interactions for some of the Mn-Mn pairs for c/a 1.
Since Ni2Mn1+x(Ga, In, Sn, Sb)1-x can be considered as a pseudobinary system which changes
gradually from ferromagnetic order (for x = 0) to antiferromagnetic order (for x = 1) meaning that
the resulting Jij for e/a > 7.5 must show signs of antiferromagnetic ordering tendencies with
increasing x. The plots in Fig. 5(e-f) show that this is a very drastic effect resulting in large negative
Mn1-Mn2 exchange interactions between Mn-atoms which have now become nearest neighbors with
one Mn-atom on the regular Mn-sublattice and the second Mn-atom on the regular Z-sublattice. The
effect is most pronounced for the Sb-based alloys. We may tentatively conclude that this onset of
antiferromagnetic tendency is not due to an increase of covalent antiferromagnetism because with
increasing e/a (more Mn replacing Z) the number of (sp)-electrons from Z is effectively reduced.
The antiferromagnetic ordering tendencies with increasing e/a are connected with the
accompanying decrease of nearest neighbor Mn-Mn distances.
We would like to point out that the antiferromagnetic exchange parameters become even stronger
when the atomic disorder increases and become particularly strong with the onset of the martensitic
phase transformation. This is the reason for the common behavior of the experimental
magnetization curves of the Mn-based Heusler alloys, which all show a sudden increase of the
magnetization at the Curie temperature of the austenitic phase and then subsequently a sudden drop
at the martensitic transformation at MS. [10, 20, 27, 39, 40, 64]. A typical experimental example of
such behavior and corresponding results of Monte Carlo simulations is shown in Fig. 6 [27, 64].

Fig. 6: (a) Temperature variation of the magnetization of Ni50Mn35Sn15 (the experimental data were
taken from [65]). (b) Results of Monte Carlo simulations using the 5-state Potts model for the spin
moment of Mn and an Ising-like model for the elastic interaction (see [27, 64], the reduced
temperature is in units of the strength of the elastic interaction): The sudden increase in
magnetization occurs at the Curie temperature of the austenitic phase while the sudden decrease
occurs at the martensitic transformation due to the onset of strong antiferromagnetic interactions in
disordered Ni50Mn35Sn15. The antiferromagntic interactions increase further in the martensitic
phase, compare also Fig. 5(c, g).
Ruderman-Kittel-Kasuya-Yosida (RKKY) Interaction versus Superexchange Interaction
The magnetic interactions in the Heusler alloys Ni2MnSn, Cu2MnAl and Pd2MnSn were
investigated early using neutron spin-wave scattering which was analyzed in terms of a Heisenberg
model showing that interactions between more than six nearest neighbor shells must be taken into
account in order to describe the neutron scattering results. This long-range oscillatory behavior was
used to propose an indirect (sp-d)-type interaction as origin of the magnetic interactions [68-70].

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The ferromagnetic interactions in magnetic Heusler alloys emerging from this Ruderman-KittelKasuya-Yosida-type of interaction have been discussed in a series of papers using first-principles
calculations and the frozen-magnon approximation [51, 52, 59, 71-76] and, very similar, the
adiabatic procedure using the rigid spin approximation [77]. Along similar lines also lifetimes of
magnons were calculated on a first-principles basis [78].
As mentioned before, it is generally accepted that the indirect exchange interaction mediated by the
(sp)-electrons of the Z-element gives rise to ferromagnetic order while the competing
superexchange interaction mediated by the same electrons leads to antiferromagnetic coupling of
the Mn-spin moments in the Mn-based Heusler alloys [59]. Since this is important in order to
understand the most crucial magnetic features of the MSM Heusler alloys, we repeat briefly the
discussion of Ref. [59].
The Anderson (s-d)-impurity model for the formation of localized magnetic moments in a metal
includes a hybridization term of strength Vk allowing to promote electrons between the s- and dstates as well as a local Coulomb term to avoid double occupancy of the d-electron states [60], may
be generalized to a lattice of magnetic impurities called periodic Anderson model [79]. Elimination
of odd powers of Vk by successive canonical transformations similar to the Schrieffer-Wolff
transformation [80], allows to derive in a systematic fashion conduction-electron mediated
magnetic interactions between the periodically arranged magnetic impurities. In fourth order of Vk
(i.e. eliminating terms of order Vk and Vk3) the RKKY interaction arises from intermediate states
involving low-energy spin excitations corresponding to electron-hole pair formation with a spin-flip
transition, and a superexchange-type of interaction induced by virtual high-energy charge
excitations, which promote electrons from the localized d-states to states above EF [59, 62, 63]. See
[59] and the original literature [62, 63] for a more detailed discussion of these terms. In reciprocal
space and at zero temperature the interactions have the following form:

where k = k + q + G (G is a reciprocal lattice vector), nk labels the band and momentum of the
conduction electron Bloch state, d is the local energy of the d-electron level, and Vnk is the
hybridization matrix element which couples conduction and localized d-electrons (in the spirit of
the Anderson model, d d may be assumed to be of the order of the Hubbard U-energy [63]).
The JRKKY interaction is an oscillating function and its magnitude is mainly determined by the
topology of the Fermi surface and may become rather large in the preasymptotic region in case of
Fermi surface nesting, also the DOS at EF determines its size. In the q = 0 limit, the interaction may
be simplified to the limiting value given in Eq. (3) where (EF) is the DOS at EF and Ed is the
energy required to promote an electron from the 3d level to EF. V4 may be considered as an average
over the Fermi surface. Ed is not well defined in the Heusler alloys due to the broadening of the Mn
3d levels (as a crude estimate, we may take from Fig. 2(d) Ed = - 1.75 eV, (EF) = 0.25/eV and V =
0.75 eV, which would yield JRKKY = 45 meV and TC = 450 K to be compared with the experimental
and Monte Carlo result of 365 K).
In fourth order, Vk4, a second term appears which describes the superexchange interaction given by

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Fig. 7: (a-d) and (e-h) show the magnetic exchange parameters of Fig. 5 multiplied by (2d/a0)3
which yields the characteristic oscillations of the RKKY interactions. Note that for the
stoichiometric systems in (a-d) these oscillations are more clearly seen compared with those in (e-h)
where disordered systems are simulated by using supercells containing 16 atoms for each system.
The oscillations decay with increasing importance of disorder and antiferromagnetic interactions as
in Ni8Mn6Sn2 and Ni8Mn6Sb2. See corresponding RKKY-type oscillations of exchange parameters
of PdMnIn, PdMn2In, CuMnIn and Cu2MnIn in Ref. [59].

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13

which is more difficult to estimate without explicit numerical work. We would just like to mention
that both types of interactions are simultaneously present in the Heusler alloys and contribute to the
magnetic interaction. In case of disordered alloys we may find nearest neighbor Mn atoms at shorter
interatomic distances because Mn atoms on the regular Mn-sublattice may be surrounded by Mn on
X- and Z-sublattices. This allows for a small overlap of Mn-3d wave functions which will influence
the magnetic interactions in addition to the contributions from Eqs. (3-4).
Since the characteristic oscillations of the magnetic exchange interactions JRKKY vary in real space
as ~ cos(2kFr)/(2kFr)3, they may become visible if we multiply the Jij of Fig. 5 with (2d/a)3. This is
shown in Fig. 7.
The Importance of Inverse Magnetic Heusler Structures
In search for new magnetic Heusler alloys with better MSM characteristics aimed to explore the
MSME at room temperature or at even higher temperatures, we have considered another class of
Heusler alloys which exhibit the so-called inverse Heusler structure.
The building blocks of the inverse Heusler structures have already been indicated in Fig. 1. It seems
that the inverse alloys may be stabilized by the existence of a network consisting of mainly X and Y
transition metal elements when passing from the regular L21 X2YZ Heusler structure to the inverse
(XY)XZ structure. For stable inverse structures we need X and Y elements for which the d-electron
numbers do not differ too drastically such as Fe and Co in (FeCo)FeGa [39, 40] and which show the
tendency to hybridize strongly giving rise to covalent magnetism in the bcc-type of structure.
Covalent magnetism in FeCo-Heusler alloys has been discussed in [81]. Covalent magnetism in the
regular and inverse Heusler alloys, Fe2CoGa and (FeCo)FeGa, respectively, is an alternative to the
Stoner rigid-band model [82, 83], and arises from the spin-dependent changes in the covalent
interactions (hybridizations) between the d-states of neighboring Fe and Co atoms which have
similar electronegativity. The latter effect suppresses very large charge transfer effects. The
resulting Curie temperatures are rather high. For convenience, we show in Fig. 8 again the
structures of the regular and inverse arrangement of the transition metal elements X and Y for the
case of Fe2CoGa.

Fig. 8: (a) Conventional L21 (Fm3m) Heusler structure of Fe2CoGa where the FeA and FeB (yellow)
occupy the X-sites and Co (blue) and Ga (violet) the Y- and Z-sites, respectively. (b) Inverse
(F43m) Heusler structure (FeCo)FeGa where Co and FeB have been interchanged (the
corresponding iron atom is marked as FeC and the interchange of X- and Y-atom is marked by an
arrow).
The Fe2CoGa (e/a = 7) alloy system is in so far remarkable as the inverse structure is much lower in
energy than the regular one. The reason is the bonding network of Fe-Co with strong hybridization

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of Fe- and Co-states in the bcc-type of structure. The covalent magnetism arising from covalent
interactions (hybridizations) in each spin channel, contributes further to the stability of the inverse
structure. Furthermore, the regular structure shows a martensitic instability whereas the inverse
structure does not show any sign of instability [39, 40, 84]. However, one may probably induce the
structural instability by enhancing the number of (sp)-electrons, for instance, by replacing Ga by Si
which enhances the nature of covalent bonding in (FeCo)Fe(Ga, Si). This is of particular interest
since it would make Fe-Co-(Ga, Si) alloys potential candidates as new magnetic shape-memory
alloys with very high Curie temperatures (> 600 K) because there are no antiferromagnetic
tendencies as in Ni-Mn-Z (Z = Ga, In, Sn, Sb) [84].
The energetic scenario of Ni2MnGa is completely different. In this case, the inverse structure is by
400 meV higher in energy compared to the regular structure. Both structures show a martensitic
instability, see Fig. 9. The reason for this different behavior of Ni-Mn-Ga and Fe-Co-(Ga, Si) is
related to the observation that Ni- and Mn-states do not show the same favorable hybridization
effects as Fe and Co, cf. the DOS of L21 Ni2MnGa in Fig. 1(d). In addition, the contribution of Mn,
which carries almost all of the magnetic moment in Ni2MnGa, to the DOS is more Stoner-rigidband-like than bearing features of covalent magnetism. So, it is essentially the nature of magnetism
(covalent versus Stoner-like) which distinguishes Fe2Co(Ga, Si) from Ni2MnGa.
The question for which Heusler system the regular or inverse structure is more stable can be
answered at least qualitatively. Iron in Fe2CoGa is best bcc-like coordinated in the inverse structure
where one of the two inequivalent Fe has four nearest neighbor Fe and four nearest neighbor Co
which comes close to the bcc environment in bulk bcc Fe. In contrast, for Ni2MnGa one of the Ni
has four nearest neighbor Ni and four nearest neighbor Mn in the bcc-like environment. This is
energetically not favorable since Ni prefers an fcc environment as in bulk Ni. Therefore, the regular
structure of L21 Ni2MnGa is energetically preferred over the inverse F43m (NiMn)NiGa structure,
see Fig. 9. In case of Fe2CoGa and Co2NiGa the inverse structure is preferred.

Fig. 9: (a) Magnetization and (b) total energies of regular Ni2MnGa and inverse (NiMn)NiGa
relative to the energy minimum at c/a < 1 of the inverse structure as a function of the tetragonal
distortion. The regular structure is by ca. 400 meV/f.u. lower in energy than the inverse structure.
(c) and (d) show corresponding results for Co2NiGa (here, the reference energy is the regular
structure at c/a = 1). In this case the inverse structure is slightly lower in energy for all c/a. For
Co2FeSi (not shown) the regular structure is again by 400 meV lower in energy compared to the
inverse one (similar to Ni2MnGa) while for Fe2CoSi the inverse structure is stable.

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The Phase Diagram of the Pseudobinary Alloy Series Ni2Mn1+x(Ga, In, Sn, Sb)1-x
For a systematic search of new promising MSMA based on Heusler intermetallics, it is worthwhile
to reconsider the structural and magnetic trends of the pseudobinary alloy series Ni2Mn1+x(Ga, In,
Sn, Sb)1-x which is shown in Figs. 10(b) and (c). Based on this discussion one may attempt to find
new alloy series with different X and Y but the same Z elements.

Fig. 10: (a) Martensitic transformation temperature (MS) and Curie temperature (TC) for different
Ni-Mn-Ga alloys as a function of the valence electron concentration (e/a) (adapted from [85, 86]).
The symbols refer to different groups of samples as defined in Ref. [85]. (b) Pseudobinary phase
diagram showing the martensite start temperatures MS(Z) and Curie temperatures of austenite and
martensite, TCA(Z) and TCM(Z), respectively, of Ni2Mn1+xZ1-x (Z = Ga, In, Sn, Sb). The phase
diagram has been adapted from [93]. (c) The corresponding theoretical phase diagram obtained
from total energy calculations of E(c/a) curves, where the energy differences as a function of e/a
between austenite and martensite phases reproduce the linear variation of MS(Z) of the experimental
curves. Free energy calculations including only the phonon dispersions show the same trend. The
Curie temperatures are obtained from ab initio exchange parameters and Monte Carlo simulations
using the Heisenberg model. We have simulated off-stoichiometric compositions using supercells
labeled 1, 2 and 3.

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The phase diagram of the off-stoichiometric Ni-Mn-Z alloys has been investigated by several
groups [85-92] (for further references and more details of the dependence of TC, MS and
premartensitic transformation on composition see [16, 37]). First systematic investigations for a
variety of compositions were discussed in [85, 86], the assembled data are reproduced in Fig. 10(a)
(most investigations concentrated on Ni excess in Ni2+x+yMn1-xGa1-y alloys). Alternatively,
pseudobinary phases can be discussed by considering the compositions between Ni2Mn(Ga, In, Sn,
Sb) and the binary alloy NiMn which is antiferromagnetic. Smooth variation of the composition
allows then to follow in detail the evolution from ferromagnetism to antiferromagnetism with
increasing content of Mn. In Fig. 10(b) we show the resulting pseudobinary phase diagram which
has been adapted from [10, 20, 93]. Finally, Fig. 10(c) shows the theoretical phase diagram
obtained from ab initio total energy and Monte Carlo calculations. An additional type of phase
diagram is obtained if one applies external compressive stress which is discussed in [94].
With increasing e/a one finds for each of the alloys a crossover from the low-temperature
ferromagnetic state to the high-temperature phase of antiferromagnetic NiMn. This is in agreement
with the behavior of the magnetic exchange parameters shown in Fig. 5. The crossover seems to be
continuous and is due to the increasing strength of antiferromagnetic correlations between Mn1 and
Mn2 atoms, cf. Fig. 5. Simultaneously, each system undergoes a martensitic transformation at a
critical value of e/a. NiMn is an antiferromagnet with CsCl structure, a high Nel and a high
martensite transformation temperature to a tetragonal phase.
The structural transformation seems to be unaffected by the gradual change from ferromagnetic to
antiferromagnetic order and can be described by a linear variation of MS with e/a. This is only
possible if the total magnetic moment/f.u. (which is mainly the sum of the moments of the Mn
atoms) of each alloy system varies also linearly with e/a. This is indeed the case: The pseudobinary
alloy series Ni2Mn1+x(Ga, In, Sn, Sb)1-x displays super-Slater-Pauling behavior as shown in Fig. 15.
The linear variation of the magnetic moments with e/a is caused by the linear variation of the
number of Mn-atoms with spin-up minus Mn-atoms with spin down. This is finally the explanation
why the linear variation of MS(Z) with e/a appears to be unaffected by the gradual change from a
ferromagnetism to antiferromagnetism for each alloy system.
What needs to be explained is the driving force of the martensitic instability and the linear variation
of MS with change of composition.
Nature of Martensitic Instability in the Pseudobinary Alloy Series Ni2Mn1+x(Ga, In, Sn, Sb)1-x
Many groups have investigated the structural transformation from the cubic Heusler intermetallics
to unmodulated or modulated tetragonal, monoclinic or orthorhombic martensitic structures. The
origin of the martensitic instability may differ in nature from one alloy series to the other. Several
explanations have been proposed. (i) Strong Fermi surface nesting in stoichiometric Ni2MnGa is
responsible for the phonon softening near the nesting vector while the origin of the structural
transformation has been attributed to the large DOS peak of Ni-eg states right below EF in the spindown channel. By the band Jahn-Teller effect the energy is then lowered due to a tetragonal
distortion which moves the high DOS-peak away from EF to E > EF in the tetragonal state [17, 19,
48, 95-98]. Both effects, nesting and Jahn-Teller distortion cooperate mutually. (ii) Now, when
changing the composition in the alloy series Ni2Mn1+xZ1-x (Z = Ga, In, Sn, Sb), the situation
becomes rather complex. In order to check this, we have used supercells with 16 atoms
[Ni8Mn4+x(Ga, In, Sn, Sb)4-x (x = 0, 1, 2, 3 and 4)] when evaluating Fermi surfaces and DOS.
We first compare the ferromagnetic Ni2MnGa (L21 structure) with the limiting binary system NiMn
(CsCl structure) which is antiferromagnetic. While Ni2MnGa is ferromagnetic and shows strong
Fermi surface nesting in the spin-down channel favoring a structural phase transformation from a
cubic to a tetragonal phase which is further supported by the band Jahn-Teller effect, this type of

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nesting behavior vanishes for NiMn. However, the band Jahn-Teller effect is still active and is
responsible for the martensitic transformation of the antiferromagnet NiMn from (bcc-like) -NiMn
to (L10) -NiMn (fcc-like structure with a tiny tetragonal or orthorhombic distortion [99]). For
completeness we show the high-temperature part of the Ni-Mn phase diagram in Fig. 11 which we
have adopted from Hansen, Adachi and Wayman [100, 101]. Note that there is some controversy
concerning a series of two-phase fields around the equiatomic region [100-104]. The phase diagram
shown in Fig. 11 agrees qualitatively with the most recent thermodynamic investigation of the NiMn system by Gu and Du [103].

Fig. 11: High-temperature region of the Ni-Mn phase diagram showing the concentration
dependence of the T (bcc fcc or L10) transformation temperature [100, 101]. The star marks
the Nel temperature (TN = 1075 K) which was obtained by Monte Carlo simulations using
magnetic exchange parameters from ab initio calculations. Note that the martensitic transformation
in NiMn appears in the magnetic state (antiferromagnetic or ferromagnetic) as in Ni2MnGa where it
occurs in ferromagnetic cubic austenite.

Fig. 12: Austenite-martensite phase diagram of NiMn showing the energy variation for two
antiferromagnetic type of orderings: AF1 has the lowest energy in the fcc state (no fct solution is
found in the calculations). The AF1 and AF2 antiferromagnetic is shown in the left panel. The
energy difference between the two minima of the AF2 curve is taken to estimate the martensitic
transformation temperature, see star in Fig. 10(c).

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The structural instability of antiferromagnetic NiMn is also reflected by the total energy curve,
E(c/a), which exhibits a local minimum at c/a = 0.9 and a second, lower energy minimum at c/a =
1.4 just as in case of Ni2MnGa. From the energy difference of the two minima we may get a rough
estimate of MS of NiMn which is marked by the star in Fig. 10(c). However, one should mention
that NiMn, depending on atomic order and slight local concentration variations, may show many
different close in energy lying antiferromagnetic solutions. Some of them were discussed by Kasper
and Kouvel [99]. In Fig. 12 we show the c/a variation of two such antiferromagnetic states denoted
by AF1 and AF2 with the magnetic ordering shown in Fig. 12.
Figure 13 shows the variation of the magnetic exchange parameters in the antiferromagnetic ground
state (layered arrangement of moments as shown in Fig. 12) of ordered NiMn. The labeling Mn1
and Mn2 is chosen with respect to the differently aligned magnetic moments of the Mn atoms.

Fig. 13: Magnetic exchange parameters of antiferromagnetic NiMn. Mn1 and Mn2 denote the Mn
atoms with opposite spins. In the plot Mn1 is at the origin. The structure is fcc with an optimized
lattice constant of 3.61 and corresponds to a complete Bain transformation of the original bcclike Heusler structure. No tetragonal distortion of the fcc lattice leading to a lower energy state has
been observed during the structural relaxation in contrast to the experimental suggestion of a
tetragonally distorted fcc lattice [99]. Monte Carlo simulations yield a Nel temperature of 1075 K.
For compositions in between Ni2MnGa and NiMn we find the same high Ni-DOS peak situated just
below EF which (in the spirit of the band Jahn-Teller effect) is responsible for the structural
transformation of all Ni-Mn-Ga alloys while Fermi surface nesting is less pronounced for the
disordered alloys and finally vanishes when approaching NiMn. Figure 14 shows the DOS of the
antiferromagnet NiMn for the cubic Heusler structure with supercell geometry Ni8Mn8 in (a) and
the two tetragonal structures, c/a = 0.9 (b) and c/a = 1.4 (c). The latter structure corresponds to an
fcc lattice with lattice constant afcc = 4.1 (squares in Fig. 12). Further volume optimization and a
change of the magnetic ordering leads to an fcc lattice with a smaller lattice constant of 3.61
(circles in Fig. 12) for which the magnetic exchange parameters are shown in Fig. 13. The DOS for
this energetically lowest state is shown in Fig. 14(d).
For the other pseudobinary systems, Ni-Mn-(In, Sn, Sb), the high Ni-DOS peak at EF is smeared out
and pushed further down below EF. This holds for large range of compositions between Ni2Mn(In,
Sn, Sb) and NiMn for which also Fermi surface nesting in the spin-down channel is largely absent.
Much less nesting is found for the majority-spin electrons of all Ni-Mn-(Ga, In, Sn, Sb) systems.

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Fig. 14: Density of states of the antiferromagnet NiMn [the formula unit is Ni8Mn8] for (a) cubic
(c/a = 1) bcc-like Heusler structure, (b) tetragonal distortion c/a = 0.9 and (c) c/a = 1.4 (fcc). The
volume is conserved for both martensitic distortions, i.e. a2c = a03. Note that for cubic NiMn a high
DOS peak of Ni-d states is just at EF which is responsible for the band Jahn-Teller distortion just as
in case of cubic Ni2MnGa. The calculations show that however for the bcc structure (c/a = 1) the
ferromagnetic solution is by a few meV/atom lower in energy compared with the antiferromagnetic
one (cf. Fig. 12) while the antiferromagnetic solution for the fcc structure (c/a = 1.4) is much lower
in energy compared to all other magnetic states in agreement with experiment. In (a-c) the
antiferromagnetic order corresponds to AF2 defined in Fig. 12. When further optimizing the
structure, we find an fcc phase with AF1 ordering at lower volume and lower energy, see Fig. 12, of
which the DOS is shown in (d). For this antiferromagnetic AF1 state the chemical and magnetic unit
cells are identical and the theoretical Nel temperature is very high, about 1075 K (cf. [99]).
In summary, we may conclude that for Ni-Mn-Ga the tetragonal distortion can be discussed in
terms of Kohn anomaly and band-Jahn Teller effect, also for the off-stoichiometric alloys.
However, we woud like to underline that these effects are weaker for the Ni-Mn-(In, Sn, Sb) alloys
because of the reduced peak height of the Ni-eg DOS near EF due to atomic disorder. On the other
hand, it has recently been shown that the excess Mn at the Sn site in Ni2Mn1+xSn1-x effectively
works so as to shift the sharp DOS peak of Ni-eg minority spin states closer to the Fermi energy,
which is induced by the hybridization of Ni-3d and Mn-3d states at the Sn site (with the Mn spin
aligned antiparallel to that of the regular Mn site in the minority spin channel) [105].
In order to get an impression of the shift of the Ni-eg minority spin states towards EF into the
unoccupied energy region with change of composition in the Ni2Mn1+x(Ga, In, Sn, Sb)1-x alloy
series, we have calculated the DOS as a function of c/a and (E EF) for all pseudobinary systems.
The plot of constant minority-spin DOS contour lines in Fig. 15 shows the linear progression of the
Ni-eg minority spin states through EF for the case of Ni2MnGa (white-light blue color stripe
extending from -0.5 to 0.9 eV and crossing EF at c/a = 1.1). Since in a rigid band picture the DOS

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curves for energies different from EF correspond to systems with different e/a, we have added to
Fig. 15 the lines of constant e/a at intervals of 0.1 obtained from the integration of the DOS curves,

Here, (E) is the DOS of spin-up and spin-down electron states at energy E. The factor is there
because the DOS was calculated per formula unit.

Fig. 15: Lines of constant density of states curves of Ni2MnGa projected onto the (E EF, c/a)
plane. The black dots indicate the two local energy minima along c/a. The Figure shows the
progression of the Ni-eg peak with c/a from lower left (-0.5 eV) to upper right (0.9 eV) crossing the
c/a line at 1.1 (stripe with many narrow contour lines and DOS values assigned by white-light
blue), which stabilizes the martensite structure relative to austenite. We have also introduced lines
of constant e/a obtained from the integration of the DOS curves, which extend from the lower axis
to the upper axis (thin black lines). The dashed line at EF marks e/a = 7.5. So, the crossing of the
Ni-eg peak can also be interpreted in terms of varying e/a in the alloy.
This crossing of the Ni-eg peak with variation of e/a becomes less pronounced for the Ni-Mn-(In,
Sn, Sb) alloys because of disorder effects.. This means that strong electron-phonon coupling of the
Ni-3d and Mn-3d electrons may still contribute to the driving force for the martensitic
transformation in Ni-Mn-(In, Sn, Sb). We have recently investigated Co2NiGa alloys which is
another system where band Jahn-Teller effect, Fermi surface nesting and phonon softening are
absent but still a martensitic transformation occurs because of strong electron-phonon coupling
[107].
We may therefore safely assume that the martensitic transformation in practically all Ni2Mn1+xZ1-x
alloys can be attributed to band Jahn-Teller effect in conjunction with strong electron-phonon
coupling. When increasing e/a more 3d-states from Y with high DOS are enclosed by the Fermi
surface which can contribute to the electron-phonon coupling. Since there are practically only 3dstates of sizable DOS near EF, the increase of electrons involved in the electron-phonon coupling
increases linearly with e/a. This may finally be the reason of the linear increase of MS with e/a. As
discussed before, the gradual change from ferromagnetic to antiferromagnetic order in the alloys
does not disturb and hence does not alter the linear variation of MS(e/a). (iii) A third point needs at
least to be briefly mentioned, namely, in how far Hume-Rothery-like rules which are applicable to

V.A. Chernenko

21

nonferrous -phase alloys [108], may also be involved in the structural instability which occurs in
magnetic Heusler alloys. Indeed one may consider Ni2MnGa alloys as belonging to the -phase
alloys with respect to their bcc-like structure (see also [86]), where the lattice stability may depend
on the lowering of the band energy by the formation of a pseudogap when varying e/a as in Cu-,
Ag- and Au-based alloys which undergo a martensitic transformation. There is however, a
difference in that the Hume-Rothery mechanism applies to simple (sp)-bonded metals for which the
pseudogap opens when the Fermi surface touches the Brillouin zone. For the MSMA the band
structure is more complicated and essentially only 3d-electrons are near the Fermi surface.
However, pseudogap formation is certainly involved in some cases and some resemblance holds for
the case of stoichiometric Ni2MnGa and its Fermi surface nesting, where one may assume that the
d-electrons take over the role of (sp)-electrons of the Hume-Rothery alloys. On the other hand, the
Hume-Rothery rules completely ignore the effect of strong electron-phonon coupling because the
(sp)-electrons usually couple only weakly to the phonons due to their low DOS.

Fig. 16: Slater-Pauling behavior of the calculated saturation magnetization of the cubic Ni-Mn-Z
alloys with Z = Ga (black), In (red), Sn (violet) and Sb (magenta) (open symbols) as a function of
e/a. Also shown is the variation of the increasing number of Mn-atoms with reversed spin (shaded
symbols) in Ni8Mn4+x(Ga, In, Sn, Sb)4-x (x = 0, 1, 2, 3 and 4) which is the supercell used in the
calculations. The magnetization of the supercell has been translated to that of the standard formula
unit Ni2Mn1+xGa1-x to make it comparable with other figures. Mn is the number of Mn atoms with
reversed spin in the cubic supercell with 16 atoms. The variation in both sets of curves is linear and
all curves converge towards the antiferromagnetic binary system NiMn. This linear variation
supports the linear increase of MS with e/a (and decreasing concentration of Z).
The discussion shows that phonon softening in relation to nesting behavior, which was discussed in
many papers as the precursor of the premartensitic or martensitic phases in Ni2MnGa alloys [109116], may be absent or very weak in most MSMA from the Ni2Mn1+xZ1-x series for compositions
away from stoichiometry.
The role of magnetism on the martensitic transformation has not really been clarified from an
atomistic point of view. The linear behavior of MS(e/a) may lead to the conclusion that the magnetic
order does not play a significant role as the linear behavior seems to be unaffected by the gradual
change from ferromagnetic to antiferromagnetic order with increasing e/a (which means decreasing
(sp)-electrons from the element Z). However, the situation is more complex. Figure 16 shows the
perfectly linear variation of the total magnetic moment, which is practically the magnetic moment
of Mn, and the number of Mn with spin-down as a function of e/a.

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Advances in Magnetic Shape Memory Materials

The Slater-Pauling (SP) behavior of the saturation magnetization was noticed before for the Ni-MnGa magnetic shape-memory alloys, for example, see [117, 118]. In this case one has to distinguish
the variation of the magnetization of L21 austenite, 5M, 7M and nonmodulated tetragonal L10 with
e/a. Figure 16 shows that the magnetization of the L21 phase of each of the pseudobinary systems
exhibits a perfect linear variation with e/a which is unaffected by the crossover from ferro- to
antiferromagnetism. This is important because it is the prerequisite for the linear behavior of
MS(e/a). It also shows that the gradual change of the nature of the exchange interaction from
RKKY-like and superexchange to direct exchange interaction (from Z-rich to Z-poor alloys) does
not alter the linear variation.
The electron concentration dependence of the magnetic moments of many ferromagnetic 3d-metals
shows SP behavior, with a change in slope from positive (for the bcc alloys) to negative (for the fcc
alloys) around e/a 8.5, for instance, see Ref. [10]. In the SP diagram of Ref. [10] the pseudobinary
intermetallics Ni2Mn1+x(Ga, In, Sn, Sb)1-x with 7.5 < e/a < 8.5 follow the general linear variation
but appear with negative slopes in the region of the bcc alloys, whereas the half metallic Heusler
alloys fall into the same region but with a positive slope, see [10] and [33]. The negative slope of
the SP curves of Ni2Mn1+x(Ga, In, Sn, Sb)1-x alloys shown in Fig. 16 changes (to positive) below a
critical lower e/a value which is different for each system: This is indicated in Fig. 16 by the
solid/dashed line starting at the maximum magnetization for each alloy. For Ni-Mn-Ga the critical
value is e/a = 7.5, for e/a < 7.5 the slope will be negative. This has been found in other calculations
[117] and agrees with the experimental data collected from different sources [119]. As discussed by
Enkovaara et al. the negative slope for e/a > 7.5 can only be explained in terms of antiparallel spins
of some of the Mn-atoms [117]. This is in agreement with our ab initio results in Fig. 16 showing
the same behavior of the slopes for all Ni-Mn-Z alloys.

Fig. 17: (a) Magnetic anisotropy energy of Ni2MnGa (e/a = 7.5) as a function of the tetragonal
distortion c/a. Note that for the cubic phase (c/a = 1) the MAE vanishes. In the tetragonal structures
the [001] axis changes from easy axis to hard axis when c/a passes through one. The data were
taken from the ab initio calculations of Enkovaara et al. [120]. (b) The MAE of Ni-Mn-Ga as a
function of the number of valence electrons compared to experimental results. The calculations
were done for c/a = 0.94 and the stoichiometric composition but the MAE was evaluated for
different band fillings simulating different e/a (solid line) [120]. The experimental values: Filled
circle (Ref. [125]), filled square (Ref. [126]), filled diamond and triangle down (Ref. [127]) and
filled triangle up (Ref. [128]). The experimental values are systematically below the theoretical
ones for various reasons, see [120].
Another key feature of MSMA is the magnetic anisotropy which was determined as a function of
e/a or Mn-content [112] and as a function of c/a [25, 120, 121] in previous work. So, any of the

V.A. Chernenko

23

new compounds [122-124] addressed briefly in the following section has to fulfill the requirements
of undergoing a thermoelastic phase transformation to a modulated martensitic phase with a large
enough magnetocrystalline anisotropy to allow for easy rearrangement of the martensitic twins
under the influence of an external magnetic field. Therefore, the value of the magnetic anisotropy
has to be checked in each case where new MSMA are proposed. However, this discussion is beyond
the scope of the present paper. Here, we just report the main features of the behavior of the
magnetic anisotropy energy (MAE) of Ni-Mn-Ga since this is the system for which substantial
magnetic field-induced twin boundary motion has been observed. Note that for all other alloys of
the pseudobinary series, i.e. Z = In, Sn and Sb, little data of the MAE is available in the literature.
For Ni-Mn-Ga the experimental data were determined for the orthorhombic structure with c/a < 1
having a short axis as the easy axis (the collected data are presented in Ref. [10] together with
results of calculations which agree with the experimental trend [120]). The essential feature is that
the magnetic anisotropy energy as a function of e/a has a maximum at the stoichiometric
composition Ni2MnGa and decreases rapidly for e/a < 7.5 and > 7.5. Since Ni-Mn-Ga is the
prototype MSMA system with its outstanding 11% of magnetic field induced strain due to the high
magnetocrystalline anisotropy and high twin mobility, all other MSMA will be evaluated compared
to the performance of this alloy system. Therefore, we show in Fig. 17 the variation of the MAE as
a function of c/a and e/a. For computational details see [25, 120].
Intermetallic Heusler Compounds and New Magnetic Shape Memory Alloys
A series of magnetic Heusler compounds have recently been proposed as new potential MSMA.
Among these we find Co2NiGa for which no phonon softening has been observed neither experimentally nor theoretically [2, 105, 123, 124], Fe2Co(Ga, Zn) [84, 122, 124] and Ni2Co(Ga, Zn) [39]
with strong preference for the inverse Heusler structure (compare Fig. 8) and FeCoNiGa [40]. The
search for new MSMA has, as mentioned before, become necessary if the MSME is to be exploited
in environments of elevated temperatures. High Curie temperatures are easy to achieve as, for
example, some of the spintronics materials with Heusler structure have high TC values and may be
forced to become martensitic by appropriate compositional changes, see the discussion for the case
of Co2FeSi. A serious problem is to give a prescription of how to fix the martensitic transformation
temperature according to the demand of a device in a special application: The experimental control
of MS for a particular alloy series or the prediction of the composition dependent MS from ab initio
calculations of free energies is far from being solved and is the main obstacle regarding the
fabrication of new MSMA. Although ab initio calculations of the various contributions to the free
energy of MSMA is possible, these calculations are time-consuming and only a few systematic
attempts were made, see [116] and references therein.
Besides the new alloy series, Fe2Co(Ga, Zn), Ni2Co(Ga, Zn), FeCoNiGa [39, 40, 84, 122] and
Co2NiGa [2, 107] investigated so far, we would like to discuss briefly a strategy to find new and
perhaps better suited MSMA based on intermetallic Heusler alloys. To achieve this, we propose to
start from the hitherto used standard paramagnetic shape-memory alloys such as Al-Cu-Zn, Ni-Ti
and V-Ni-Ti and to construct new magnetic Heusler alloys by substituting one or two of the
nonmagnetic elements by magnetic or strongly paramagnetic elements. For example, instead of bcc
Ni-Ti or V-Ni-Ti one may think of Fe2Ti(Al, Ga) or instead of Al-Cu-Zn one may use as starting
point Pd2FeZn. The other possibility has been discussed above: One may start with typical materials
suited for spintronics applications which have high Curie temperatures such as the half-metal
Co2FeSi (which supports strain without loosing its large magnetic moment and high Curie
temperature) and try to induce a martensitic instability by appropriate substitution or co-alloying.
There are plenty of possibilities. The calculated E(c/a) curves of Co-Fe-Si discussed in Fig. 4 show
that one can force typical spintronics materials with half-metallic behavior to support large strain
effects with a trend to become martensitic. In this context it is interesting to note that, for example,
Co3-xFexSi/MgO multilayers adapt themselves at the interface between the Heusler alloy and MgO

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Advances in Magnetic Shape Memory Materials

with a lattice mismatch of 4% which was recently discussed [129]. High magnetostrictive materials
such as Fe-Ga alloys may be particularly interesting. Little work has been done along these lines to
find better shape-memory alloys.
Summary
In this contribution we have discussed the magnetic particularities of some of the magnetic Heusler
alloys which are of interest for magnetic shape-memory devices. Some new Heusler alloys based on
Fe, Co and Ni have also been discussed. The understanding of the changes of the magnetic
properties of the alloys with changes of their composition is needed in order to develop strategies
for designing new and better MSMA. One also has to understand in a better way the occurrence of
inverse structures in contrast to the regular structures. According to Gilleen et al. we should find
stable cubic (inverse) structures for e/a < 7.25 and stable tetragonal (inverse or regular) structures
for e/a > 7.25 [38]. The first-principles calculations which we have performed show that it is in
many cases difficult to design new ferromagnetic Heusler alloys such as Fe2Co(Ga, Zn) for which
the inverse structure undergoes a martensitic phase transformation. Another important issue is how
far one can predict on an ab initio basis the martensitic transformation temperature. The Curie
temperature can be calculated rather accurately by performing Monte Carlo simulations using the
magnetic exchange parameters determined from first-principles calculations. Unfortunately, there is
no corresponding simple tool to calculate the martensitic transformation temperature, apart from the
crude estimate which one may obtain by discussing energy differences between austenite and
martensite phases from total energy calculations.
We have also highlighted the nature of the martensitic transformation in the pseudobinary alloy
system Ni2Mn1+xZ1-x (Z = Ga, In, Sn, Sb) and have noted that the influence of strong electronphonon interaction may play a decisive role. Although it has been recognized that the electronphonon interaction is important for martensitic phase transformations (for example, see [130-133])
and can explain the precursor effects observed in Ni2MnGa [107, 114], detailed work on how the
displacement fields may impart energy to electrons near the Fermi level [132], which finally may
induce the structural transformation, is still not at hand. Furthermore, similar work as the recent
direct observation of phase-transformation dynamics in iron [1349/] would be highly welcome for
the shape-memory alloys.
Acknowlegements
Discussions with Manfred Wuttig, Mehmet Acet and Sebastian Fhler are greatfully acknowledged.
This work was supported by the SPP 1239 of the DFG.
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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.31

Magnetic Anisotropy of Ferromagnetic Martensites


Victor Lvov1,2,a and Volodymyr Chernenko3,4,b
1

Taras Shevchenko University, Department of Radiophysics, Kyiv 03127, Ukraine


2

Institute of Magnetism, Vernadsky str. 36-b, Kyiv 03142, Ukraine

Universidad del Pas Vasco, Dpto. Electricidad y Electronica, P.O. Box 644, Bilbao
48080, Spain
4

IKERBASQUE, Basque Foundation for Science, Bilbao 48011, Spain


avictor.a.lvov@gmail.com, bvladimir.chernenko@gmail.com

Key words: magnetic anisotropy, Ni-Mn-Ga ferromagnetic martensite, magnetostress, magneticfield-induced strain, MFIS, multiscale twinning, magnetoelastic model

Abstract. The analytic survey of experimental and theoretical studies of the magnetic anisotropy of
ferromagnetic shape memory alloys (FSMAs) is presented. The interdependence between the
magnetic anisotropy of FSMAs, their lattice parameters, microstructure, and magnetostrain
properties is considered. The temperature dependencies of the magnetocrystalline anisotropy energy
density (MAED) and magnetically induced mechanical stress are described in the framework of
magnetoelastic model based on Landau theory of phase transitions. The magnetic anisotropy of thin
martensitic platelets/films and wires is considered. The effect of compensation of
magnetocrystalline anisotropy by the magnetostatic one is studied. The reduction of MAED as a
result of internal twinning of single crystal is discussed. The possibility of observation of reversible
magnetic-field-induced strain in the twinned FSMAs with reduced MAED is demonstrated.
1. Introduction
The ferromagnetic shape memory alloys (FSMAs) are a subject of intensive studies nowadays and
the topicality of these studies is commonly recognized (see, e. g., Refs. [1,2]). The martensitic
transformation (MT) of FSMA is accompanied by the lowering of the crystal lattice symmetry and
the appearance of the uniaxial or biaxial magnetocrystalline anisotropy, which is absent in a cubic
phase by the symmetry reasons. The coordinated experimental and theoretical studies are carried out
for the experimental determination and/or theoretical evaluation of magnetocrystalline anisotropy
constants of FSMAs (see review articles Refs. [3, 4] and references therein). The motivating factor
of these studies is the interrelation of magnetocrystalline anisotropy with the practically important
characteristics of FSMAs, such as giant magnetic-field-induced strain (MFIS) and related
phenomena. Consistent consideration of this interrelation and the relevant underlying physics is the
logic line of the present analytic review article. With such a particular scope, the article mainly deals
with the publications, which concern the magnetic anisotropy of NiMnGa alloys.
2. Characteristics of martensites interrelated with magnetocrystalline anisotropy
2. 1. Magnetic-field-induced strain. The giant magnetic-field-induced strain (MFIS) was found in
the NiMnGa alloys [58] and later observed in some other shape memory materials, as FePd and
Fe3Pt [3]. The MFIS is caused by the rearrangement of the differently oriented twin variants of
martensitic phase (martensite reorientation) under the applied magnetic field [58]. The martensite
reorientation happens because the magnetic field application results in the internal mechanical
stressing of ferromagnetic FSMA [6, 9, 10], which is equivalent to the stressing under the axial
mechanical load. The value of magnetically induced stress (magnetostress) has been estimated from
the experimental stressstrain loops; for the saturating value of magnetic field it was roughly equal

32

Advances in Magnetic Shape Memory Materials

to 3 MPa in the case of 5M martensite [11, 12] and 1.7 MPa in the case of 7M one [13]. These
stresses are enough to induce the giant MFIS of about 6% and 10% in the 5M and 7M martensites,
respectively [7, 8, 13].
The phenomenological models elaborated in Refs. [10, 14] establishes a direct proportionality
between the magnetically induced stress (magnetostress) and the uniaxial magnetocrystalline
anisotropy constant K u whereby these models assert that the giant MFIS can be observed in the
FSMAs with the strong magnetocrystalline anisotropy only.
According to magnetoelastic model developed in Refs. [9, 1517] the giant MFIS is "triggered"
by magnetoelastic interaction, and so, the magnetostress is directly proportional to magnetoelastic
energy constant, which is involved in the Gibbs potential of the alloy. In the case when the K u
constant is directly proportional to the spontaneous deformation of crystal lattice arising in the
course of MT (referred below as MT strain or M ), the magnetoelastic model nominally conforms
the phenomenological models mentioned above (see [12]), while giving rise to the essential physical
implications. In the case of nonlinear function K u ( M ) , the further substantial difference between
the phenomenological and magnetoelastic models arises, and moreover, the magnetoelastic model
enables the observation of giant MFIS in the alloys with moderate (or even low) magnetocrystalline
anisotropy (see Section 5 of this article).
2. 2. Lattice parameters. The magnetic anisotropy energy of the tetragonal, rhombohedral and
hexagonal crystal lattices is expressed in the form
F (i ) = K1mi2 K 2 mi4 + .... ,

(1)

where the subscript i denotes the projection of the unit magnetic vector m = M ( H , T ) / M ( H , T ) on
the principal crystallographic axis, M ( H , T ) is a magnetization vector, H is an external magnetic
field, T is the temperature of alloy. A simplified expression
F ( i ) = K u mi2 ,

(2)

is often used for the interpretation of experimental data. The constant of uniaxial magnetocrystalline
anisotropy K u is expressed through the first-order and second-order anisotropy constants as
K u = K1 + 2K 2 ,

(3)

and can be evaluated from the experimental magnetization curves M (H ) .


It is of importance that the density-functional theory predicts the linear interdependence between
the lattice distortion and magnetocrystalline anisotropy energy density (MAED) of the NiMnGa
alloys [18], in a similar way as the magnetoelastic model linearly relates the anisotropy constant K u
to the axial distortion 1 c(T ) / a (T ) of the non-modulated crystal lattice [17]. (Here a and c are
the lattice parameters, c = ce i , ort e i is aligned with the principal crystallographic axis). As long as
the MAED is characterized by the Equation (3), the result of density functional theory agrees with
the magnetoelastic model of ferromagnetic martensite.
2.3. Martensite structure. The martensitic phases of shape memory alloys exhibit a hierarchical
twinning in the micro-, meso- and/or nanoscales.
The microtwinned tetragonal, rhombohedral or hexagonal lattice of ferromagnetic martensite
consists of the alternating crystallographic domains (twin components) possessing the uniaxial
magnetocrystalline anisotropy. In the case when K u > 0 , the magnetic vector of every twin
component is aligned with its own principal axis.

V.A. Chernenko

33

In the case of mesoscale twinning, the magnetic vectors of twin components can follow the
alternating directions of the principal axes of twin components only if the twin width exceeds the
width of magnetic domain wall. In the opposite case the twinned crystal will possess a more
complicate magnetic structure, which is not properly studied yet.
The nano-twinning is produced by a periodic shifting of atomic layers forming stacking
sequence which also can be considered as periodic modulation of the crystal lattice. The fivelayered tetragonal (5M) and seven-layered orthorhombic (7M) modulated phases are inherent to the
ferromagnetic NiMnGa martensites alongside the non-modulated tetragonal phase. It is not clear
so far to what extent the directions of magnetic vectors can follow the displacements directions of
atomic layers.
A twinning reduces the symmetry of crystal lattice. In the case when the magnetic vectors of twin
components cannot follow the quick reorientation of the principal axes of the unit cells in the
nanoscale and fine mesoscale twins, the twinning affects the magnetocrystalline anisotropy of the
crystal [15]. A simple theoretical consideration of the twin structure formed by the alternating
variants of tetragonal lattice showed that the magnetic anisotropy energy of modulated martensitic
phases should be expressed in the form

F (ij ) = A1mi2 + A2 m 2j ,

(4)

where the subscripts i, j = x, y, z mark the directions of the four-fold symmetry axes in the
alternating variants of the tetragonal lattice [15]. The Eq. (4) corresponds to the symmetry groups
belonging to orthorhombic crystallographic system. The symmetry reduction caused by the periodic
modulation/twinning of tetragonal lattice in nano- or mesoscale was ignored in the Refs. [58, 10,
13, 14, 1724] and the equation (2) was used for the interpretation of experimental data obtained for
the 5M martensite.
Table 1.

Ref.

Ku (kJm-3)

T(K)

1 c/a

Specimen

[5,6]
[19]

117
80

265
Room

0.062
0.025

[20]
[21]
[7,22]
[8]

245
300
170
180
150
186
248
213
11
140

256
170
290
Room

No data
0.078
0.059
No data

No data

No data

Single crystal (SC)


Polycrystal (PC),
Ni55Mn20Ga25
SC disk, Ni51.3Mn24.0Ga24.7
SC with Tm = 190 K
SC, Ni48Mn31Ga21
SC, Ni49.8Mn28.5Ga21.7
SC, Ni48.1Mn29.4Ga22.5
SC, Ni49.6Mn28.4Ga22
SC, Ni49.7Mn28.7Ga21.6
SC, Ni48.2Mn30.8Ga21

No data

0.15

[23]

[24]

Mode of
determination

Maximal
magnetostrain
observed (%)

From M(H)
From M(H)

0.15
No data

From M(H)
From M(H)
From M(H)
From (H)

4.3
No data
5.1
6
0.3
5
5.3
7.3
No data
No data

From FMR

100 m thick ribbon

SC, Ni54Mn23Ga23

From M(H)

The determined from experiments values of magnetocrystalline anisotropy constant are shown in
the Table 1. These constants were determined from the measurements of magnetization,
ferromagnetic resonance (FMR) frequencies or magnetically induced deformation.
The temperature dependencies of the magnetic anisotropy constants of the 5M martensites have
been studied in Refs. [4, 2529]. The main physical factors contributing to these dependencies have
been analyzed in the framework of magnetoelastic model [30].

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Advances in Magnetic Shape Memory Materials

In distinct to 5M martensite, the unit cell of 7M phase has the orthorhombic symmetry with the
lattice parameters: a = 0.619 nm, b = 0.580 nm, c = 0.553 nm [31]. The anisotropy constants of
7M martensite, K a 170 kJ/m 3 and K b 90 kJ/m 3 , were determined by the measurements of
magnetization of the single-crystalline specimen along a and b axes, which are perpendicular to
the easy magnetization axis c [32, 33]. The temperature dependencies of these magnetic anisotropy
constants of 7M martensite have been studied in Refs. [33, 34]. In view of the obvious symmetry
reasons, the observed biaxial character of magnetic anisotropy of 7M martensite is caused by the
combination of two factors, such as: i) the orthorhombic shape of the unit cell, and ii) the periodic
modulation/nanotwinning of a crystal lattice. To our best knowledge, the contributions of these
factors to the biaxial magnetocrystalline anisotropy have not been separated and evaluated yet from
the available experimental data.
To demonstrate the role of twinning in the formation of magnetocrystalline anisotropy of FSMA,
the experimental magnetization curves of the internally twinned and single-variant states of nonmodulated NiMnGa martensite with c / a > 1 have been compared in Ref.[35]. The quasi-single
variant state was prepared by tension of the single crystalline specimen along c axis and the
twinned one was induced by compression in a perpendicular direction. The linear magnetization
curve appeared to be inherent to the quasi-single variant state, while the twinning caused the
nonlinearity of this curve [35].
The Table 1 shows, that the experimental data do not demonstrate the direct proportionality
between the values of parameters K u and 1 c / a . This fact may be caused, in particular, by:
i) the difference in magnetization values arising from the difference in the alloy compositions
and/or test temperatures;
ii) ignoring or improper treating the magnetostatic energy during an examination of the
experimental data;
iii) the nonlinear interrelation between K u and 1 c / a parameters, which may be peculiar to
some of the experimentally studied alloys;
iv) the periodic modulation or/and mesoscale twinning of crystal lattice.
We consider these factors to be crucial in the course of determination of MAED value as follows
from the next Section.

3. Temperature dependence of MAED and its interrelation with magnetostress


In this section, the temperature dependence of the equilibrium value of MAED of ferromagnetic
single crystals undergoing the cubic-tetragonal MT will be modelled using the Landau expansion for
the free energy. This expansion is the sum of magnetic, elastic, and magnetoelastic energies:

F = Fm + Fe + Fme

(5)

where

Fm = K1( c ) (mx2 m y2 + mx2 mz2 + m y2 mz2 ) + K 2( c ) mx2 m y2 mz2


+

1 2
M (T )(m D m) mHM (T ),
2

(6)

is the sum of magnetocrystalline, magnetostatic and Zeeman energies of the crystal,


Fme = M 2 (T )[ 3u2 (mx2 m 2y ) + (2mz2 m 2y mx2 )u3 ]

(7)

V.A. Chernenko

35

is the energy of anisotropic magnetoelastic interactions. Fe is the elastic energy dependent on the
linear strain tensor components
u2 = 3 ( xx yy ), u3 = 2 zz yy xx

(8)

and elastic constants. The parameters K1( c ) and K 2( c ) are the magnetocrystalline anisotropy
constants, M is the magnetization value, D is the matrix formed by the demagnetization coefficients,
H is the external magnetic field, is the dimensionless magnetoelastic constant.
According to the basic principle of Landau theory, the Eqs. (6) and (7) are obtained by the
construction of the invariant (with respect to the symmetry group of cubic phase) combinations of
magnetic vector and strain tensor components. The constants K1( c ) and K 2( c ) describe the MAED of
cubic phase. The cubic-tetragonal MT is accompanied by the spontaneous deformation of cubic
lattice in 100 crystallographic directions. For z-variant of tetragonal phase, this deformation is
approximately described by the strains

zz M = (c a) / a0 = (2 / 3)(1 c / a),
yy = xx = (1/ 3)(1 c / a),

(9)

where a0 and a, c are the values of lattice parameters in the cubic and tetragonal phases,
respectively. The spontaneous deformation of the crystal lattice is accompanied by the appearance
of the uniaxial MAED
Fu = K u (T )mz2 ,

(10)

where
K u (T ) = 6M 2 (T )[1 c(T ) / a (T )] .

(11)

The Equation (11) for the magnetocrystalline anisotropy constant immediately follows from the
Eqs. (710) and the obvious relationship between the components of unit magnetic vector
m x2 + m y2 = 1 m z2 .
The constant of magnetoelastic coupling in the NiMnGa FSMAs is negative. All presented
below theoretical evaluations and dependencies have been obtained using the value 23 which
is typical for the tetragonal phase with c / a < 1 [17]. Thus, the inequality K u > 0 is true and the
energy Eq. (10) is minimal when the magnetic vector is aligned with the principal axis c||z of the
tetragonal unit cell. So, the equilibrium value of MAED is equal to K u (T ) .
According to Eq. (11), the temperature dependencies of the lattice parameters and magnetization
are the main factors, which contribute to the temperature dependence of the equilibrium value of
MAED. This equation enables a separation of contributions of these factors. The stoichiometric
Ni2MnGa alloy may be considered as the illustrative and well-studied example of FSMA. The
experimental temperature dependencies of lattice parameters and magnetization of this alloy are
reported in Refs. [36] and [37], respectively. A substitution of experimental values into the Eq. (11)
results in the theoretical temperature dependence K u (T ) depicted in Fig. 1.
The semi-empiric dependencies in Fig. 1 lead to the following conclusions.
A) The MAED of tetragonal phase can be described in the uniaxial approximation because the
uniaxial anisotropy constant K u substantially exceeds the anisotropy constants K1( c ) 2.7 kJ/m 3
and K 2( c ) 6.1 kJ/m 3 [20].

36

Advances in Magnetic Shape Memory Materials

B) The MAED of FSMA drastically depends on the temperature.

Fig. 1. Theoretical temperature dependence of the equilibrium MAED of cubic-shaped Ni2MnGa


single crystal (circles and solid line). The dependence was obtained using the experimental
temperature dependencies of lattice parameters [36] and magnetization. The circles mark the values
computed with the use of experimental values of magnetization [37], the solid line is fitted to the
circles by the spline tool. The dashed line illustrates the contribution of the temperature-dependent
lattice parameters to the total temperature dependence of MAED; the dot-dashed line shows the
contribution of the temperature-dependent magnetization value.
The temperature dependence of MAED of the alloy with MT temperature TM 200 K is caused
mainly by the temperature variation of lattice parameters, because the Curie temperature of this
alloy ( TC 380 K ) exceeds considerably TM. In this case the magnetization value is roughly
constant when T < TM , and so, its contribution to the temperature dependence of MAED is small.
The temperature dependence of MAED of the NiMnGa alloy with MT temperature of about
300 K is almost equally contributed by two factors mentioned above [30]. It should be expected that
the temperature variation of magnetization controls the temperature dependence of MAED if the
MT temperature is close to the Curie temperature of the alloy.
Noteworthy, the experimental values K1 = 200 5 kJ/m 3 and K 2 = 50 5 kJ/m 3 were measured
at T = 170 K for the alloy with MT temperature of 190 K [21]. These values result in the estimation
K u = 300 kJ/m 3 (see Eq. (3) and Table 1). The same estimation was obtained from the
computations performed above for the stoichiometric alloy with MT temperature of 200 K (see long
dashed arrows in Fig. 1). The majority of experimental K u values presented in the Table 1 are much
smaller, but they were measured at the temperatures much higher than 200 K for the
nonstoichiometric alloys with elevated MT temperatures.
The Gibbs potential of the alloy that is stressed with the stress zz is expressed as

G = F zz zz .

(12)

The energy of magnetoelastic coupling Eq. (7) involves the term zz( me ) ( H , T ) zz , where the function

zz( me) ( H , T ) is defined as

zz( me ) ( H , T ) 2M 2 (T )[2mz2 ( H ) m y2 ( H ) mx2 ( H )] .

(13)

This function may be interpreted as the mechanical stress arising in the course of magnetic ordering
of FSMA.

V.A. Chernenko

37

In zero magnetic field mz = 1, m y = mx = 0 , the magnetoelastic stress Eq. (13) is negative (since

< 0 ) and hence, the magnetic ordering characterized by magnetic vector m || z stabilizes the zvariant of martensitic phase. The magnetic ordering of the bulk single crystal of the alloy with
TC < TM results in the appearance of the austenite with coexisting magnetic domains with m || z ,
m || y and m || x in the temperature range TM < T < TC . The cooling to the temperatures T < TM
leads to the formation of ferromagnetic martensite; the stress of Eq. (13) promotes the formation of
i-variant of martensite in the domain with m || i ( i = x, y, z ) and hinders the formation of
martensitic phase in two other domains.
Let the saturating magnetic field be applied to z-variant of martensite in [010] direction. In this
field the state with mz = mx = 0 , m y = 1 is stable. Therefore, the magnetic field induces the
temperature-dependent magnetostress

zz (T ) zz( me ) ( H S , T ) zz( me ) (0, T ) = 6M 2 (T ) ,

(14)

The magnetostress is positive, and so, the magnetic field H x destabilizes z-variant of martensite
and stabilizes x-variant. The Equations (11) and (14) result in the relationship

zz (T ) =

K u (T )
,
1 c(T ) / a (T )

(15)

which is commonly used for the evaluation of magnetostress. It should be noticed that the
magnetostress concept is introduced here in a simplified manner, which is admissible only for the
symmetric directions of saturating magnetic field. A consistent consideration of magnetostress in
the framework of magnetoelastic model is presented in Refs. [12] and [38]. This consideration leads
to the conclusion, that the affect of the external magnetic field H on the twin structure formed by
the neighboring martensite variants with c || [001] || z and c || [010] || y is equivalent to the
mechanical stressing of the twinned alloy with the stress

1
2

eq (H, T ) = [ [ 001] (H, T ) + [ 010 ] (H, T )] ,

(16)

where [ 001] (H, T ) and [ 010 ] (H, T ) are the magnetostress values in the neighboring martensite
variants (twin components) [38]. These values depends on the magnetic field vector and
temperature as

[ 001] (H) = 6M 2 (T ){cos[2 [ 001] (H)] cos[2 (0)[ 001] ]},

[ 010 ] (H ) = 6M 2 (T ){cos[2 [ 010 ] (H)] cos[2 (0)[ 010 ] ]},

(17)

where [ 001] (H ) and [ 010] (H ) are the angles between the [001] direction and the unit magnetic
vectors of the martensite variants with c || [001] and c || [010] , respectively. The equation for
determination of the angles is

sin 2

2H
sin( ) = 0 ,
H A (T )

(18)

where the sign "+" applies to the y-variant and the sign "" to the z-variant, is the angle between
the magnetic vector and z-axis, H A (T ) = 2 K u (T ) / M (T ) is the magnetic anisotropy field [38].

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The experimental temperature dependence of the saturation magnetization of NiMnGa alloys


with c / a < 1 are satisfactorily described by the standard equation
T M (T )
M (T ) = M (0) tanh C

TM (0)
with

M ( 0 ) = 0 .7 T

and

two

(19)

different

values

of

Curie

temperature

TC = TCA

and

TC = TCM = TCA + 30 K relevant to austenitic and martensitic phases, respectively [39]. The
temperature dependence of the equivalent stress, which is induced by the saturating magnetic field
H = H A applied in [001] direction, is shown in Fig. 2.

Fig. 2: Theoretical temperature dependence of the equivalent stress that is induced by the saturating
magnetic field applied in [001] direction.

Fig. 3. The angular dependencies of the equivalent stress computed for the different values of
external magnetic field (T = 295 K).
The computed equivalent stress is a decreasing function of the temperature, which is not equal to
zero in both austenitic and martensitic phases. In the austenitic phase the equivalent stress causes
only the ordinary magnetostriction. In the martensitic phase this stress causes the magnetostriction,
which is different for different martensite variants, and therefore, breaks the equivalence of the
variants and stipulates the possibility of martensite reorientation as the elastic strain caused by the
mechanical loading does. According to Fig. 2, the equivalent stress function takes on a value about
of 2 MPa at room temperature. This value is sufficient for the triggering of martensite reorientation

V.A. Chernenko

39

in the NiMnGa single crystals with low values of the shear elastic modulus, C ' 10 GPa and
yield stress, y ~ 1 MPa [40]. For the majority of NiMnGa specimens, the shear modulus and
related yield stress satisfy this condition only in the certain temperature interval around MT
temperature, and therefore, the maximal values of MFIS | zz | 1 c / a are attainable only in the
vicinity of MT temperature range, as a matter of fact [41].
The equations (16)(19) enable the determination of the angular dependence of the equivalent
stress. The dependencies computed for the room temperature (295 K) and different values of
magnetic field are presented in Fig. 3. These dependencies show that the stronger is the magnetic
field, the wider is the angular range for observation of giant MFIS. Let the threshold stress value,
which starts the transformation of y-variant into z-variant ( y z martensite reorientation) is equal
to 2 MPa. In this case the MFIS can be observed if the deviation of the magnetic field vector from
z-axis is less then 2.50, 120 or 160 for the magnetic field values equal to H A , 2 H A or 4 H A ,
respectively. More details concerning the MFIS observation in the inclined magnetic field are
presented in Ref. [38].
It may be concluded now that
i) the temperature dependencies of lattice parameters and magnetization are the main factors
which control the temperature dependence of MAED;
ii) a direct proportionality between the magnetocrystalline anisotropy constant and magnetostress
value takes place only if the magnetic field vector is oriented in one of 100 crystallographic
directions.
The other possibility of the nonlinear interdependence between the magnetocrystalline anisotropy
constant and magnetostress will be considered in Section 5.

4. Influence of demagnetizing field on the magnetic anisotropy and magnetically induced


deformation of FSMA
4.1. Introductory remark. It is known that the total magnetic anisotropy energy density of
ferromagnetic crystal consists of the MAED and the energy density caused by the shape anisotropy
(SA) of the specimen. The latter is related to the internal magnetostatic (demagnetizing) field, which
is induced by the ordered magnetic moments of atoms. According to Eqs. (6) and (10), the total
magnetic energy density of the single crystal with tetragonal, rhombohedral or hexagonal lattice is
approximately expressed as
Fm = K u (T )mi2 +

1 2
M (T )(m D m) mHM (T ) ,
2

(20)

where i-axis is directed along the principal crystallographic axis.


It is of the profound academic and practical interest, when the magnetocrystalline anisotropy and
the shape anisotropy compensate each other. The compensation effect is conditioned by the strong
temperature dependence of lattice parameters, and therefore, is peculiar to FSMAs [17]. The effect
is the most pronounced in the thin platelets/films and wires/needles, because for these objects, the
value of magnetostatic field is close to the upper theoretical limit.
4.2. Magnetic anisotropy of thin martensitic platelet/film and a spontaneous reversibility of
MFIS. Let the normal to the platelet/film surface be oriented in [001] crystallographic direction
aligned with z-axis. It is of common knowledge that the elements of demagnetization matrix of the
thin magnetic platelet/film with the faces perpendicular to z-axis are Dzz 4 , Dyy = Dxx = 0 . In
this case the energy Eq. (20) is expressed as
Fm(i ) = K (i ) (T )mi2 mHM (T ) ,

(21)

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Advances in Magnetic Shape Memory Materials

where the temperature-dependent parameters

K ( x ) (T ) = K ( y ) (T ) K u (T ) + K ms (T ) > 0,
K ( z ) (T ) K u (T ) K ms (T )

(22)

are conventionally referred to as the "magnetic anisotropy constants" of the x-, y-, and z-variants of
martensite formed in the film. The value K ms (T ) 2M 2 (T ) characterizes the shape anisotropy of
the film and may be referred to as the SA constant. The SA constant is related to the internal
magnetostatic field H ms (T ) = 2 K ms (T ) / M (T ) as the magnetocrystalline anisotropy constant K u (T )
is related to the magnetic anisotropy field H A (T ) that was introduced above.
For the NiMnGa alloys with c / a < 1 the inequalities K ( x , y ) (T ) > 0 are true, the SA reinforces
the magnetocrystalline anisotropy, and therefore, the equilibrium directions of magnetic vectors of
x- and y-variants lies in the film plane. For the z-variant of martensitic phase the compensation
effect arises: the equilibrium direction of magnetic vector is normal to the platelet/film plane if
K u (T ) > K ms (T ) and lies in this plane otherwise.
It may be expected that the martensitic state of the platelet cut of the FSMA sample with
K u (T ) < K ms (T ) will be formed mainly by the x-and y-variants of martensitic phase, but the small
fraction of z-variant will also be present. In zero external field the magnetic vectors of all variants
lie in the film plane, because the inequality H ms > H A is fulfilled. The increasing magnetic field
applied in z-direction will compress the platelet in this direction and initiate the x z and y z
martensite reorientation (forward reorientation cycle), which will be finished in the saturation field
H H A + H ms . In this field the magnetic vectors of all martensite variants will be oriented normally
to the film plane. A decrease of the field to zero value will be accompanied by the reorientation of
the magnetic vectors to the plane of the platelet and by the z x and z y martensite
reorientation (reverse reorientation cycle).
It may be concluded, that the reversible MFIS of about of r ~ 1 c / a may be observed in the
NiMnGa platelets/films with reduced magnetocrystalline anisotropy constant. Hereafte, it will be
argued that the sufficient reduction of magnetocrystalline constant may be caused by i) the reduced
magnitude of the spontaneous lattice distortion (the value 1 c / a 4% is sufficiently low); ii) the
nonlinear interrelation between the magnetocrystalline anisotropy constant and spontaneous lattice
distortion; and iii) the mesoscale twinning of crystal lattice.
4.3. Magnetic anisotropy of thin martensitic wire and MFIS reversibility. Let the
wire/needle be oriented in z-direction. In this case the elements of demagnetization matrix are
Dzz 0 and D yy = Dxx = 2 , so the magnetic anisotropy constants involved in Eq. (21) are

K ( x ) (T ) = K ( y ) (T ) = K u (T ) K ms (T ) / 2,
K ( z ) (T ) = K u (T ) + K ms (T ) / 2 > 0.

(23)

The magnetostatic field destabilizes x- and y-martensite variant and stabilizes z-variant. Let the
inequality K u (T ) < K ms (T ) / 2 be true for the considered FSMA sample. In this case the reversible
MFIS may be observed. It may be expected that the martensitic state of the wire/needle will consist
mainly of the z-variant of martensitic phase, but the small volume fractions of x- and y-variants will
be also present. In the absence of external field the magnetic vectors of all variants will be aligned
with the axis of the wire/needle, because the inequality H ms / 2 > H A is fulfilled. The magnetic field
application in x-direction will compress the platelet in this direction and initiate the z x and
z y martensite reorientation (forward reorientation cycle), which will be finished in the
saturation field H H A + H ms / 2 . The saturation field will direct the magnetic vectors of all

V.A. Chernenko

41

martensite variants normally to the wire. The lowering of the field to zero value will be
accompanied by the rotations of the magnetic vectors to the axis of the wire whereby favoring the
reverse martensite reorientation. It means that the reversible MFIS r ~ 1 c / a may turn out to be
observable.
4.4. Illustrative examples. The considered above Ni2MnGa and studied in Ref. [30]
Ni1.99Mn1.14Ga0.87 alloys are suitable to illustrate the possibilities of complete and partial
compensation of magnetic anisotropy of "unfavorable" (destabilised by SA) martensite variant.
The Figure 4 depicts the temperature dependencies of the magnetic anisotropy constants of zvariants of martensite in the thin Ni2MnGa and Ni1.99Mn1.14Ga0.87 platelets/films. These
dependencies were computed from the Eqs. (19) and (22) using the values that are specified in
Fig. 2.

Fig. 4. Theoretical temperature dependencies of the "magnetic anisotropy constants", (a), and
magnetic saturation fields, (b), computed for the z-variants of Ni2MnGa (solid lines) and
Ni1.99Mn1.14Ga0.87 (dashed lines) martensites in the thin platelets/films. The circles and squares
depict the values obtained by using the experimental values of magnetization and lattice parameters
[30, 36, 37].
The Figure 4 shows that the complete compensation of the magnetocrystalline anisotropy of zvariant takes place when the temperature of Ni2MnGa thin film reaches the value of about of 100 K.
The reorientation of the magnetic moments of atoms from the film plane to the film normal is
expected at this temperature. The presented in Fig. 4 (b) field H SZ | H A H ms | corresponds to the
finish of the from-plane-to-normal (when T > 100 K ) and from-normal-to-plane (when T < 100 K )
reorientation of the magnetic vector of z-variant under the applied magnetic field.
The computations show that only the partial compensation of magnetocrystalline anisotropy by
the shape anisotropy is attainable in z-variant of Ni1.99Mn1.14Ga0.87 martensite. However, a drastic
reduction of the critical field H SZ to the value of 150 kA/m 2 kOe should be observed on
approach of MT temperature. This value may be measured by the deflection of magnetization curve.
It may be concluded, that the reduction of magnetocrystalline anisotropy of martensite without
lowering magnetostress value is a practically important task. In the case of linear relationship
between the magnetocrystalline anisotropy constant and magnetostress (see Eq. (15)) this task can
be performed only by the expense of diminution of MT strain. However, the fundamental principles
of the theory of phase transitions allow the nonlinear coupling between the magnetic vector and
strain tensor components and disclose the additional possibility of fulfilling this task.
5. MAED of the martensite with nonlinear magneto-strain coupling
The symmetry conforming theory of phase transitions starts from the expression for the
thermodynamic potential of high-symmetry phase. As already mentioned above, this expression

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Advances in Magnetic Shape Memory Materials

must be invariant with respect to the symmetry group of the high-symmetry state of the system,
which undergoes the phase transition. In accordance with this basic requirement, the Equation (7)
for the magnetoelastic energy is invariant with respect to the symmetry group of cubic crystal. Note
that the nonlinear terms
u3[u3 (2mz2 my2 mx2 ) + 3 3u2 (mx2 m y2 )]
= 36( xx yy mz2 + xx zz m 2y + yy zz mx2 ),

(24)

are also invariant with respect to this group. Strictly speaking, these terms must be included in the
expression for magnetoelastic energy as well. As so, the linear in strains Equation (7) must be
replaced by the nonlinear one
Fme = M 2 ( + ' u3 )[ 3u2 (mx2 m y2 ) + u3 (2mz2 my2 mx2 )] .

(25)

The dimensionless parameter ' can be referred to as the second-order magnetoelastic constant
(SOMEC). According to the Eqs. (8) and (9), the magnetoelastic energy term of tetragonal
martensitic phase, Eq.(25), can be presented in the form of uniaxial MAED, Eq. (10), with the
magnetocrystalline anisotropy constant
K u = 6 M 2 [ 2 ' (1 c / a )](1 c / a ) .

(26)

It should be expected that the constants and ' are of the same sign, because the tendency to
saturation of the MAED dependence on the lattice distortion must take place in the limiting case of
large distortions. As can be seen, a SOMEC-related energy reduces the MAED of the alloys with
c / a < 1 . For these alloys 2(1 c / a ) 0.1 and the drastic reduction of MAED will be observed
under the condition

' 10 ,

(27)

which may be true for some of FSMAs. In contrast to this, an ordinary magnetostriction of NiMn
Ga alloys does not exceed the value of 104. By substituting the magnetoelastic strain u3( me ) into the
Eq. (25) one can see that the SOMEC-related energy could be comparable with the linear terms only
under a very strong condition: | ' / |> 103 . It means that when 1 <| ' / |< 103 holds, the FSMAs
are characterized by the "normal" magnetostress values (see Eqs. (13), (14) and Figs. 2, 3) but
reduced values of magnetocrystalline anisotropy constant. In this case the Eq. (15) must be replaced
by the inequality

zz (T ) >

K u (T )
.
1 c(T ) / a (T )

(28)

Presented here theoretical considerations point to the possibility of giant MFIS in the alloys with
reduced magnetic anisotropy. It is important to recall that the reduction of MAED value promotes
the reversibility of MFIS (see Sections 4.2 and 4.3). The magnetically induced reorientation of Ni
MnGa martensite with reduced MAED ( K u 50 kJ/m 3 ) was observed recently in the course of
experiments with the rotating disk-shaped single crystal [38].

6. MAED of the fine-twinned martensite


Ttwin structures formed by two alternating variants of low-temperature phase are typical for the Ni
MnGa alloys. The alloys with c / a < 1 posses the magnetic anisotropy of the "easy-axis" type and

V.A. Chernenko

43

it may be expected that the magnetic vectors of the neighboring variants are perpendicular to each
other and the twin boundary is, in the same time, a 90-degree magnetic domain wall (DW). The
magnetic DW has a finite width, which is controlled by the competition of the anisotropic
interactions of magnetic moments of atoms with the spin exchange interaction. The DW width is
roughly estimated as l0 ~ a0 H E / H A , where a0 is the lattice parameter, H A 103 kA/m is the
magnetocrystalline anisotropy field and H E 105 kA/m is the molecular field that characterizes the
intensity of spin exchange process [16]. The estimation leads to the inequality
l0 > 10a0 .

(29)

The obtained inequality shows that the magnetic moments of atoms cannot strictly follow the
periodic change of the orientation of unit cells in the five- or seven-layered martensite. Moreover,
the deviations of magnetic moments from the c-axes must be noticeable even in the mesoscale twin
structure. These deviations must reduce the magnetocrystalline anisotropy field and the
magnetocrystalline anisotropy constant determined from magnetization curves or FMR frequencies.
A simplest model describing the magnetic anisotropy of twinned NiMnGa single crystals was
proposed long time ago [15] but only little experimental work was performed so far (see Ref. [35]
and references therein). So, the consistent experimental and theoretical studies of the interrelation
between the fine twinning and magnetic anisotropy of NiMnGa alloys have not been carried out
yet. Hence, only the simplest considerations concerning this subject can be presented hereafter.
The maximum possible affect of fine twinning on the magnetic anisotropy of the ferromagnetic
single crystal can be illustrated under the assumption that the crystal can be described by the
magnetic anisotropy constants, which are related to the average distortion of the twinned tetragonal
lattice [15]. The twin structure formed by the z- and y-variants of tetragonal lattice is characterized
by the average strains

ii( zy ) = ii( z ) + (1 ) ii( y ) ,

(30)

where

zz( z ) = M , yy( z ) = xx( z ) = M / 2 ,

(31)

and

zz( y ) = xx( y ) = M / 2 , yy( y ) = M

(32)

are the MT strains for the z- and y-variants, respectively (see Eq. (9)), ( z ) is the volume
fraction of z-variant of tetragonal lattice in twinned crystal. Using the Equations (8) and (30) (32),
one can find the following expressions for the average strain tensor components and their linear
combinations:

zz( yz ) = (3 1) M / 2 , yy( yz ) = (2 3 ) M / 2 , xx( yz ) = M / 2,


u2( yz ) = 3 3 ( 1) M / 2 , u3( yz ) = 3(3 1) M / 2 .

(33)

A substitution of the averaged linear combinations into the Eq. (7) gives:

Fme FA( zy ) = 3M 2 M [m x2 + (3 2)m y2 + (1 3 )m z2 ] .

(34)

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Advances in Magnetic Shape Memory Materials

Finally, the condition m 2 = 1 and Eqs. (9), (11) result in two equivalent expressions for the MAED
of twinned crystal:

FA( zy ) = K u [mx2 + (2 1)m y2 ] ,

(35)

FA( zy ) = K u [mz2 + (1 )m y2 ] .

(36)

According to Eq. (36), the averaging of deformations proves to be similar to the averaging of
MAEDs of twin components (martensite variants). When the volume fraction of z-variant is equal to
unit or zero, the Eq. (36) results in the expressions for MAED of the z- or y- variant, respectively
(see Eqs. (10) and (20)).
In the case when the volume fractions of z- and y-variants are equal to each other ( = 1 / 2 ), the
Equation (35) transforms into the expression
FA( zy ) =

1
K u mx2 ,
2

(37)

which describes the ferromagnet with magnetocrystalline anisotropy of the "easy plane" type,
because the anisotropy constant K u is positive (see Eq. (11) and take into account the inequalities
< 0 and c / a < 1 ). According to the model, the fine yz-structure is isotropic in yz-plane when the
volume fractions of twin components are equal to each other. The yz-plane may be magnetically
isotropic also in the case if the volume fractions of twin components are not equal to each other, but
z- and y-directions are physically equivalent in the macroscopic scale. In this case the zy-structure
with ( z ) = , ( y ) = 1 must be presented together with the yz-structure with ( z ) = 1 ,
( y ) = and the spatial domains occupied by these structures must be approximately equal to each
other. So, the average MAED is expressed in the form
1 ( zy )
1
( FA + FA( yz ) ) = K u mx2
2
2

(38)

that corresponds to the MAED of ferromagnetic crystal with the magnetically isotropic plane yz.
The external magnetic field applied in hard magnetization direction (i. e. along the x-axis) deviates
the magnetic vector from the easy plane and the field value H = H A / 2 is sufficient for the
alignment of magnetic vector with hard magnetization direction. This is a half of the field value that
is needed to reorient the magnetic vector of uniform crystal lattice from-easy-to-hard magnetization
direction.
According to the simplest theoretical model, the ideal yz-structure with the equal volume
fractions of twin components appears magnetically isotropic in yz plane and possesses the reduced
magnetic anisotropy in yx and zx planes. The considered model does not pretend to describe
quantitatively the magnetic anisotropy of mesoscale twin structure, but grasps the tendency to the
reduction of the magnetic anisotropy of the single crystal by twinning. This tendency must be
observable for both easy-axis and easy-plane types of magnetic anisotropy of martensite variants.
Under the real experimental conditions, only some of spatial domains of the crystal will
demonstrate the reduced magnetic anisotropy as long as they possess the properly orientated with
respect to the applied magnetic field twin structure. As so, the magnetic saturation of different
spatial domains will be reached at the different field values. This will lead to the nonlinearity of
magnetization curves, as it was assumed and experimentally proved in Ref. [35].
No common opinion about the physical reasons of 5M and 7M modulation of the NiMnGa
martensite exist at present. It may be supposed, in principle, that the modulated martensites are the
thermodynamically stable phases. On the other hand, the periodic modulation of crystal lattice may

V.A. Chernenko

45

be considered as the extremely fine twinning (see Ref. [35] and references therein). In this case the
MAED of 5M and 7M martensites can be described by the Eqs. (35) and (36) with = 2 / 5 and
= 2 / 7 , respectively. In both cases the MAED of the crystal is expressed by the Eq. (4), which
corresponds to the biaxial magnetic symmetry. It should be stressed, however, that the 5M
modulation with z = 2 / 5 , y = 3 / 5 is physically equivalent to the modulation with y = 2 / 5 ,

z = 3 / 5 . If these types of modulation are equiprobable, the uniaxial symmetry of the crystal will be
restored as it was described above. This may explain the obvious disagreement between the
monoclinic symmetry of the modulated crystal lattice and experimentally observed uniaxial
symmetry of MAED.
The presented above theoretical model results in the orthorhombic symmetry of MAED (see
Table 1 and references therein). The symmetry reduction to the monoclinic system can be obtained
by the improvement of approximate Eqs. (33). The improved equations would involve the small
terms, which are nonlinear with respect to MT strain M [15].

7. Summary
The analytic survey of experimental data on the magnetic anisotropy of ferromagnetic shape
memory alloys demonstrates that the comprehension of obtained experimental results is a baffling
problem. A consistent consideration of the magnetoelastic coupling facilitates progress in the
problem solution. The magnetoelastic model of ferromagnetic martensites relates the
magnetocrystalline anisotropy energy density and magnetostress to the temperature dependent
lattice distortion arising in the course of martensitic transformation of the FSMA. The temperature
dependence of lattice distortion gives the main contribution to the temperature dependence of
MAED of the NiMnGa alloys with low MT temperatures; this contribution is also important if
MT temperature is close to the room temperature. The nonlinear dependence of the
magnetocrystalline anisotropy constant on the lattice distortion gives an expectation of the
observation of giant magnetic-field-induced strain in the alloys with moderate MAED. The fine
internal twinning of the alloy specimen may also cause the reduction of MAED. The internal
magnetostatic field makes possible the observation of spontaneous reversibility of MFIS in the thin
martensitic platelets/films and wires.

VL is grateful to UPV/EHU, Bilbao , Spain for financial support of his stay at the Dept.
Electricidad y Electronica. The financial support from the Spanish Ministry of Education and
Science (Project No. MAT2008 06542-C04-02) is acknowledged. This work has been supported by
the ACTIMAT project, sponsored by the Industry Department of the Basque Government (Ref:
IE10-272).
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[40] V. A. Chernenko and V. A. Lvov: Mater. Sci. Forum. Vol. 583 (2008), p. 1.
[41] O. Heczko and L. Straka: J. Appl. Phys. Vol.94 (2003), p. 7139.

(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.49

Entropy Changes in Ferromagnetic Shape Memory Alloys


E. Cesaria, D. Salasb and S. Kustovc
Dept. de Fsica, Univeristat de les Illes Balears, Cta. de Valldemossa, km 7.5 E-07122 Palma de
Mallorca, Spain
a

eduard.cesari@uib.cat, bdaniel.salas@uib.es, csergey.kustov@uib.es

Key words: Ferromagnetic shape memory alloys. Martensitic transformation. Entropy change.
Metamagnetic alloys. Magnetic-field-induced transformation.

Abstract. Several features of the entropy change S related to the martensitic transformation (MT)
in metamagnetic alloys are discussed. In these alloys a change in magnetic order is concomitant with
the MT, as it occurs between ferromagnetic austenite and non-magnetic (weakly magnetic)
martensite. In this case it has been shown that S strongly decreases as the MT temperature range
go far below the Curie temperature of austenite. The behavior of S can be understood considering
the different signs of the lattice and magnetic contributions to the total entropy change. It has been
shown that the so called kinetic arrest of the MT is directly related to the decrease of S, which in
the limit S 0 leads to the suppression of the driving force for the transformation.
Introduction
Ferromagnetic shape memory alloys (FSMA) are a class of multiferroic materials as they combine
ferroelasticity (as in conventional non magnetic- shape memory alloys), through a thermoelastic
martensitic transformation (MT), and ferromagnetism. The interest in FSMA has increased since
the discovery of large magnetic field induced strains due to rearrangement of crystallographic
domains (twin variants) in Ni2MnGa alloys [1]. This effect is closely related to the high
magnetocrystalline anisotropy of the martensite which, in its turn, depends on the tetragonality ratio
c/a [2]. The strains can reach up to 10% (at ambient temperature, in a magnetic field of ~ 1T) in
close to stoichiometric Ni-Mn-Ga alloys with 14M martensitic structure and low detwinning
stresses (1-2 MPa) [3]. Another way to get large strains is based on the fact that in FSMA the MT
can be induced by changing the temperature or stress as in classical SMA - but also by applying a
magnetic field (magnetic field induced transformation: MFIT). The application of a magnetic field
can shift the MT range according to the Clausius-Clapeyron equation:
dT0
M
0
.
dH
S

(1)

where T0 is the equilibrium temperature between austenite and martensite or any other characteristic
temperature TM of the MT, M and S are the changes in magnetization and entropy across the
transformation, respectively. It is well known that, in agreement with the Clausius-Clapeyron
equation, the magnetic field stabilizes the phase with higher magnetization. In conventional FSMA
like Ni-Mn-Ga and Ni-Fe-Ga the MT takes place usually between ferromagnetic phases, thus the
shift of the MT range is small due to small values of M. However, as the sensitivity of TM to
composition changes is much higher than that of Curie temperature of austenite [4], it is possible to
bring near the MT and Curie temperatures in such a way that the MT takes place between
paramagnetic austenite and ferromagnetic martensite ( Tcaustenite < Tcmartensite), thus increasing the
value of M. Under this condition, shifts in TM of about 0.8 K/T have been found in Ni-Mn-Fe-Ga

50

Advances in Magnetic Shape Memory Materials

and in ternary Ni-Mn-Ga [5,6]. Provided larger values of dT0 / dH and/or large fields would be
available, the direct MT could be induced by the application of a magnetic field, if the
transformation hysteresis is not too wide. Therefore, upon switching off the field, a magnetic shape
memory effect (MSME) could be possible, with associated large strains and recovery stresses as in
the temperature induced shape memory. It is worth to note that the recovery stresses in the reverse
MT are much larger than the magneto-stresses of around 2MPa at play in the reorientation of
martensite variants. Moreover, the MSME would allow for larger actuation frequencies than in the
conventional temperature induced shape memory effect.
More recently the possibility to induce the reverse martensitic transformation by the application of a
magnetic field has been demonstrated in a Ni-Mn-In-Co alloy [7], which belongs to the so called
metamagnetic shape memory alloys, as Ni-Mn-X (X=In, Sn, Sb) very often accompanied by Co
additions. Indeed, the MSME has been observed, for example, in Ni-Mn-In [8] and in Ni-Mn-Sn
[9]. The field induced reverse MT has also been found in alloys as Ni-Co-Mn-Al [10] and Ni-MnGa-Co [11], derived from the conventional Ni-Mn-Ga alloys. In all these systems a common feature
is that the MT takes place between a ferromagnetic austenite phase and a low magnetization
martensite, thus leading to large values of M across the transformation, and corresponding large
absolute values of dT0 / dH , which are usually in the range 2 4 K /T . However, as it is obvious
from Eq. 1, the shift in the MT temperatures under a magnetic field is not only related to M but
also to the MT entropy change. In this respect, apart from the interest in alloys showing the MSME,
some specific features of S have been found, which appeared to be relevant for the progress of the
MT and therefore for the practical use of the FSMA.
When the MT in FSMA takes place between phases with different magnetic order, that is when the
MT is a magnetostructural transformation, other concomitant effects appear: Giant
magnetoresistance and large direct or inverse magnetocaloric effects. It is known that during a
first order magnetic phase transition the major contribution to the magnetic entropy change SM is
due to the entropy of the phase transformation S; in other words the magnetic entropy change is
much smaller out of the transformation temperature range, and in the transformation range |SM |
|S| [12]. Therefore from the analysis of S, relevant information on the magnetocaloric effect
associated to a magnetostructural transformation is directly obtained. In this paper the behavior of
S associated to the MT in several alloy systems as Ni-Mn-In and Ni-Mn-In-Co will be discussed.

Entropy changes in metamagnetic alloys


Details on the magnetic and MT behaviors in three alloy series (Ni50Mn25+xIn25-x,
Ni45Co5Mn25+xIn25-x and Ni42.5Co7.5Mn25+xIn25-x) were reported by Ito et al. [13]. The MT entropy
changes were obtained as
S

L
.
T0

(2)

where L is the latent heat measured by DSC, and T0 is the equilibrium temperature for the
transformation; T0 was approximated by (Af + Ms )/2. Analyzing the reported S values for the
different composition series, it is worth to note a strong dependence of S on the difference Tc Ms.
An example for the series Ni45Co5Mn25+xIn25-x is shown in Table 1. The MT temperature
dependence on the composition is the responsible for the increase of Tc Ms, as the Curie
temperatures are only slightly dependent on the composition (Tc ranges from 367 to 372 K for the
compositions shown in Table 1).

V.A. Chernenko

51

Tc-Ms
S
[K] [J/(kg K)]

Ni

Mn

In

Co

e/a

Ms[K]

45

37.5

12.5

7.95

361

58.7

45

36.5

13.5

7.92

323

54

32.9

45

36.6

13.4

7.91

305

69

28.5

45

36.4

13.6

7.91

286

93

23.0

Table 1. Alloy compositions for the series Ni45Co5Mn25+xIn25-x (at %), number of electrons per
atom, martensite start temperature Ms, distance between the Curie temperature of austenite Tc and
the MT, and MT entropy change (absolute values). From ref. [13].
The decrease of S as Tc-Ms increases has been found in several other series, as Ni50Mn50-xInx for
10 x 25, Ni45Mn50-xInxCo5 for 10 x 14, and in Ni42.5Mn50-xInxCo7.5 for 10.5 x 12.6, as it is
shown in Fig. 1.

Figure 1.Entropy change S due to MT vs Tc-Ms for several compositions of ternary Ni-MnIn and quaternary Ni-Mn-In-Co. From ref. [13].

The same behaviour has been found in some Ni-Mn-Ga-Co with compositions close to Ni43Mn30-Ga20-Co7 (at %) for which S goes from 20.1 J/(kg K) for Tc-TM = 102 K to 4.5 J/(kg K) for
Tc-TM= 210 K [11]. These data together with the systematic dependence of S on Tc-Ms for the
ternary and Co containing Ni-Mn-In alloys clarified the S behavior after some confusing values
published earlier for the ternary alloys [14].

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Advances in Magnetic Shape Memory Materials

In addition to the large changes in S values, a strong decrease in Ms vs. In content was found when
the MT takes place from a ferromagnetic parent phase. This behavior can be correlated with that of
S vs. In content for the three series studied in [13]. As it can be seen in Fig. 2, the effect of In
concentration on S is small in the region where the austenite is paramagnetic, but it drastically
changes to a strong dependence when the austenite becomes ferromagnetic.

Figure 2. Entropy change due to the MT vs. indium composition for three alloy series
(ternary Ni-Mn-In , and 5 and 7.5 at% Co content). From ref. [13].
Such experimental results on the Ms and S have been qualitatively explained considering the
magnetic contribution to the Gibbs free energy when the parent phase becomes ferromagnetic. This
contribution, added to the free energy of the austenite, makes the equilibrium temperature parentmartensite to decrease as the temperature goes below Tc. In this way both the decrease in T0 and in
S can be qualitatively understood.
In order to further clarify the origin of strong variations in S, the effect of long-range order in a
fixed composition of a Ni-Mn-In-Co alloy has recently been studied [15]. The degree of long-range
L21 ordering is known to shift both the MT and para- to ferromagnetic transition temperatures [1619], not affecting the e/a ratio and only slightly changing the spontaneous magnetization of
ferromagnetic austenite [20-21]. The order degree was changed by varying the heat treatment
temperature and cooling rate [15]. Differential scanning calorimetry (DSC) was used to determine
the MT temperatures and to estimate the associated entropy change through the expression (2),
where the DSC peak temperature Tp was used instead of T0. Fig. 3 shows the absolute values of
entropy change S vs the difference between Curie and MT temperatures. By optical and
transmission electron microscopy the absence of decomposition or precipitation processes in the

V.A. Chernenko

53

50

Ni-Mn-In-Co

45

S, J/(kg*K)

40
35
30
25
20
15
10
5
0
0

40

80

120

160

200

Tc-Tp, K

Figure 3. Entropy change S vs Tc-Tp for a Ni45.0-Mn36.7-In13.3-Co5.0 at% alloy. Blue: direct
MT, red: reverse MT.

25

Ni-Mn-In

S, J/(kg*K)

20

15

10

0
0

40

80

120

160

Tc-Tp, K

Figure 4. Entropy change S vs Tc-Tp for a Ni50.6-Mn32.7-In16.7 at%alloy. Blue: direct


red: reverse MT.

MT,

samples has been checked. It is worth to mention that, according to the data of Fig. 3, a factor of
about 7 gives the range of S variation, from low MT temperatures and low S in highly ordered
samples to high transformation temperatures and high S values in specimens with low degree of
long-range order. Fig. 4 shows a quite similar behaviour for a ternary Ni-Mn-In.
Eq. (1) can be used to estimate the relative importance of S and M on the MT temperature shift,
T, due to a magnetic field. Large differences in S will lead to different shifts in the MT,

54

Advances in Magnetic Shape Memory Materials

provided the change in the magnetization M is not changing much due to different MT
temperature range. The analysis of the relative importance of S and M variations on the MT
temperatures has been performed in ref. [15]. One can estimate the change in magnetization M(T)
as the spontaneous magnetization Is(T) of the parent phase, since the MT occurs between
ferromagnetic austenite and non-magnetic martensite (weakly magnetic?), and not too close to the
Curie temperature:

I (T ) Tc
M (T ) m p I s (T ) = M 0 th s
M0 T

(3)

where M 0 is the magnetization at T = 0 K. The ratio T/Tc lies in the range 0.9 0.55, thus
variations of M are between 0.5 and 0.95 M0 , less than a factor two. However, the variations of
T with T-Tc are more than six-fold. Therefore, it has to be concluded that the main contribution to
the variation of T, according to eq. (1), lies in S variations with T-Tc. Data on S vs (Tc-T) from
Fig. 3 and temperature dependence of the magnetization change, eq. (3), allows one to calculate the
expected shift of the MT with magnetic field using Clausius-Clapeyron equation (1). The calculated
T values for 0H = 1.7 T and M0 = 130 emu/g are shown in Fig. 5, together with experimental
values from samples with different order degree, that is with different MT temperatures. The results
show good correspondence between calculated and experimental S values, pointing to the

Figure 5. Calculated and experimental values of the shift of MT, T, vs. reduced difference
between Curie and MT temperatures t = (Tc-TM)/Tc for 0H = 1.7 T in a Ni45.0-Mn36.7-In13.3Co5.0 at% alloy. From ref. [15].
importance of using proper S values in order to get good a priori estimations of the temperature
shift produced by the application of a magnetic field.
An important issue in relation to the shifts T produced by a magnetic field has to be discussed:
Very different T values are obtained at the MT start and finish temperatures. For slowly cooled
samples, having low S values, these shifts are about 7 and 22 K at Af and As, respectively, under
0H = 1.7 T ; see fig. 3(a) of ref. [15]. This indicates that the effective entropy change can be
rather different at the beginning and at the end of the MT, especially in the cases when S is small
and the transformation temperature range is extended.

V.A. Chernenko

55

The discrepancies reported in [13], between the calculated shift in the MT due to the application of
a magnetic field, T using the expression (1) and the experimental shift in Ms can be now easily
understood: The estimation of S using the expression (2) means an average for the whole
transformation range. As it has been shown, S for a given composition strongly depends on TcTM. At the same time, the decrease of the S value results in broadening of the MT range, as a
stronger overcooling is needed to provide sufficient chemical driving force. The large difference
between Ms and Mf, in its turn, provokes even further decrease of S at Mf as compared to S at
Ms. From Fig. 6 it becomes obvious the different shifts produced by the magnetic field close to Ms
or to Mf. Therefore, the S value obtained through (2) is in fact an underestimation at Ms and an
overestimation at Mf , or in other words, the austenite transforming close to Mf has a lower entropy
change (absolute value) than that estimated using (2). The discrepancies can be expected to be larger
as S is lower because of the corresponding larger MT temperature range, as it has been mentioned
above, and is confirmed comparing the results for Ni50Mn34In16 and Ni45Mn36.5In13.5Co5 in ref [13].
The different values of the entropy change at play close to Ms or to Mf are also responsible for the
different shifts produced by a magnetic field: As the change in magnetization M is supposed not
varying much from Ms to Mf, the shift due to the field at the end of the transformation is larger than
at Ms because of the lower value of S close to Mf. The same reasoning applies to As and Af.
There is another point, related to the different T vs. S, which deserves more detailed discussion:
It has been found that in highly ordered samples (i.e. slowly cooled), the direct MT transformation,
under an applied field of 1.7 T, is not completed even at low temperatures as ~ 140 K , see Fig. 6.
Therefore the MT transformation becomes arrested under a field of 1.7 T in the samples with low
S. When the field is switched off at the lowest temperature of the thermal cycle, the MT is
completed, at constant temperature, in a time dependent process (indicated by the vertical arrow and
the inset in Fig. 6). Even though to discuss the isothermal features of the MT in ferromagnetic shape
memory alloys is not within the scope of this paper, it has to be mentioned that the arrest of the
transformation is not a prerequisite for the appearance of time dependences in the MT, as isothermal
features have been found even the absence of applied magnetic field [22].
The decrease in S, as seen in Figs. 3 and 4, clearly shows that for even lower transformation
temperatures, the total entropy change approaches a zero value. In this case, the absence of any
driving force S.T for the transformation should lead to complete arrest of the MT, even in
absence of an applied magnetic field. It has been recognized that the arrest of the MT will take place
at temperatures where the lattice and magnetic contributions to S, having different signs,
compensate each other [15, 23]. As
pm
p m
S pm = S lattice
+ S magn
.

(4)

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Advances in Magnetic Shape Memory Materials

Fig. 6. Resistance of a slowly cooled sample of Ni45.0Mn36.7In13.3Co5.0 at%, as a function of


temperature in three consecutive thermal cycles, with and without applied field of 1.7 T. The
vertical arrow shows the time dependent completion of the direct MT at T = 143 K after
switching off the field. The inset shows the corresponding time dependences of applied magnetic
field and resistance. From ref. [15].

the compensation is possible in metamagnetic alloys, as the MT takes place between ferromagnetic
p m
p m
austenite and non-magnetic martensite, thus S magn
> 0 , and S lattice
< 0 . Moreover, as the
difference TC-TM increases so does the magnetic ordering of the austenite, thus increasing the
positive contribution to S pm . In the same direction, the application of a magnetic field reduces the
p m
magnetic entropy of the parent phase, favoring the increase in S magn
and therefore the arrest of the
MT as it has been observed. It is interesting to point out that in conventional ferromagnetic shape
memory alloys, where the MT usually takes place between ferromagnetic phases, the magnetic
contribution to the MT entropy change is much smaller than in metamagnetic alloys; as an example,
p m
for Ni-Fe-Ga alloys, an average S magn
value close to -3.2 J/(kg K) has been estimated [24].
The so called kinetic arrest of the MT has been reported earlier in Ni-Mn-In [25] and in Ni-Mn-Sn
alloys [26], in both cases accompanied by time dependent effects as seen by changes in the
magnetization or in the DC resistance, respectively. Although in references [25] and [26] the
relation between the arrest and magnetic contribution to the entropy change is not mentioned, it is
shown that the arrest and the associated time dependent effects, are more pronounced under the
application of a magnetic field, thus supporting the role of the magnetic contribution to S.
The role of S in the arrest of the transformation has been even further confirmed by the results
presented in the references [23, 27, 28]. From magnetization and electrical resistance vs. magnetic
field experiments carried out at different temperatures, one can determine the critical field to induce
the reverse MT , HAf , and the critical field, HMs, for which the direct MT starts in the field
decreasing part of the magnetization field cycles. Thus an equilibrium magnetic field H0 can be
defined in similar way as for T0:
H 0 = ( H Ms + H Af ) / 2 .

(5)

V.A. Chernenko

57

(c)

Figure 7. (a) Magnetization and (b) Electric resistivity curves vs. magnetic field at
temperatures below Mf for a Ni-Mn-In-Co alloy. (c) Magnetic field-temperature phase
diagram, where the fields were evaluated from the curves shown in (a) and (b).
From ref. [27].
As an example, results from reference [27] will be commented in some detail. As it can be seen in
Fig. 7 (c), H0 is almost constant for temperatures below 150 K. Taking into account the parallelism
between T0 and H0, and the Clausius-Clapeyron equation given by (1), the derivative dH0/dT 0
means that S 0, as the change in magnetization due to the MT remains in the range close to 120
emu/g below 150 K (see Fig. 7 (a)). Thus the behaviour of H0 clearly shows that it is related to a
decrease of S, with the limit S 0 .This means that the driving force for the thermally induced
transformation G ST practically disappears below 150 K, and the transformation can not
progress. Taking into account the driving force for the transformation which goes to zero as S 0,
the arrest of the MT can be considered rather a thermodynamic arrest than a kinetic one. A parallel
behaviour to that of dH0/dT has been found in stress-induced transformations in a Ni-Mn-In-Co
alloy: the temperature derivative of the equilibrium stress, d0/dT, goes to zero for temperatures
below ~ 150 K thus confirming again that S 0 in this temperature range [29].
In Figures 7 (a) and (b), apart for the giant magneto resistance effect, it is worth to notice the
increase in the field hysteresis, which raises from 2-3 T at temperatures close to 200 K up to more
than 10 T at 4 K. At this temperature, both the magnetization and the DC electric resistance show
discontinuous, jump-like, behaviour. In the reference [27] the authors relate the lack of MT progress
in the very low temperature region to the decrease of the mobility of the habit plane at parentmartensite interfaces, as this idea is supported by the jump-like behaviour observed at 4 K.

58

Advances in Magnetic Shape Memory Materials

Further evidence of discontinuous behaviour has been found in thermo-magnetization studies of the
same Ni-Mn-In-Co alloy [30]. Measuring the magnetization vs temperature under low magnetic
fields (after a magnetic field cooling under 7 T from 300 to 6 K, thus after the transformation has
been fully arrested) sudden jump-like drops of magnetization have been observed under heating,
indicating that some direct MT steps occur. Afterwards the magnetization decreases in a smooth
way on heating up to about 160 K. This behaviour, together with discontinuous magnetization
changes observed in M H curves under decreasing field (after FC under 7 T from 300 K to the
measuring temperature) point out to characteristics of isothermal MT. Indeed, time dependences of
the magnetization under different temperatures and fields, and the corresponding incubation times
for the occurrence of the isothermal MT, from arrested parent phase, have been measured [30].
Taking into account the isothermal MT characteristics found in the arrested parent phase, as well as
the fact, commented above, that arrest of the transformation is not a necessary condition for the
appearance of isothermal transformation [22], it can be considered that the MT in these
metamagnetic alloys shows characteristics of both athermal and isothermal transformation even in
absence of a magnetic field, as it has been shown in [22]. As it is discussed by Massalski in ref. [31]
when there are thermally activated processes which occur on continuous cooling, the
transformations have been called anisothermal, although this term has never been very popular. It is
suggested that the isothermal martensites could be named thermally activated martensites (TAM),
normally the thermal activation being present only at the initiation stage, although thermal
activation in the growth stage could be considered in some cases [31].
It is interesting to recall here the works of Kakeshita et al. [32, 33] where a Fe-24.9Ni-3.9Mn
(wt%) shows an isothermal transformation which becomes athermal under the application of a
magnetic field (It has to be pointed out that in this Fe-based alloy the martensite phase corresponds
to the high magnetization one, thus the magnetic field favours the MT, opposite to the
metamagnetic alloys case). It is concluded in [32] that the effect of the magnetic field on the
originally isothermal transformation has the same physical basis that in the athermal one. The same
idea could be applied to the metamagnetic alloys. In this case the magnetic field - stabilizing the
parent phase, thus opposing the MT progress- favours the isothermal characteristics, appearing
either under field cooling [25,26] or on switching off the field in an arrested transformation [15].
Furthermore, incubation times for the isothermal MT, from an arrested parent phase, have been
measured [30]. Therefore, the martensite in these metamagnetic alloys is a TAM, in which the
magnetic contribution to S and/or the effect of the magnetic field can bring the arrest of the
transformation and associated isothermal characteristics.

Acknowledgements
Partial financial support from FEDER and DGI (Spain), ref. MAT2008-01587, is acknoweledged.
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[29] X. Xu, W. Ito, R.Y. Umetsu, R. Kainuma and K. Ishida: Appl. Phys. Lett. 95 (2009) 181905
[30] W. Ito, R.Y. Umetsu, R. Kainuma, T. Kakeshita and K. Ishida: Scripta Mat. 63 (2010) 73
[31] T.B. Massalski: Mat. Trans. 51 (2010) 583
[32] T. Kakeshita, K. Kuroiwa, K. Shimizu, T. Ikeda, A. Yamagishi and M. Date: Mater. Trans. JIM
34 (1993) 415
[33] T. Kakeshita, K. Kuroiwa, K. Shimizu, T. Ikeda, A. Yamagishi and M. Date: Mater. Trans. JIM
34 (1993) 423

(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.61

Stress-Temperature Phase Diagram of Ni2MnGa and Structural Relations


between Its Constituent Phases
Takashi Fukuda a, Tomoyuki Terai, Hidefumi Maeda,
and Tomoyuki Kakeshita
Department of Materials Science and Engineering, Graduate School of Engineering,
Osaka University, 2-1, Yamada-oka, Suita, Osaka 565-0871, Japan
a

fukuda@mat.eng.osaka-u.ac.jp

Key words: Stress-induced transformation, ferromagnetic shape memory alloy, single crystal,
incommensurate structure

Abstract. The ferromagnetic shape memory alloy Ni2MnGa exhibits a successive martensitic
transformation from the L21-type structure to the so-called intermediate phase and then to the
martensite phase with an incommensurate structure during cooling under zero stress. In addition to
these phases, a new phase, which we call the X-phase, appears when Ni2MnGa is cooled under
compressive stress applied in the [001] direction. In this paper, we discuss the structural relations
between the X-phase and the other phases on the basis of experimental results of compressive tests,
transmission electron microscope observations and neutron diffraction patterns. It is likely that a
multicritical point exists in the stress-temperature phase diagram of Ni2MnGa.
Introduction
The Heusler-type intermetallic compound Ni2MnGa has attracted considerable attention because of
its characteristic features attributable to the interplay of magnetism and martensitic transformations.
One important feature is the giant magnetic field-induced strain of several percent caused by the
rearrangement of martensite variants [1-5]. This feature is realized by a large magentocrystalline
anisotropy and a small stress for the movement of twinned interface between variants of Ni2MnGa.
Another important feature is the magnetocaloric effect caused by magnetic field-induced structural
transformation [6, 7]. This feature is realized by the large difference in magnetization between the
parent phase and the martensite phase.
The appearance of the intermediate phase (I-phase) in between the L21-type parent phase
(P-phase) and the martensite phase with the so-called 10M structure (M-phase) is also an important
characteristic feature of the alloy [8, 9]. The transformation from the P-phase to the I-phase is
considered to be the consequence of the phonon softening in the TA2 branch, because a mode in the
TA2 branch becomes nearly zero on approaching the P-I transformation temperature and satellites of
the I-phase appear nearly at the same point where phonon softening occurs [10-13]. Some theoretical
approaches were attempted on the interpretation of the transformation from the P-phase to the I-phase
[14-15]. The structure of the martensite phase is also of interest because the so-called 10M phase in
stoichiometric Ni2MnGa is reported to have an incommensurate structure [16, 17]
In addition to the P-, I- and M-phases, we recently found that a new phase, which we hereafter call
the X-phase, appears under the application of compressive stress in the [001] direction [18]. In this
paper, we describe the phase boundary between the X-phase and the other phases and then discuss the
structural relations among the constituent phases. It becomes apparent that the X-M transformation is
clearly of the first order at any temperature. On the other hand, the X-I transformation is of a weak
first order and the transformation shows a critical phenomenon when external stress approaches zero.
The P-X transformation is most likely of the second order with no transformation strain and
hysteresis.

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Stress-Temperature Phase Diagram of Ni2MnGa


Figure 1 shows the stress-temperature phase diagram obtained by using a single crystal of Ni2MnGa
[19]. Details of the experimental procedure and the method for obtaining the phase boundary are
described elsewhere [19]. There are two characteristic points in the phase diagram.
The first is located at 208.9 K and 9.6 MPa. This point is the triple point at which three phase
boundaries of first order transformations (I-M, I-X and M-X) meet. The triple point naturally appears
if there are three different phases that replace one another by first order transformations. As we see
later, this condition is satisfied in Ni2MnGa: hence, the appearance of the triple point in Fig. 1 is quite
normal.
The other characteristic point is located at about 250 K and 0 MPa. It seems that the I-X and P-X
phase boundaries merge each other at this point. To the best of our knowledge, there are no reports of
such a point in shape memory alloys. However, there is a similar point in the stress-temperature phase
diagram of SrTiO3 [20]. In the case of SrTiO3, this similar point is interpreted as the multicritical point
at which two phase boundary merge: one corresponds to the second order cubic-trigonal
transformation, and the other corresponds to the first order trigonal-pseudotetragonal transformation.
Considering the resemblance between the stress-temperature phase diagram of Ni2MnGa and
SrTiO3, it is expected that the latter point described above (Fig. 1) is a multicritical point. Therefore,
in the following sections, we review the transformation behavior and structural relations between the
X-phase and the other phases.
Incidentally, the existence of the X-phase was confirmed by Karaca et al. [21]. In addition, the
anomalies corresponding to the appearance of the X-phase under a compressive stress were reported
in the literature [22-24] although the X-phase was not regarded to be different from the I-phase when
these papers were published.

Figure 1 Stress-temperature equilibrium phase diagram of stoichiometric Ni2MnGa under


compressive stress applied in the [001]P direction[19]. Solid circles, solid triangles and solid
squares indicate the equilibrium stresses of the P-X, I-X and X-M transformations, respectively,
obtained by compressive tests. Open circles, open triangles and the open diamond specify the
equilibrium temperatures of the P-X, I-X and I-M transformations, respectively, obtained by
magnetic susceptibility measurements.

V.A. Chernenko

63

Thermally Induced PXI Transformations


The P-X and X-I transformations in Ni2MnGa can be clearly detected by measuring the temperature
dependence of magnetic susceptibility under a low magnetic field. Figure 2 (a) shows the magnetic
susceptibility of single-crystal Ni2MnGa measured under a compressive stress of 7.5 MPa applied in
the [001] direction. (In this paper, the orientation is indicated by referring to the basis of the cubic
lattice of the P-phase.) The measurements were made by applying a magnetic field of 400 A/m in the
[001] direction. We notice a bend point at 257 K on both the cooling and heating curves as indicated
by a double arrow. This temperature corresponds to the equilibrium temperature of the P-X
transformation. Because the magnetic susceptibility changes continuously and no hysteresis appears
between the cooling and heating processes near the equilibrium temperature, the P-X transformation
will most likely be of the second order. We also notice a sharp increase in magnetic susceptibility
during cooling at 226 K and a sharp decrease in the heating process at 235 K, as indicated by single
arrows. These sharp changes correspond to XI and IX transformations, respectively. The sharp
change and hysteresis between the cooling and heating processes imply that the XI and IX
transformations are of the first order under the compressive stress of 7.5 MPa.
The first order nature of the IX transformations weakens when the magnetic field is reduced to
zero as shown in Fig. 2(b). That is, the increase in magnetic susceptibility in the cooling process and
the decrease in the heating process become gradual as indicated by single arrow in Fig. 2(b), and the
temperature hysteresis becomes very small. The result of magnetic susceptibility suggests that the
IX transformation shows a critical phenomenon when the external stress approaches zero.

Figure 2 Magnetic susceptibility of Ni2MnGa measured under a magnetic field of 400 A/m applied
in the [001] direction. A uniaxial compressive stress of (a) 7.5MPa and (b) 0 MPa was applied in
the same direction of the magnetic field during the measurement.

Figure 3 Electron diffraction pattern taken at (a) 276K, (b) 256 K and (c) 245K of Ni2MnGa with
zone axis [001] [25].

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Advances in Magnetic Shape Memory Materials

The continuous structural change in the PXI transformation can be more clearly seen by
comparing the electron diffraction patterns of the three phases under zero stress [25]. Figure 3 shows
the electron diffraction patterns of Ni2MnGa taken at 276K, 256K and 245 K. According to the phase
diagram shown in Fig.1, the specimen is in the P-phase state at 276 K, the I-phase state at 245 K and
likely to be in the X-phase state at 256 K. All three diffraction patterns have a common characteristic
feature. That is, diffuse streaks appear in the <110> direction and weak spots appear near 1/6 of in
between the strong Bragg reflections of the L21-type structure. There is no discontinuous change in
electron diffraction pattern between 276 K and 245 K. The angle is 90.0 degree for all three
temperatures, and the intensity of the satellite increases monotonically with decreasing temperature.
The electron diffraction patterns imply that both the PX and XI transformations are close to the
second order under zero stress. In contrast to the PXI transformation, the IM and XM
transformations are obviously of the first order.
Stress-induced IX and PX transformations
The transformational behavior can also be deduced from a stress-strain curve [19]. The stress-strain
curve obtained at 260 K shows a bend point near 20 MPa, as indicated by an arrow in Fig. 4(a). This
bend point corresponds to the stress-induced PX transformation. The stress-strain curve at 260 K
shows no plateau, and the hysteresis is negligibly small. This result is the consequence of the second
order nature of the PX transformation. Incidentally, Youngs Modulus is very small for both the Pand X-phases; it is about 10 GPa for the P-phase and about 9 GPa for the X-phase at 260 K.
On the other hand, the stress-strain curve obtained at 219 K shows an obvious plateau and a
hysteresis as shown in Fig. 4(b). The appearance of this plateau is due to the stress-induced IX
transformation. The appearance of this plateau and the hysteresis implies that the IX
transformation is obviously of the first order. Youngs modulus is about 15GPa for the I-phase and
about 7 GPa for the X-phase at 219 K. These values are one-third to one-tenth of Youngs modulus of
Ti-Ni-based shape memory alloys.
From the stress-strain curve of the IX transformation, we obtain the transformation strain, and
its temperature dependence is shown in Fig. 4(c) [18]. The transformation strain decreases with
increasing temperature, and it becomes nearly zero at 255 K. This result implies that the first order
nature of the IX transformation weakens with increasing temperature and disappears around 250 K,
suggesting the existence of a critical point for the IX transformation.

Figure 4 Stress-strain curves of Ni2MnGa obtained by applying compressive stresses in the [001]
direction at 260 K(a), 219 K (b), and the temperature dependence of transformation strain for the
stress-induced IX transformation (c) [18, 19].

V.A. Chernenko

65

Comparison of neutron diffraction pattern with electron diffraction pattern


As mentioned before, the structure of the X-phase is almost the same as that of the I-phase under zero
stress. To better understand the structural relation between the X-phase and the other phases, we need
to carry out a structural analysis under compressive stress. For this purpose, neutron diffraction is
highly effective. However, there is a discrepancy between the crystal structure of the martensite phase
of Ni2MnGa determined by a neutron diffraction [26] and that determined by electron diffraction [27].
In the following discussion, we will confirm that the same structure appears in the electron diffraction
pattern and the neutron diffraction pattern.
Figure 5 (a) shows a bright field image at 20 K of the M-phase taken from a single variant region.
The corresponding diffraction pattern (b) exhibits six satellites in between the two fundamental
reflections of the Heusler-type structure. The intensity profile between the fundamental reflections of
040 and 400 in (b) is also shown in (c). It should be noted that the nearest satellites from the
fundamental reflections can be represented as qM with qM = 0.427(5) g-220. Moreover, the second and
third nearest reflections can be represented as 2qM and 3qM, respectively. The appearance of
satellite reflections of the M-phase at positions incommensurate to the fundamental reflections is
consistent with the X-ray diffraction results reported previously [16]. The satellites also appear
exactly at the same position between 200 and 020 as seen in Fig. 5(b).
Figure 6 compares the electron diffraction and neutron diffraction patterns in reciprocal space
between 200 and 020 reflections. The profile (a) and (a) are of the M-phase near 100 K, and (b) and
(b) are of the I-phase near 210 K. We notice that the satellites in the neutron diffraction pattern
appear exactly at the same position as those in the electron diffraction pattern for both the M-phase
and the I-phase. Therefore, in the following section, we discuss the structural relation between the
X-phase and other phases on the basis of the position of satellites obtained by neutron diffraction.

Figure 5 Bright field image (a) and corresponding electron diffraction pattern (b) of Ni2MnGa
obtained near 20 K. (c) is the intensity profile measured between 400 and 040 reflections in (b). [25]

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Advances in Magnetic Shape Memory Materials

Figure 6 Intensity profiles of


the M-phase (a) and (a) and
I-phase (b) and (b). (a) and
(b) are of electron diffraction,
and (a) and (b) are of
neutron diffraction. [25]

Stress-induced IXM transformation examined by neutron diffraction.


Figure 7 shows the neutron diffraction patterns measured in successive stress applying process at
225 K [28]. At this temperature, the stress-induced IXM transformations occur as seen in Fig. 1.
Before the compressive stress is applied, a satellite reflection of the I-phase appears at h = 0.338.
Under a compressive stress of about 10 MPa, a new satellite reflection appears at h = 0.360 in addition
to that of the I-phase, which stays in almost the same position. The new satellite is due to the
formation of the X-phase, and the coexistence of the two satellites at different positions means that
the IX transformation is of the first order. Under a compressive stress of about 25 MPa, the
reflection of the I-phase completely disappears and the satellite of the X-phase moves to h = 0.369. In
addition, another satellite appears at h = 0.419 due to the formation of the M-phase. The coexistence
of the X- and M-phases means that XM transformation is of the first order. By comparing the
profile at = 10 MPa with that at = 25 MPa in Fig. 7, we notice that the satellite position of the
X-phase depends on the applied stress. We will discuss the stress and temperature dependence of the
satellites in the next section.

Figure 7 Neutron diffraction profiles of


Ni2MnGa showing the stress-induced IXP
transformation. Measurements were made at
225 K at 1 MPa, 10 MPa and 25 MPa between
the 200 and 020 reflections. [28]

V.A. Chernenko

67

Stress and temperature dependence of satellite position


Figure 8 shows the neutron diffraction profiles of the X-phase at 255 K under different
compressive stresses of 1 MPa, 50 MPa and 100 MPa [29]. In the case of 1 MPa, an extremely weak
satellite reflection appears at an incommensurate position of h~0.341 (the index h represents the
satellite position of [h, 2-h, 0]). Although this satellite comes from the X-phase, its position is close to
that of the I-phase under zero stresses as seen in Fig. 7. The reason why satellites of the X- and
I-phases appear at almost the same position will be discussed later. When the stress is increased to
50 MPa, the satellite position moves from h = 0.341 (under 1 MPa) to h = 0.369, and the intensity
increases significantly. Under a stress of 100 MPa, the profile of the satellite reflection is asymmetric
in shape. This asymmetric profile can be fitted by considering two peaks: one from the X-phase and
the other from the M-phase. In addition to position and intensity, it should be noted that in Fig. 8 the
full width at half maximum (FWHM) of the X-phase depends directly on applied stress. For example,
the FWHM of the satellite reflection under 1 MPa is ~0.016, and that under 50 MPa is ~0.030. Such
an increase in FWHM implies that the variance in modulation wave length increases with the
application of external stress.

Figure 8 Neutron diffraction profiles of the


X-phase satellite at 255K under different
compressive stresses. The profile under
100MPa comprises the X-phase (left peak) and
M-phase (right peak).

Figure 9 Neutron diffraction profile of the


X-phase at 220 K, 240K and 260 K at 10 MPa.

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Advances in Magnetic Shape Memory Materials

Figure 10 Neutron diffraction profile of the


M-phase satellite at 190 K under different
compressive stresses.

Figure 11 Neutron diffraction profile of the


M-phase at 190 K, 200K and 210 K at 10 MPa.

The position and intensity of the satellite reflection of the X-phase also strongly depend on
temperature as shown in Fig. 9. In Fig. 9, the satellite profiles are obtained at 220 K, 240 K and 260 K
under a compressive stress of 10 MPa. At 220 K, the satellite reflection of the X-phase appears at an
incommensurate position of h = 0.361. With increasing temperature, the satellite reflection moves
toward the nearest fundamental reflection of [0 2 0], and its intensity drastically decreases. In addition
to the change in position and intensity, the FWHM of the X-phase decreases from 0.024 at 220 K to
0.020 at 260 K.
Figure 10 shows the stress dependence of the satellite profile of the M-phase, and Fig. 11 shows
the temperature dependence of the satellite profile of the M-phase. Compared with the X-phase, the
satellite position and intensity in the M-phase are less sensitive to both stress and temperature. In
addition, the FWHM of the satellite of the M-phase is also less sensitive compared with that of the
M-phase.

V.A. Chernenko

69

Figure 12 Temperature and stress


dependence of (a) satellite positions and
(b) satellite intensities relative to the
fundamental reflection. Triangles, circles
and squares indicate the M-, I- and
X-phases respectively

The satellite positions and intensities for the X- and M-phases are summarized in Fig. 12, together
with those of the I-phase under zero stress. The stress dependency of the satellite position and
intensity of the X-phase at 255K is also shown by the open squares in Figure 8. We will now discuss
the structural relationship between the X-phase and the other phases by referring to Fig. 12. Firstly,
with regards to the structural relationship between the X- and M-phases, it can be seen from Fig. 12
that the satellite position and intensity of the X-phase are clearly different from those of the M-phase
for all temperature and stress ranges examined. In addition, the FWHM of the X-phase is nearly twice
that of the M-phase, as shown in Fig. 7. Consequently, the XM transformation is of the first order
regardless of the applied stress or temperature as mentioned before. Secondly, with reference to the
structure relationship between the X- and P-phases, Fig. 12 (b) shows that the satellite intensity of the
X-phase continuously and linearly approaches zero nearing the XP transformation temperature.
This suggests that the XP transformation is continuous. This interpretation is consistent with the
result shown in Fig. 2 and Fig. 4(a). Finally, regarding the structure relationship between the X- and
I-phases, except for in the vicinity of the IX transformation temperature under zero stress, (which is
254K for the specimen, as seen in Fig. 1, and denoted as T0IX), the IX transformation is of the first
order. This conclusion is derived because the I- and X-phases coexist in association with the
transformation as seen in Fig. 7, and a hysteresis exists for the transformation as seen in Fig. 2 and Fig.
4(b).
In the vicinity of T0IX, however, the transformation is continuous, as shown in Fig. 12. In other
words, the satellite position of the X-phase nears that of the I-phase on approaching T0IX. In addition,
the intensity of the I-phase at zero stress approaches that of the X-phase under 1 MPa on nearing
T0IX. Therefore, the satellite reflection of the X-phase under zero stress is indistinguishable from
that of the I-phase. This is the reason why the X-phase, which exists even under zero stress, has not
been found by the neutron, X-ray and electron diffraction experiments reported to date.
The difference in IX transformation behavior between high and zero compressive stress
strongly suggests the existence of a critical point. This interpretation is supported by the temperature
dependence of the transformation strain shown in Fig. 4(c).
From the above discussion, it is most likely that in Ni2MnGa, a continuous PX transformation
is followed by another continuous XI transformation under zero stress, and these two
transformations occur at the same temperature. In all probability, there is a multicritical point in
Ni2MnGa, similar to that observed in SrTiO3 [20].

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Summary
Ni2MnGa with stoichiometric composition has a multicritical point where the P-X phase boundary
merges with the X-I phase boundary. The P-X phase transformation is second order like, while the
X-I transformation is of the first order. The first order nature of the X-I transformation gradually
disappears on approaching the multicritical point. Further information of the X-phase is needed to
explain the appearance of the multicritical point in Ni2MnGa.
Acknowledgements
This work was supported by the Global COE program Center of Excellence for Advanced Structural
and Functional Design by MEXT Japan.
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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.73

Neutron Diffraction Studies of Magnetic Shape Memory Alloys


J.M. Barandiarana, J. Gutirrezb, P. Lzpitac and J. Feuchtwangerd
Faculty of Science and Technology, University of the Basque Country (UPV/EHU)
P.O Box 644, 48080 BILBAO, Spain
a

manub@we.lc.ehu.es, bjon@we.lc.ehu.es, cpatricia.lazpita@ehu.es, dfeucht@gmail.com

Key words: Crystal structure, magnetic moment, neutron diffraction

Abstract. The characteristics of neutron diffraction applied to the study of Ferromagnetic Shape
Memory Alloys are revised. Main studies refer to crystal structure, preferential site occupancy,
variant reorientation and magnetic moment distribution in the alloys
1 Introduction
FSMA have complicated crystallographic and magnetic structures [1-3]. The martensitic transition
itself, as well as the premartensitic and intermartensitic ones, are also complex. They involve
phonon softening modes mechanisms and several modulated and non-modulated ending structures,
very sensitive to the exact composition of the alloys. Such structures are sometimes mixed up in a
given alloy. Different degrees of order among the different atomic species can also be present in the
same sample and evolve as a function of time and annealing.
In addition different magnetic atoms are involved in the ferromagnetism. For instance NiMnGa
alloys, the most common ones, have been shown to have localized 3d magnetic moments linked to
Mn and Ni atoms, with ferro and antiferromagnetic contributions [4,5]. Probably also some itinerant
contribution related to s electrons, shared by all components, is also present.
The modulated martensitic structures and competing magnetic interactions have raised a number of
studies carried out by X rays, TEM, synchrotron radiation and neutron dispersion [2,3,6-8]
Neutron diffraction is a well-established technique for crystal and magnetic structure studies. As
compared with X-ray and electron diffraction, it presents a number of advantages, and some issues
that can be summarized as follows:
a) advantages
- Crystal diffraction is sensitive to the nuclear interaction, described as point like potentials [9,10].
Scattering from neutrons can, therefore, be described by a single parameter, the scattering length.
This gives a special sensitivity to large diffraction angles because scattering lengths are simple
numbers and do not depend on the scattering angle.
X-rays

Z=

NEUTRONS

Mn

Ni

Ga

25

28

31

Mn

Ni

bC (fm) = -3.73

7.28

Ga
10.3

Fig. 1.- "Visibility" of Mn, Ni and Ga based on the scattering factors for X-rays (proportional to the
Atomic Number Z) and neutrons (Coherent Scattering Length bC)
- Neutron scattering factors are not proportional to the atomic number, as in x-rays and electrons,
and can even be negative, so that there can be a large contrast between elements that locate close in
the periodic table and are impossible to distinguish by X-rays or electron diffraction. This
advantage is very clear in NiMnGa alloys that have faint contrast in X-rays for the superstructure
peaks, but very large for neutrons (Figs 1 and 2 and Table I). Such a contrast arises because the Mn
neutron scattering length is negative.

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- Neutron penetration in matter is very large as compared with x-rays (a few microns) and electrons
(a few nanometers), so that bulk samples can be fully explored by neutrons, in contrast with near
surface analysis by the other techniques. This feature is especially valuable for large crystal
diffraction. A side outcome of the penetration power of neutrons is that especial equipment, as
cryostats and furnaces or superconducting magnets, can be employed with little perturbation of the
beam and diffraction pattern.
- Neutrons are sensitive to the magnetic moment of the atoms and are invaluable to study magnetic
structures. Polarized neutron beams are specially suited for that.
TABLE I: Structure factors F(hkl) of diffracted peaks in the L21 superstructure
N

F(hkl) = f n exp(2i(hx n + ky n + lz n ))
n=1

Miller indices (hkl)


All even: h + k + l = 4n
All even: h + k + l = 2n
All odd

Example
(220)
(200)
(111)

Structure factor
4 f Mn + 4 f Ga + 8 f Ni
4 f Mn + 4 f Ga 8 f Ni
4 f Mn 4 f Ga

Order
Simple Cubic
B2
L21

Fig. 2.- Comparison between x-rays and neutron diffractograms for two NiMnGa alloys in the
martensitic phase. Superstructure peaks are only visible in neutron diffraction. Ni52Mn26Ga22
(at%) has a tetragonal 5M modulated structure, while Ni49.2Mn30.5Ga20.3 (at%) is orthorhombic
7M modulated. Stars (*) indicate the peaks corresponding to the modulation.
b) issues
- A serious issue for neutron diffraction is the need for a large amount of sample. The beam
intensity is usually much weaker than x-ray ones and time is scarce so that at least one gram is
required for efficient powder diffraction data acquisition. For single crystals the mass is not so
important and 0.1 g can give enough signal.
- Another issue of neutron beams is that they are very expensive and only available at large
facilities. Beam time is accorded only after a panel discussion and under very competitive
conditions. That procedure delays the experiments by about 6 months from the proposal submission
and more from the experiment conception itself.
Regarding the subjects that have been explored by this technique in FSMAs, we can classify them
in the following groups:
a) Crystal structure and changes at the transition(s) and/or as a function of annealing or stress.
b) Order between atomic species in non-stoichiometric compounds
c) Magnetic structures and magnetic moment distribution among the different atomic species.
c) Phonon modes and special features at the transition.

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In this work we shall review only neutron diffraction studies, i.e. sections a) b) and c) above,
leaving phonon studies away as they are performed in very different instruments, like inelastic
neutron spectrometers, and have very different data analysis procedures. However, a number of
papers in this field have been very important to clarify the soft mode condensation for NiMnGa
alloys. They are listed under references [11-14]
The paper is organized in the following way: section 2 reviews the different neutron sources and
diffractometers currently available for experiments; section 3 is devoted to crystal structure and the
martensitic transition studies; section 4 deals with preferential atomic order in non-stoichiometric
compounds; section 5 refers to the magnetic studies, and section 6 summarizes the main
conclusions.
2 Neutron diffraction instrumentation
A number of large facilities for neutron diffraction exist all over the world. Probably the most
intense source is still the high flux reactor at the Institute Laue Langevin (ILL) located in Grenoble,
France, and run by a European consortium. An alternative to nuclear reactors are pulsed neutron
sources, based on the expallation mechanism, like ISIS at the Rutherford Appleton Laboratory,
Didcot, UK and LANSCE, at Los Alamos National Laboratory, New Mexico, USA. A new
generation of pulsed neutron sources is now taking the leadership. These include the SNS at Oak
Ridge, Tennessee, USA and the Parq-J at Tsukuba, Japan. They, however, are not at full operation
yet and the old facilities (both reactors and spallation sources) give most of the available data on
FSMAs today. In order to give an idea of the different instruments that can be used in FSMAs
research, we review below some of the actually used by the authors at the ILL:
High intensity two axis diffractometer with variable resolution D20
This instrument is a very high intensity diffractometer equipped with a large microstripe detector.
Due to the extremely high neutron flux a complete pattern, covering a wide scattering range, can be
obtained in a few seconds and followed as a function of temperature, pressure or other parameter.
Different monochromators allow using wavelengths between 1.07 and 2.41 . The variable
monochromator take-off angle, up to 120, increases the flexibility of the instrument, providing
high resolution over the complete diffraction pattern at the highest take-off angle with a neutron
flux of up to 107ns-1cm-2 or a high flux of up to 108ns-1cm-2 at medium resolution at lower take-off
angle.
Two axis diffractometer D1B
D1B is a high intensity powder diffractometer. Due to the high flux at 2.52 and the large multidetector, a fast detection of phase transitions can be obtained by scanning temperature. A complete
thermal variation of the diffraction patterns from 1.5 K up to 300 K can be achieved in few hours.
Moreover, the high spatial resolution, achieved at small angles, makes this instrument very
interesting for studies on magnetic structures.
High-resolution two axis diffractometer D2B
This high resolution two axis powder diffractometer is designed to achieve the ultimate resolution,
limited only by powder particle size. It is suitable to perform experiments on magnetism and high
resolution large d-spacing materials using wavelengths between 2.4 and 6 . A complete diffraction
pattern takes typically 30 minutes.
Four-circle Single crystal diffractometer D10
This instrument is a four-circle single crystal diffractometer that offers a high reciprocal-space
resolution and low intrinsic background. It can be used for crystallographic studies of nuclear and
magnetic structures. In the four-circle mode, it can be equipped with a helium-flow cryostat or a
hot-air furnace both with four-circle accessibility. Different wavelengths between 1.1 and 6
can be set up with the different available monochromators.
Thermal neutron diffractometer for single crystal D15
This diffractometer is used for the study of a wide range of physical problems including the
determination of magnetic phase diagrams. It is also used for determination of magnetic and nuclear
structure in preparation for spin density studies with polarized neutrons. Three wavelengths can be
set up ( = 0.885 , 1.176 and 1.54 ) with different flux at the sample.

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Spin polarised hot neutron beam facility D3.


D3 is a modular polarised neutron instrument used for the study of magnetization densities and
magnetic structures. The high field setup with vertical polarization, using a 10 Tesla magnet, with a
wide opening angle and the detector mounted on a lifting arm makes full use of the relatively short
wavelengths to explore the large positions of the reciprocal space. This setup allows studying para-,
ferro- and some antiferromagnetic form factor as well as magnetization distributions.

Fig. 3.- A single crystal of NiMnGa (marked by the blue arrow) is mounted on the D10, 4 circle
diffractometer at the ILL. The cryostat head is removed to see the crystal.
3 Crystal structure and Martensitic transformation
Crystal structure and its changes on temperature can be followed by either X-ray or neutron
diffraction. The latter is representative of the bulk of the sample and has several other advantages,
as mentioned above. Neutron thermo-diffractograms are easily obtained in several high flux
instruments on neutron beams. Particularly D20 at ILL is a suitable instrument for such studies.
The majority of elastic neutron scattering studies performed on NiMnGa alloys have been
confined to the stoichiometric composition or to compositions containing 50 at.% nickel. Webster
[15] and Soltys [16,17] performed much of the early work in exploring the room-temperature
structure of Ni2MnGa austenite. Webster et al. [1] and Brown et al. [8] later analyzed the
martensitic phase of the stoichiometric alloy and observed the tetragonal splitting characteristic of
the lower symmetry phase. Overholser et al. studied the B2 and L21 ordering transition in several
different Ni50MnxGa1-x alloy compositions (15 < x < 35) upon cooling from temperatures above
the melting temperature to 400K [18]. More recently, Sanchez-Alarcos et al. investigated the
influence of long-range L21 atomic order on the martensitic and magnetic temperatures as well as
on the magnetic moments in non stoichiometric NiMnGa alloys subjected to different thermal
treatments. Neutron diffraction, calorimetric and magnetic studies confirmed the dependence of the
transformation temperatures and magnetic moments on the degree of atomic order [19, 20].
Moreover, Glavatska et al. [21] and Cong et al. [22] reported neutron diffraction results on offstroichiometric compositions containing less than 50% Ni. Following this line of research, Ranjan
et al. [23] and Banik et al. [24] presented structural studies based on x rays diffraction experiments
in non stoichiometric compounds with 50% atomic Ni. In the last years, Righi et al. [25, 26] have
solved the crystal structure of non stoichiometric alloys by applying the superspace approach. They
determined an incommensurate structural modulation in the martensitic phase.
- off-stoichiometric NiMnGa alloys have also been studied by the authors, but these works are
mainly related to site occupancy of the different atomic species and will be discussed later, in
section 4.
- NiFeGa alloys have been studied recently by neutron diffraction [27, 28].
In these alloys the advantage of neutrons is not so evident as far as Ni, Fe and Ga have all positive
scattering lengths. Some of our neutron diffraction data on bulk samples, obtained in D1B, are
displayed in Fig. 4, as a representative example. Despite the thermo-diffractograms have neither

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77

great resolution nor a large span, they make possible to follow the transformation and gain some
insight into the austenite and martensite crystal structures. Noteworthy, that the strong preferential
orientation of the crystals is obvious due to the large changes of the diffraction patterns upon
minute angular changes of the sample orientation in the neutron beam. This texture prevents a
reliable structure determination. Only matching of the observed peaks with assumed structures is
possible.

Fig. 4.- Neutron thermo-diffraction of Ni55Fe19Ga26 obtained at the D20 diffractometer (ILL;
Grenoble, France). Temperature increases from the front (150 K) to the back (300 K) of the picture
as indicated by the arrow. Martensitic indexing (hkl)m is referenced to the cubic cell of the
austenitic phase.
The austenite phase match a L21 Heusler structure [29] but a considerable contribution of a cubic
solid solution (-phase) [30] has to be included to account for the main peaks. The mentioned strong
texture of the crystals can favor an inverse intensity ratio at many crystal orientations misleading
the amount of each phase present. The martensite phase is matched tentatively with a 14M
modulated orthorhombic cell [29, 30], although a restricted number of reflections are not enough to
make this assignation confident.
Further measurements at selected temperatures have been conducted by D20 diffractometer using
powder samples. This made possible to eliminate a texture influence whereby confirm
aforementioned structures. The transformation was also followed, by plotting the intensities of
some representative peaks as a function of the temperature (Fig. 5).

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Fig. 5.- Evolution of the integrated intensity with the temperature during a cooling process to
determined the martensitic start and finish transformation temperature for a NiFeGa alloy.
Further studies of the martensite modulated structure have been recently carried out in one of these
samples [31]. The modulated martensitic phase Ni55Fe19Ga26, stable at low temperature, was
determined by Rietveld refinement from neutron powder diffraction data obtained in D20
diffractometer of the ILL, working with wavelength 1.88 . The diffraction pattern was recorded at
150K, well within the temperature region of the martensitic phase stability. The structure
refinement shows that the martensitic phase exhibits an incommensurate modulated structure. As a
matter of fact, the actual modulated crystal structure represents a new martensitic phase in the
FSMA family with characteristics different from those encountered before.
The structural modulation of the Ni55Fe19Ga26 martensite was studied with a model, described in the
framework of superspace formalism, consisting of a (3+1)-dimensional structure having symmetry
I2/m(0)00 with a modulation vector q=0.3521c* (for details see Ref [25]). All the observed
reflections are fitted by either this modulated martensite or a -phase, excluding the presence of any
additional phase. This modulation vector significantly differs from those found in modulated NiMn-Ga martensites but the modulation function is close to that of Ni-Mn-Ga 14M modulation, so
that, although the atomic species and composition of martensitic phases are completely different,
the corresponding modulated structures belong to the same type.
Figure 6 shows a segment of this typical zig-zag stacking arrangement of nearly close-packed (00l)
atomic planes with the modulation function superimposed to the atomic positions. An approximated
three-dimensional representation of the incommensurate structure requires a large long-period
superstructure having 17 consecutive unit cells (q 6/17*c). Surprisingly, the single crystal
diffraction pattern calculated on the basis of this large superstructure shows the appearing of five
and not six satellites between main reflections as classical 14M modulation exhibits. TEM
investigations reported for Ni-Fe-Ga martensitic phase with similar composition show the presence
of a new modulated structure characterized by five satellites and called 6M [32, 33].

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Fig. 6.- 17-fold superstructure related to the incommensurate structure showing the zig-zag
distortion of the atomic layers perpendicular to the c axis for a NiFeGa alloy.
A further subject studied by neutron diffraction is variant reorientation under stress. This was done
recently in NiMnGa-polymer composites that show very large energy absorption and were
developed as efficient dampers. Such an study was already published in the former volume of this
series [34] and in other journals [35, 36] so that it will only be mentioned briefly here.
X-ray diffraction in NiMnGa alloys is less sensitive that way neutron diffraction to low angle peaks
that are the most representative of the variants orientation. Dynamic neutron experiments were
performed following in real time the diffraction of samples being simultaneously deformed. The
diffractometer was outfitted with a hydraulically driven Instron testing machine such that the strain
drive of the machine was used to trigger the acquisition of the neutron diffraction patterns, one
hundred 20 ms diffraction patterns were taken over each deformation cycle and this was repeated
over several hundreds of cycles, the corresponding diffraction patterns were added to achieve an
acceptable statistic. The stress and strain on the sample were also collected and excellent correlation
between strain and variant orientation was demonstrated.
4 Atomic order studies
The chemical order in NiMnGa alloys is increasingly disrupted as the composition deviates
increasingly from stoichiometric Ni2MnGa. Many of the compositions which show magnetic-field
induced strain are far from stoichiometry. A small degree of chemical disorder introduces defects
of a structural and magnetic nature that may alter the net magnetic moment per formula unit (FU)
and/or impede the motion of twin boundaries, in turn, affecting the output strain obtained. The
majority of elastic neutron scattering studies performed on NiMnGa alloys have focused on the
martensitic structure and did not address the state of chemical order or the magnetic moment in the
off-stoichiometic alloys.
In recent papers [37, 38] we reported neutron studies on non-stoichiometric alloys in order to
demonstrate the influence of composition on chemical order in the austenite phase. Neutrons are
specially suited for such studies. Changes in the diffracted intensities are depicted in fig 7. Because
the martensitic transition is diffusion-less, the obtained order is also preserved in the martensite. It
is found that for Ni concentrations of 50% or less the excess Mn occupies the vacant Ga and, if
available, Ni sites. For the nickel-rich compositions the excess Ni displaces Mn atoms from the
proper Mn sites, and the excess Mn and displaced Mn atoms occupy vacant Ga sites. No vacancies
have been found in the studied alloys to account for the excess and deficient species. Such models
were also tried, but did not provide a better fit to the observed pattern.

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Fig. 7.- Powder neutron ( = 1.37 ) diffraction patterns in the paramagnetic austenite phase
from different non stoichiometric samples. Intensities have been normalized and the baseline is
offset for each sample.
The chemical order so obtained is supported by elastic energy considerations. Because Ga is the
largest atom of the three present (Ga atomic volume, 11.9 cm3/mol [39]), Mn (7.4 cm3/mol [40])
could more likely occupy the larger sites and maintain its magnetic moment (Ni atomic volume is
6.59 cm3/mol [39]). The strain energy is reduced when excess Ni occupy Mn sites and the displaced
and excess Mn occupy Ga sites as compared to the case when all excess species occupy Ga sites.
The exact chemical order determination is important for determining the magnetic properties of
these alloys, a point developed in the next section.
Neutrons have been used recently to follow atomic ordering upon quenching and annealing by
Prez de Landazabal et al. A summary of his work can be found elsewhere in this volume [V
Snchez-Alarcos, JI Prez-Landazbal and V Recarte: Long-range atomic order in Ni-Mn-Ga
ferromagnetic shape memory alloys]
5 Magnetic structure determination
Direct magnetic structure determination from unpolarized neutron diffraction data is practically
impossible, due to the faint magnetic scattered intensity. Fig 8 shows the peak intensity evolution of
a single crystal through the Curie temperature, that demonstrates how magnetic intensity changes
are almost within the experimental error.
However, in NiMnGa alloys the magnetic moment distribution can be deduced from the
atomic position of Mn and Ni and the fact that Mn atoms a close distances couple
antiferromagnetically. The antiferromagnetic coupling between nearest neighbors Mn atoms is
expected due to the variation of the exchange interaction that becomes antiferromagnetic for small
interatomic distances, both in direct exchange (Bethe-Slater curve) and indirect exchange through
conduction electrons (RKKY interaction). The antiferromagnetic coupling has been predicted by
Enkovaara, et al. [41] in Mn-rich alloys, but the only elaborated model of the effect of chemical
order on the magnetic properties of off stoichiometry NiMnGa alloys is described in [37, 38].
In order to clarify the main assumptions of such a model we explicitly state the following
hypothesis:
a) The magnetic moment of the alloys is mainly localized at Mn atoms that carry 3.51 B each
b) Ni atoms also carry a small localized moment of 0.33 B
c) Mn atoms couple ferromagnetically when located at proper sites in the L21 structure
d) Mn atoms at shorter distances have antiferromagnetic interactions
e) Ni always couple ferromagnetically to proper sited Mn atoms
f) The magnetic moment does not change appreciably at the martensitic transformation.

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Fig. 8.- Magnetization under a 1 kOe applied field (full symbols) and structure factor square of the
(00-2) plane (open symbols) around the Curie Temperature of a NiMnGa single crystal.
The measured saturation magnetic moments of the alloys agree with calculated alloy moments for
excess or balance Ni under the assumption that Ni off site Mn moments couple
antiferromagnetically always with the net moment. However, for samples with large Ni
deficiencies, this preliminary model does not fit the experimental value and must be improved to
account for the behavior of defective Ni alloys.
The Ni-deficient samples present three different Mn-Mn distances that can affect the
exchange interaction: If a is the lattice constant in the cubic phase, Mn atoms on proper sites
(Mn/Mn) are at ( 2 /2)a from other Mn/Mn atoms, Mn atoms on Ni sites (Mn/Ni) are at ( 3 /4)a
from Mn/Mn ones, and finally Mn at Ga sites (Mn/Ga) are at a/2 in the cubic lattice. Similar
distances are obtained in the martensite structure. In samples with large Ni deficiencies, there are
Mn atoms at Ni sites, that present the shortest distance to the Mn/Mn and Mn/Ga atoms. In such a
case, the antiferromagnetic coupling between Mn/Ni and Mn/Mn or Mn/Ga atoms is stronger than
that between Mn/Ga and Mn/Mn ones and overcomes it. Consequently, in Ni deficient alloys, some
Mn/Ga and Mn/Mn atoms will couple ferromagnetically. Therefore the presence of Mn/Ni atoms is
decisive in the coupling between Mn/Ga and Mn/Mn atoms that can change from antiferromagnetic
to ferromagnetic.

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Table II. Magnetic moments of NiMnGa alloys determined experimentally at 5 K (exp.) and
calculated in the proposed model (calc.). The deviation of the model calculation and the
experimental value is shown as a % of the latter.
Alloy
Ni2MnGa
Ni43.8Mn37.8Ga18.4
Ni49.2Mn30.5Ga20.3
Ni50.2Mn29.0Ga20.8
Ni52.1Mn26.0Ga21.9
Ni52.9Mn25.6Ga21.5
Ni51.4Mn26.6Ga22.0
Ni50.4Mn27.5Ga22.1
Ni49.6Mn28.6Ga21.8
Ni48.3Mn29.8Ga21.9

exp.(5 K) (B/FU)
4.17
3.06
3.41
3.60
3.59
3.37
3.63
3.83
3.99
3.39

calc.(B/FU)
4.17
2.96 (3.3%)
3.46 (1.5%)
3.55 (1.2%)
3.48 (3.1%)
3.31 (1.9%)
3.57 (1.7%)
3.71 (3.1%)
3.69 (7.4%)
3.62 (6.9%)

Such a combination of atomic positions determined by ND, and exchange considerations give
proper account of the observed moment (Table II). However, actual magnetic moment
determination needs polarized neutron diffraction. Previous studies for the stoichiometric
composition were presented by Brown et al. [8].
We have performed such studies on two selected off-stoichiometric samples in the D3
diffractometer at the ILL [42- 44], and the following conclusions were attained:
- Magnetic moment density maps show a localized moment in the Mn and Ni atoms, while there is a
negative spin density in the interatomic positions that could be assigned to a magnetic polarization
of the conduction band electrons.
- Neutron polarization diffraction measurements for Ni52Mn26Ga22 and Ni52Mn26Ga22 samples show
that Mn atoms at Ga positions couple antiferromagnetically to the properly-sited Mn ones in the
austenite phase. These results confirm the assumptions of the model described previously.

Fig.9.- Spin density map in the Mn-Ga (110) plane for Ni52Mn26Ga22 at 300K and under 2T
magnetic field

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6 Conclusions
As a simple conclusion, we can state that neutron diffraction is an extremely valuable tool for
studies of crystal structure, phase transitions and magnetism in FSMAs. The results so far
summarized indicate that the technique has a promising future and will be of general use in the
field. Although powder techniques and even single crystal diffraction are commonly used at
present, a further need of polarized neutron techniques is seen, in order to get a deeper knowledge
of the magnetic structure of these alloys.
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memory alloys, presented at the E-MRS 2010 Spring Meeting. Strasbourg, France
[44] J. M. Barandiarn, Magnetic moment distribution in non-stoichiometric Ni-Mn-Ga
ferromagnetic shape memory, presented at the V meeting of the Spanish Society of Neutron
Users (SETN) Oviedo 2010. To be published on Journal of Physics: Conference Series.

(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.85

Influence of Long-Range Atomic Order on the Structural and Magnetic


Properties of Ni-Mn-Ga Ferromagnetic Shape Memory Alloys
V. Snchez-Alarcos a, J. I. Prez-Landazbalb and V. Recartec
Departamento de Fsica, Universidad Pblica de Navarra, Campus de Arrosada, 31006
Pamplona, Spain
a

vicente.sanchez@unavarra.es, bipzlanda@unavarra.es, crecarte@unavarra.es

Key words: Atomic order, Ferromagnetic shape memory, Ni-Mn-Ga, Martensitic transformation,
Curie temperature, Thermal Treatments.

Abstract. This chapter presents a review of the most recent and systematic works performed on the
study of the effect of atomic order on the structural and magnetic properties of Ni-Mn-Ga
ferromagnetic shape memory alloys. It is shown that a correlation between long-range atomic order
and the martensitic and Curie temperatures can be established from the analysis of its evolution
under high and low temperature thermal treatments. In particular, it is demonstrated that,
irrespectively of the thermal treatment, both transformation temperatures increase with the
increasing L21 atomic order degree, showing practically the same linear dependence on the nextnearest-neighbors atomic order parameter, in such a way that the effect of the atomic order on the
relative stability between austenite and martensite can be quantitatively determined. In this respect,
it is shown that the effect of atomic order on the martensitic (and also the premartensitic)
transformation is directly related to the variation of the magnetic exchange coupling.
1. Introduction
Ferromagnetic shape memory alloys (FSMA) have awakened a great interest over the last few years
since, together with the properties of the conventional shape memory alloy, such as superelasticity
and shape memory behavior, some other peculiar properties have been found to arise from the
coupling between structure and magnetism. The most interesting one is the possibility of achieving
extremely large strains as a consequence of the application of an external magnetic field, the socalled magnetic shape memory (MSM) effect, which results especially interesting for practical
application in magnetic sensors and actuators [1]. MSM originates from the magnetic-field-induced
rearrangement of the crystallographic domains (twin variants) formed as a result of a thermoelastic
martensitic transformation (MT); a solid-solid displacive, diffusionless, first order transition taking
place from a high-symmetry high temperature phase called austenite to a lower-symmetry low
temperature phase called martensite [2]. The fundamental requirement for obtaining large magneticfield-induced strains (MFIS) is to have a ferromagnetic twinned martensite structure showing high
magnetic anisotropy and a low twinning stress [3]. Likewise, MSM effect can be also obtained from
the magnetic field-induction of the MT (MFIMT), although higher applied fields are usually
required [4]. In this sense, it has been recently shown that, in some alloys, the fact that the
magnetization of the martensitic phase is lower than in the austenitic phase may favour the MFIMT
[5]. Alongside MSM, several interesting properties associated to the occurrence of a MT in a
ferromagnetic material, such as the magnetocaloric effect and magnetoresistance, are being
extensively investigated because of its potential applications in magnetic refrigeration and sensing,
respectively [6,7].
MSM was first reported in 1996 in a Ni-Mn-Ga alloy closed to the stoichiometric composition
Ni2MnGa [8]. Stimulated for the extraordinary high strains achieved in these alloys, up to 10% [9],
numerous works devoted both to understanding and modeling the MSM effect and to the
characterization and optimization of the structural and magnetic properties of this alloys system has
been performed during the last decade [10]. In parallel, an exhaustive research for new FSMA
showing better magneto-mechanical properties than Ni-Mn-Ga alloys has been also carried out [11].
Up to now, MSM properties has been reported in Ni-Mn-X (X=Ga, In, Sb, Sn, Al) [12-15], Ni-FeGa [16], Co-Ni-Ga [17] and Co-Ni-Al [18] Heusler alloys, as well as in some Fe-based alloys such
as Fe-Pd or Fe-Pt [19,20]. Nevertheless, the highest MFIS are still found in the Ni-Mn-Ga, which
are by far the most studied FSMA and, indeed, the prototype MSM system.

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Ni-Mn-Ga FSMA are Heusler alloys. Heusler alloys are intermetallic compounds with the
stoichiometric formula X2YZ showing a L21 crystallographic structure (space group Fm 3 m ). This
structure consists on four interpenetrating fcc sublattices, as shown in Figure 1. In the Ni2MnGa
stoichiometric compound, Mn atoms occupy the (i) sublattice, Ga atoms the (ii) sublattice, and Ni
atoms the (iii) and (iv) sublattices (Figure 1b). Actually, on cooling through the equilibrium phase
diagram, Ni-Mn-Ga alloys do not solidify directly from the melt to the Heusler L21 phase but to a
bcc CsCl-type B2 structure (space group Pm 3 m ) in which the Ni atoms occupy the centre of a cube
whose vertices are occupied by Mn and Ga atoms randomly distributed (Figure 1a). The austenitic
L21 Heusler phase is then reached through a B2-L21 ordering process taking place on further
cooling, at temperatures around 1000K though slightly depending on composition [21-27]. As
shown in the figure, the next-nearest-neighbors atomic ordering process makes the L21 cubic lattice
parameter be twice the B2 one. The thermoelastic MT takes place from the ordered L21 austenite to
a martensitic phase [28], which, due to the diffusionless character of the transformation, inherits the
austenite atomic order. This structural transformation is driven by a Jahn-Teller mechanism and its
origin relies on the Fermi surface nesting [28-30]. The martensitic phase may display several
crystallographic structures depending on composition, though the most common are the L10
tetragonal structure (T martensite), whose relation with the L21 structure is shown in Figure 1c, and
the modulated structures resulting from its monoclinic distortion at 10 and 14 atomic layers along
the cubic <110> directions (10M and 14M martensite, respectively) [31-32]. The MT temperature,
Tm, also depends strongly on the alloy composition, and the compositional dependence has been
traditionally described as a function of the electron per atom ratio, e/a, just as it occurs in the HumeRothery compounds [33,34]. In some Ni-Mn-Ga alloys, the MT is preceded by a weak first order
transformation from the austenitic cubic phase into a near-cubic intermediate phase with a sixlayered modulation [35,38]. Such premartensitic transformation is attributed to the strong
magnetoelastic coupling on these alloys [39].

iv
ii
iii
i

Fig. 1: Crystal structures on Ni-Mn-Ga. (a) High temperature B2 structure, (b) L21 austenitic
structure, and (c) tetragonal L10 martensitic structure. Ni (black), Mn (grey) and Ga (white).
As most of Heusler alloys in which the X and/or Y elements are 3d transition metals, Ni2MnGa
alloys show magnetic order. In these alloys (and, in general, in all those Heusler alloys in which the
Y elements is Mn) the magnetic moment is confined to the Mn atoms, and it shows a value typically
around 4B [40,41]. The ferromagnetism on Ni-Mn-Ga is therefore due to the ferromagnetic
coupling between the Mn atoms, in which the magnetic moment of the alloy is mainly located, and,
in a lesser extent, to the Ni-Mn coupling [40,43]. Since the magnetic Mn atoms are not in direct
contact, the exchange mechanism is indirect through the conduction electrons. The indirect nature
of the magnetic exchange explain the fact that, in spite of the magnetic moment is almost the same
in all Ni-Mn-based alloys, magnetic properties such as the Curie temperature (TC) or even the type
of magnetic ordering (that is, ferromagnetism of antiferromagnetism) may be so different depending
on the third element [44]. In this sense, the main role of the X element is the determination of the
lattice parameter, whereas the Z element modifies the electron concentration and then the exchange
intensity.

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1.1 Atomic order in Ni-Mn-Ga. The structural and magnetic properties of the Heusler alloys
strongly depend on the configurational ordering of the constituting elements in the crystal lattice. In
particular, the change of long-range atomic order (LRO) affects both the MT and the alloy magnetic
moment due to the modification of both the electronic structure and the lattice sites occupancy by
the magnetic atoms. The atomic order degree is usually evaluated in terms of the occupation of the
sublattices in Fig. 1b by the element A, p sA , where A can be Ni, Mn or Ga (s=i, ii, iii or vi). Since
the L21 structure is characterized by piA piiA p Aiii = p Aiv p Ai , the L21 atomic order degree may be
expressed (if the B2 next-neighbors atomic order remains constant) by means of the order
ii
i
parameter, L 21 = pGa
pGa
, which range from 1 for the maximum next-nearest-neighbors atomic
order allowed by stoichiometry to 0 for the absence of L21 atomic order.
The atomic order can be modified either by changing the alloy composition or by subjecting an
alloy to different thermal treatments. With respect to the composition, it has been shown that the
configurational order is not trivial, in the sense that the excess of atoms with respect to the
Ni2MnGa stoichiometry does not always occupy those sublattices corresponding to the elements in
defect. In turn, it has been demonstrated that the alloys with less than 50% nickel have the excess
Mn atoms occupying Ni and Ga sites, Ga-rich alloys have the excess Ga atoms occupying the Mn
sublattice no matter if Mn is deficient or not, and Ni-rich alloys have the Ni excess occupying Mn
sites while the Mn excess occupies Ga sites [45,46]. On the other hand, both first principle
calculations and experimental measurements have demonstrated that Mn atoms in Ga sites couple
antiferromagnetically with Mn atoms in the correct Mn sublattice [47]. This leads to a reduction of
the magnetic moment of the alloy which is reflected, for example, in a reduction of the Curie
temperature and the saturation magnetization.
When studying the effect of atomic order on the MT, the modification of the alloy composition is
not a useful procedure since it implies the modification of e/a, which highly affects the MT.
Therefore, most of the studies on the correlation between LRO and the structural and magnetic
properties of Ni-Mn-Ga alloys are based on the modification of atomic order through thermal
treatments. In this sense, Kreissl et al. shown that Tm of a Ni2MnGa stoichiometric compound
decreased from 200K to 100K when the quenching temperature increased from 1073K to 1273K,
associated to an increase of the quenched atomic disorder [48]. On the other hand, Hosoda et al.
analyzed the relation between LRO and the thermal characteristics of almost stoichiometric, Mnrich and Mn-poor alloys [49]. They demonstrated that the next-nearest-neighbors atomic order
degree in quenched alloys decreases on increasing the quenching temperature, and that the
modification of both Tm and TC may be linearly related to the squared L21 and B2 order parameters.
The martensitic structure, in turn, seems to be unaffected by the quenching temperature [50]. It has
been also shown that both Tm and TC of a quenched off-stoichiometric alloy increase upon postquench low-temperature aging treatments, as a consequence of the increase of the L21 atomic order
degree [51]. Meanwhile, the effect of atomic order on the relative stability between martensitic
structures was analyzed by Segu et al [52].
During the last four years, we have performed several systematic studies on the effect of longrange atomic order on the structural and magnetic properties of Ni-Mn-Ga FSMA [53-56]. In these
works, the relation between the atomic order and the structural and magnetic transformation
temperatures has been analyzed from the comparison of their respective evolutions under common
thermal treatments. This allowed us to establish a quantitative correlation between atomic order and
the MT temperatures as well as some interesting conclusions about the effect of magnetism on the
MT. The aim of the present chapter is precisely to review such recent works. In order to do so, the
chapter is organized in three parts; in the first and second parts (sections 2 and 3) the effect of high
and low temperature thermal treatments on the LRO as well as on the structural and magnetic
properties is summarized, and in the third one (section 4) the obtained results are analyzed in terms
of the influence of magnetism on the martensitic transformation.

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2. High temperature thermal treatments


Annealing at high temperature followed by quenching into air or ice water is probably the most
common thermal treatment applied to Ni-Mn-Ga alloys. Usually, this method is only used to
provide a known and repeatable thermal history to the alloy, since, contrary to what occurs in other
shape memory alloys, such as Fe-Pd or Cu-based ones, in Ni-Mn-Ga there is no need to quench any
metastable phase from what the MT can proceed. As mentioned above, such thermal treatments
considerably affect the structural and magnetic properties of Ni-Mn-Ga alloys due to the
modification of the atomic order. The correlation between the physical properties and the atomic
order can be established from the comparison between its separate evolutions under the same
thermal treatments.
The annealing temperature affects both Tm and TC of the quenched alloys. This can be seen in
Figure 2a, where the transformation temperatures of a polycrystalline Ni49.5Mn28.5Ga22 (at%) alloy
annealed 30 minutes at different temperatures (1173K, 1073K, 973K and 873K) and then quenched
into ice water are shown as a function of the quenching temperature, Tq [53]. Similar variations
(around 18K) are observed in both transformation temperatures, which experience a parallel
decrease as the quenching temperature increases up to 1073K, and a subsequent increase as the
quenching temperature increases up to 1173K. Likewise, magnetic properties such as the saturation
magnetization (MS) of the martensitic phase are also considerably affected by the quenching
temperature. This is shown in Figure 2b, where the Ms values were obtained from the fitting of the
temperature dependence of the low-temperature magnetization under 6T (inset) to the Bloch law
M = M S (1 3/ 2 ) , whit a fitting parameter. It can be seen that the evolution of MS is similar to
that of the transformation temperatures.

Fig. 2: (a) MT and Curie temperatures obtained from DSC measurements (inset) as a function of
the quenching temperature. (b) Saturation magnetization as a function of the quenching
temperature. Inset: temperature dependence of the magnetization under a 6T applied magnetic field.
The long-range atomic order can be determined from neutron diffraction measurements. The
typical powder neutron diffractogram corresponding to the L21 austenitic structure is shown in
Figure 3a, where the intensity peaks have been indexed according to the associated Bragg
reflections [53]. Concerning the values of the unit cell structure factor corresponding to the different
types of ordering, three classes of reflections can be considered in the austenite diffractogram: (i)
superstructure reflections exclusively produced by the L21 type of ordering, in which the h, k, l
indices are all odd, (ii) superstructure reflections linked to the B2 ordering, with even h, k, l indices
satisfying (h+k+l)/2 = 4n + 2 (n integer), and (iii) fundamental reflection associated to the
disordered bcc lattice (A2 order), for which the h, k, l indices are all even and h+k+l = 4n (n
integer) is satisfied.

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Fig. 3: (a) Measured neutron diffraction pattern (dots), calculated profile (full line) and difference
between the measured and calculated profiles (dashed line) for the austenitic phase at 415K of a
Ni49.5Mn28.5Ga22 alloy slowly cooled from 1173K. (b) Temperature dependence of the integrated
intensity of the (111) and (200) reflections on a Ni49.5Mn28.5Ga22 alloy quenched from 1173K.
The evolution of the next-neighbors and the next-nearest-neighbors atomic order under certain
thermal treatments can be then estimated from the evolution of the integrated intensity of the
reflection peaks exclusively linked to such types of ordering. Figure 3b shows the temperature
dependence of the integrated intensity of the (111) and (200) reflections associated to the L21 and
B2 order, respectively, divided by the integrated intensity of the fundamental (220) reflection in
order to compensate the Lorentz and Debye-Waller factors [53]. The (111) intensity, and therefore
the L21 atomic order, experiences a drastic fall on heating above 750K until it completely vanishes
at the L21B2 ordering temperature (T0~1050K). Therefore, some retained L21 disorder is always
expected when the alloy is quenched from temperatures above 750K. In this sense, a B2 structure
could be also expected when quenching from above T0. However, up to now it has not been possible
to quench a perfect B2 order, and a L21 austenitic structure is always obtained. Rietveld structural
refinements performed from powder neutron measurements on a Ni49.5Mn28.5Ga22 alloy both slowly
cooled and quenched from 1173K confirms that, in effect, the alloy displays a L21 structure in both
cases (Table 1) [53].
Table 1: Structural parameters obtained from Rietveld refinement on a Ni49.5Mn28.5Ga22 alloy.
Sample

Atom

Wyckoff
letter

Slowly cooled
a = b = c = 5.8309 []

Mn 1
Ga 1
Mn 2
Ni
Mn 1
Ga 1
Ga 2
Mn2
Ni

4a
4b
4b
8c
4a
4a
4b
4b
8c

As-quenched
a = b = c = 5.8257 []

Position
X
0
0.5
0.5
0.25
0
0
0.5
0.5
0.25

Y
0
0.5
0.5
0.25
0
0
0.5
0.5
0.25

Occupancy
Z
0
0.5
0.5
0.25
0
0
0.5
0.5
0.25

1
0.9
0.1
1
0.95
0.05
0.88
0.12
1

Nevertheless, the analysis of the occupancy parameter indicates that, in effect, the quenching
process affects the next-nearest-neighbors atomic order degree. In the slowly cooled alloy, the
excess of Mn atoms occupy the Ga sublattice, in such a way that the obtained occupancies
correspond to the maximum degree of LRO allowed by stoichiometry. In the as-quenched alloy, in
turn, the presence of Ga atoms in the Mn sublattice and the higher amount of Mn atoms in the Ga

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sublattice indicates a lower L21 order degree. On the other hand, it is worth noting that the
martensitic structure is not affected by the atomic order variation, as shown in Figure 4, where it
can be seen that, irrespectively of the thermal treatment, the powder neutron diffractograms below
Tm correspond to the 14M modulated martensite [53].

Fig. 4: Diffractograms corresponding to the


martensitic phase at 273K on a Ni49.5Mn28.5Ga22
alloy quenched from 1173K, and 873K, and
slowly cooled from 1173K.

The effect of quenching on the L21 atomic order can be estimated from the analysis of the
integrated intensity of the (111) reflection on the alloy just quenched from different temperatures, as
shown in Figure 5a. The L21 intensity decreases as Tq increases up to 1073K, and then slightly
increases when Tq increases up to 1173K. Surprisingly, the sample quenched from 1073K is even
more disordered than the sample quenched from 1173K. This fact could be attributed to the
presence of a higher vacancy concentration at 1173K which may favor the atomic ordering, as
assumed in Ni-Fe-Ga alloys [57]. In any case, the evolution of the atomic order is practically the
same than that of Tm, TC and MS (Figure 2), so a direct relation between such magnitudes and the
long-range atomic order may be inferred. In fact, a quantitative correlation between LRO and the
transformation temperatures can be estimated if the intensity values in Figure 5a are normalized
taking into account that the slowly cooled alloy show the maximum L21 atomic order degree (that
is, Ls 21c = 1 ).

Fig.5: (a) Integrated intensity of the (111) reflection of a Ni49.5Mn28.5Ga22 alloy as a function of the
quenching temperature. (b) MT and Curie temperatures as a function of the L21 atomic order
degree.
The correspondence between the L21 atomic order degree and the transformation temperatures is
shown in Figure 5b. It can be seen that Tm and TC show an almost linear dependence on , in such a
way that the correlation can be quantitatively expressed just by giving the equation of the linear

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trend shown in the figure. It is interesting to note that the dependence of Tm and TC on is
practically the same. This seems to point out that the MT may be highly influenced by the
magnetism, as suggested from theoretical results [58]. This fact will be analyzed in the two next
sections. On the other hand, taking into account that the Mn atoms at the Ga sublattice couples
antiferromagnetically with the Mn at the correct sublattice, the decrease on the saturation
magnetization with the increasing quenching temperature may be explained as a consequence of the
increase of the antiferromagnetic coupling with the decreasing , which leads to a decrease of the
magnetic moment.
3. Low temperature thermal treatments
We have just seen that the low L21 atomic order present at high temperatures is partially retained as
a consequence of the quenching process. The L21 order degree on the as-quenched alloys is
therefore lower than the equilibrium value, which is only obtained after a slow cooling treatment.
Nevertheless, if the as-quenched alloys are heated up to temperatures at which atomic diffusion is
possible, an ordering process may proceed leading to the restoring of the equilibrium order degree
of the alloy. This metastable-to-stable, and therefore irreversible, ordering process can be easily
detected from calorimetric measurements due to the appearance of an exothermic peak in the DSC
thermograms. Because of the irreversible character of the ordering process, the associated
exothermic peak is only observed in the first post-quench heating ramp, and it appears neither in the
cooling ramp nor in the subsequent aging treatments. The exothermic peaks associated to the postquench ordering process on a Ni49.5Mn28.5Ga22 alloy quenched from different temperatures are
shown in Figure 6a. The ordering process takes place at temperatures between 550K and 650K,
depending on the quenching temperature. In fact, the temperature of appearance of the ordering
process linearly depends on the quenching temperature, as shown in Figure 6b, where the
temperature of the peak maximum, TP, has been taken as the ordering temperature.

Fig. 6: (a) DSC thermograms on a Ni49.5Mn28.5Ga22 alloy quenched from 873K, 973K, 1073K and
1173K. (b) Temperature of the ordering exothermic peak as a function of the quenching
temperature.
The correspondence between the DSC exothermic peaks and the increase of the L21 atomic order
can be checked by studying the evolution of the atomic order under the same post-quench heating
treatments. This is shown in Figure 7, where the evolution of the integrated intensity of the (111)
reflection (associated to the L21 atomic order) of the Ni49.5Mn28.5Ga22 alloy quenched from 1173K is
now shown on heating up to 1173K and on subsequent slow cooling [53]. It can be seen that, as
shown in the previous section, the L21 intensity on the as-quenched sample is lower that that slowly
cooled one, and that, in effect, the next-nearest-neighbors atomic order of the as-quenched sample
increases with the increasing temperature until the maximum order degree (that is, that of the slowly

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cooled sample) is reached around 700K. The temperature range in which the atomic order of the asquenched alloy increases agrees indeed with the temperature range for the DSC exothermic range

Fig. 7: Temperature dependence (heating and


subsequent cooling) of the integrated intensity of the
(111) reflection on a Ni49.5Mn28.5Ga22 alloy
quenched from 1173K

The kinetics of the L21 ordering process associated to the high temperature DSC exothermic peak,
and in particular its activation energy, may be investigated using the well-known Kissingers
method, which is based on the analysis of the variation of the DSC peak temperature as a function
of the heating rate [59]. In this method the activation energy of a thermally activated process can be
obtained from the equation

E
Ln 2 = a + B
R TP
TP

(1)

where TP is the temperature of the peak maximum, is the heating rate, R is the ideal gas universal
constant, Ea is the activation energy and B is a constant. The DSC thermograms obtained at
different heating rates on the alloy just quenched from 1173K are shown in Figure 8a, where, in
order to check the irreversibility of the ordering process, the displayed thermograms consist of two
consecutive heating curves recorded between 265K and 673K [56].

Fig. 8: (a) DSC thermograms obtained at different heating rates on the Ni49.5Mn28.5Ga22 alloy just
quenched from 1173K, and (b) evolution of Ln / TP2 against 1/TP for that alloy.

2
Figure 8b shows the plot of Ln / TP against 1/TP for the quenched alloy. Taking into account
that the slope of the linear fit shown in the graph is equal to -Ea/R (Eq.1), an activation energy Ea =
1143 kJ/mol (= 1.18 eV) is obtained for the pos-quench ordering processes. Such activation energy

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varies with the quenching temperature, in such a way that, for example, the activation energy
obtained for the same alloy quenched from 873K is slightly higher, Ea = 1443 kJ/mol. In any case,
it is worth noting that those values are very close to the experimental value of the activation energy
of the Mn self-diffusion, Ea(Mn) = 1143 kJ/mol, recently obtained from radioactive tracers
measurements performed on a stoichiometric Ni2MnGa alloy [60]. This is in agreement with the
observed fact that the ordering process mainly consists on the diffusion of Mn atoms from the Ga
sublattice to their its own sublattice (table 1). Furthermore, it means that the temperature of the
post-quench ordering process is directly related to the temperature required for the Mn diffusion to
begin. In this sense, the dependence of the exothermic peak temperature on the quenching
temperature shown in Figure 6 points out that the L21 atomic disorder favors the Mn diffusion
assisting the ordering process, which is in perfect agreement with observed increase of the
activation energies when the quenching temperature is decreased from 1173K to 873K.
The L21 atomic order variation taking place as a result of the consecution of the post-quench
ordering process also affects the structural and magnetic properties of Ni-Mn-Ga alloys. The effect
of post-quench thermal treatments on the MT and Curie temperatures can be directly estimated from
the analysis of the DSC thermograms obtained on the as-quenched sample subjected to several
consecutives heating/cooling thermal cycles performed between 273K and a maximum temperature
higher for each new cycle (Figure 9a), in such a way that each thermal cycle is equivalent to a lowtemperature aging treatment. This procedure makes possible to observe in-situ the evolution of Tm
and TC (obtained from the forward MT peak on cooling and from the step on the baseline slope,
respectively) as a consequence of the partial development of the ordering process.

Fig. 9: (a) DSC thermograms performed on several consecutive thermal cycles. (b) Increment on
the transformation temperatures of a Ni49.5Mn28.5Ga22 alloy quenched from 1173K, as a function of
the post-quench aging temperature (DSC exothermic peak overlapped).
Figure 9b shows the increment on Tm and TC as a function of the post-quench aging temperature,
Taging, corresponding to the maximum temperature of the DSC cycles [53]. In can be seen that, once
Taging lies inside the temperature range of the DSC exothermic peaks associated to the L21 ordering
process, both transformation temperatures increase on heating up to Taging. Furthermore, the
transformation temperatures show a parallel increase as a consequence of the increase of the L21
atomic order degree, just as it occurred as a consequence of quenching (Figure 2a). The same
parallel evolution of Tm and TC under post-quench aging is observed for the alloy quenched from
different temperatures, though as the quenching temperature decreases the observed variation is
lower and takes place at higher temperatures [53]. It is also worth mentioning that just a slight
decrease (around 2K) on the thermal hysteresis associated to the MT is observed as a consequence
of the ordering process, as shown in Figure 10.

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Fig. 10: Thermal hysteresis associated to the MT,


as a function of the post-quench aging
temperatures, for a Ni49.5Mn28.5Ga22 alloy
quenched from 873K, 973K, 1073K and 1173K
[55].

3.1 Magnetic properties. The increase of the atomic order caused by the low-temperature postquench aging treatments also affects the magnetic response of Ni-Mn-Ga alloys. The evolution of
the low field magnetization (100 Oe) in both the austenitic and the martensitic phases as a result of
the ordering process is plotted in Fig. 11a as a function of the aging temperature [54]. The data have
been extracted from the cooling curves of the magnetization measurements performed on the alloy
quenched from 1173K and then heated up to several temperatures (see inset). It can be seen that, in
both cases, an initial decrease is followed by an increase of the magnetization versus the aging
temperature, coinciding with the development of the ordering process.

Fig. 11: (a) Magnetization under a 100Oe applied magnetic field at 260K (martensite) and 330K
(austenite), as a function of the post-quench aging temperature, for a sample quenched from 1173K.
Inset: temperature dependence of the low field magnetization on cooling/heating between 400K and
250K. (b) Evolution of the saturation magnetization with the post-quench aging temperature. Inset:
temperature dependence of the magnetization on cooling from 100K to 10K under 6T.
On the other hand, Figure 11b shows the evolution of the saturation magnetization of the
martensitic phase against the post-quench aging temperature, where Ms was calculated from the
fitting of the temperature dependence of the magnetization at 6T in the as-quenched state and after
thermal treatments to the Bloch law (see inset) [54]. Again the development of the ordering process
considerably modifies the magnetization of the alloy. In fact, the behavior of the magnetization at
low and high magnetic fields is the same. Focusing on the high aging temperature behavior (above
473 K), the coexistence of ferromagnetic and antiferromagnetic MnMn interactions can explain
the influence of the atomic ordering on the magnetic properties of the alloy. In particular, the

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increase of the Curie temperatures and the high field magnetization during the ordering process can
be related to the redistribution of Mn atoms inside the L21 crystallographic cell. The disordered
alloy has more Mn atoms in the Ga sites (next nearest neighbor) that couples antiferromagnetically
to the Mn atoms at the Mn sites. At the same time, the Mn sites are occupied by Ga atoms, in such a
way that the ferromagnetic coupling, and then the effective magnetic moment of the alloy, is
reduced. On the contrary, as the L21 order degree increases, the Mn atoms comes to occupy their
own sublattice, which favors the ferromagnetic coupling between Mn atoms and therefore the
increase of the magnetic moment and TC of the alloy (the modification of the electronic structure of
Mn atoms as a result of annealing has been recently proved [61]). It must be mentioned that the
coupling between the low magnetic moment in the Ni atoms and the Mn atoms has been neglected.
With respect to the small decrease observed in both the high and low field magnetization when
the as-quenched alloy is heated up to 473 (below the ordering process), the same reasoning could
lead to related it to some loss of next-nearest-neighbors atomic order during the early stages of the
ordering process. In particular, the magnetization decrease could be due to the increase of the
antiferromagnetic coupling at some of the intermediate phases of the six-jump-cycle (6JC)
mechanism proposed for the atomic diffusion in the L21 structure [60]. However, no significant
variation of the L21 LRO is observed from neutron diffraction measurements on heating the asquenched alloy below 500K.
3.2 Single-crystal measurements. The correlation between the post-quench ordering process and
the structural and magnetic transformation temperatures has been also established on a singlecrystalline Ni49.4Mn27.7Ga22.9 alloy. Figure 12a shows the integrated intensity of the (111) reflections
measured at 415 K on the alloy as-quenched from 1173K, before and after heating it up to 600K
and 673 K, that is, under the same thermal cycle performed in the DSC measurements from which
the evolution of Tm and TC was determined (see inset) [56]. Again, the superstructure reflection
intensity increases with the increasing aging temperature, thus confirming that an ordering process
occurs when the single-crystal is heated up to the DSC exothermic peak temperature. In this case,
the degree of L21 atomic order in the alloys can been estimated by normalizing the intensity values
in figure 12a by considering that the L21 atomic disorder retained after quenching the SC alloy is
completely restored once the alloy is heated up to temperatures above the DSC exothermic peak
[53].

Fig. 12: Integrated intensity of the (111) reflection of a single-crystalline sample quenched from
1173K, as a function of the aging temperature. (b) Tm and TC of the single-crystalline sample
quenched from 1173K and then heated up to 600K and 673K, as a function of the L21 atomic order
degree.

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The dependence of the transformation temperatures on the L21 order parameter is shown in Figure
12b. Again, Tm and TC show almost the same linear dependence on , just as it occurred in the
polycrystalline alloy quenched from different temperatures (Figure 5b). In fact, the dependences of
Tm and TC on are almost identical for both alloys despite different thermal treatments were applied
to change the atomic order, in such a way that a common linear dependence is obtained if we plot
the shift on the transformation temperatures of both the quenched polycrystalline alloy and the postquench aged single-crystal as a function of the shift on (Figure 13) [56]. The equation of the linear
trend shown in the graph is the first quantitatively correlation established between the MT and
Curie temperatures and the L21 LRO on Ni-Mn-Ga alloys.

Fig. 13: Shift of the transformation temperatures as


a function of the shift on the degree of L21 atomic
order.

From the above results, the effect of the L21 atomic order on the relative stability between the
austenitic and the martensitic phases can be quantitatively determined from the change in the free
energy difference between both phases. This change can be represented as

G aust mart = S aust mar Tm

(2)

where S
is the entropy change per unit volume associated to the MT and Tm is the shift
on the MT temperature due to the variation of the atomic order. The latter shift can be expressed as
Tm = L 21 , where is the slope of the linear curve shown in Figure 13, so Eq. (2) yields
aust mart

G aust mart = S aust mar L 2

(3)

The rate of the free energy change as a function of the degree of L21 atomic order can be then
expressed as

G aust mart
= S aust mar
L 2

(4)

The entropy change at the MT has been calculated from the DSC thermograms obtained on both
the single-crystal and the polycrystalline alloys subjected to the corresponding thermal treatments as
aust mart
is the enthalpy change at the MT and T0 represents
S aust mart = H aust mart / T0 , where H
the mean value between the reverse and forward MT temperatures. A mean value
S aust mart = 12 1mJ / gK has been obtained in both alloys, in such a way that Eq. (4) yields

V.A. Chernenko

97

G aust mart
= 0.774 Jg 1 46.44 Jmol 1
L 2

(5)

This quantitative evaluation of the effect of atomic order on the MT in Ni-Mn-Ga alloys can be
compared, for example, with the result on the relative stability between the 14M and T martensites
in Ni-Mn-Ga alloys, G 14 M 2 M / L 21 25 Jmol 1 , obtained by Segu et al. [52]. It can be seen
that the rate of the free energy change as a function of the degree of L21 atomic order is slightly
higher (in absolute value) in the case of the MT. Nevertheless, it is worth noting that the shift of the
14MT intermartensitic transformation temperature is, in turn, much higher than the shift of the
MT temperature under similar variations of [52]. This is due to the fact that the different
martensitic structures are energetically closer than austenite and martensite, as inferred from the fact
that the entropy change at the intermartensitic transformation is almost 10 times lower than the MT
entropy [62], in such a way that, under similar G / L 2 rates, lower S leads to higher (Eq.4)
1

4. Influence of magnetism on the martensitic transformation


It is especially interesting to note that both the structural and the magnetic transformation
temperatures show exactly the same dependence on the L21 atomic order degree. As mentioned, this
seems to indicate that the structural transformation temperature reflecting the relative stability
between austenite and martensite may be influenced by the magnetism of the alloy, as suggested
from theoretical studies [58]. In this respect, Figure 14 shows the increment of the entropy change,
S, at the MT of the Ni49.5Mn28.5Ga22 alloy as a function of the post-quench aging temperature [55].

Fig. 14: Evolution the entropy change at the


martensitic transformation as a function of the
post-quench aging temperature, for the
polycrystalline alloy quenched from 1173K.

It can be seen that S increases on aging at the temperatures of appearance of the exothermic peak,
in such a way that the increase may be attributed to the post-quench ordering process. Taking into
account that, due to the diffusionless character of the MT, there is no configurational contribution to
the entropy change, it can be consider that S has three main contributions:

S = Svib + Sel + Smag

(6)

where Svib is the vibrational contribution, Sel is the contribution of the conduction electrons, and
Smag is the contribution from magnetic subsystem. Since the austenitic and martensitic structures
do not change at all as a consequence of the atomic order variation (and taking into account that
neither does the Debye temperature of Ni-Mn-Ga alloys when atomic order variations are
introduced through composition [63]), no variation on the density of vibrational states is expected in
the studied alloys. Therefore, Svib can be neglected. On the other hand, the electronic contribution

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is also expected to be very small in ferromagnetic Heusler alloys [64], even more if the alloy
composition is not modified, so Sel can be also neglected. The increase on the entropy change at
the MT with the increasing L21 atomic order must be then related to the increase of the magnetic
contribution, as proposed in a previous study on the effect of composition on the entropy change at
the MT of Ni2+xMn1-xGa [64]. Therefore, the variation of the relative stability between austenite and
martensite (that is, the variation of Tm) as a result of the L21 atomic order variation seems to be
linked to the magnetism of the alloy. In particular, as a result of the increase of the magnetic
moment with the increasing , the higher shift on the magnetic entropy of the martensite with
respect to that of the austenite may lead to an increase of the magnetic contribution to the entropy
change at the MT, in such a way that S, and therefore the driving force for the MT, increases, thus
causing the stabilization of the martensitic phase. This hypothesis is, in fact, quite feasible if we
take into account that, since the saturation magnetization of the martensitic phase in Ni-Mn-Ga is
higher than that of the austenitic phase [65] (due to the lower Mn-Mn distance in the lowtemperature phase), higher variations of the magnetic moment could be expected in the martensite
as a result of the same atomic ordering.
The influence of magnetism on the MT is indeed confirmed from the analysis of the effect of posquench aging on the transformation temperatures in a Ni56.0Mn26.7Ga20.7 alloy transforming from
paramagnetic austenite into paramagnetic martensite (that is, Tm>TC), in which the effect of
magnetism on the MT can be obviously neglected [55]. Figure 15a shows the DSC thermograms
obtained on the alloy quenched from 873K and then subjected to post-quench thermal cycles
consisting on heating the alloy up to different temperatures, just as shown in Figure 9a. The direct
measurement up to 673K showing the exothermic peak linked to the L21 ordering process is also
shown in the figure (dashed line). In such thermograms, the peaks around 430K corresponds to the
MT whereas the steps in the baseline around 360K are associated to the ferro-para magnetic
transition taking place at the martensitic Curie temperature (TCmart). This is confirmed by the
magnetization measurements shown in Figure 15b, where it can be seen that the magnetization of
the as-quenched sample remains zero on cooling until it suddenly increases around 360K as a
consequence of the martensitic magnetic transition. The same magnetization measurement
performed on the as-quenched sample heated up to 550K shows the effect of the atomic order on
TCmart.

Fig. 15: (a) DSC thermograms performed on several consecutives thermal cycles (line) and on
heating up to 673K (dashed line), on a Ni56.0Mn26.7Ga20.7 alloy quenched from 873K. (b)
Temperature dependence of the magnetization for the as-quenched sample (black circles) and for
the quenched sample heated up to 550K (open circles).

V.A. Chernenko

99

The evolution of the transformation temperatures with the post-quench aging temperature is shown
in Figure 16, where the exothermic peak has been added in order to better correlate the aging
temperatures with the ordering process [55].

Fig. 16: Increment on the transformation


temperatures of a Ni56.0Mn26.7Ga20.7 alloy
quenched from 873K, as a function of the postquench aging temperature (DSC exothermic peak
overlapped).

It can be seen that, in effect, TCmart considerably increases with the increasing post-quench aging
temperature whereas Tm is almost unaffected (less than 2K) by the development of the ordering
process associated to the DSC exothermic peak. This confirms that the variation of the L21 atomic
order degree exclusively affects the magnetism of the alloy, and, therefore, that LRO affects the
martensitic transformation only if the MT occurs between magnetic ordered phases. In this sense,
the fact that LRO affects the MT via the magnetism implies that the MT may be more or less
affected by the atomic order depending on how far Tm is from TC, since the ferromagnetic exchange
coupling is stronger as the temperature decreases.
The last point has been checked on a Ni49.7Mn24.1Ga26.2 alloy undergoing a MT below 100K, in
which the condition Tm<<TC is met. The temperature dependence of the low-field magnetization of
the alloy just-quenched from 1173K and then heated up to 673K is shown in Figure 17. It can be
seen that, in effect, the shift of Tm on heating the alloy up to 673K (Tm ~50K) is considerably
higher than in the above mentioned ferro-ferro transforming alloys (see Figures 9 and 12), thus
demonstrating that the magnetic ordering plays a crucial role in the way the atomic order affects the
MT.

Fig. 17: Temperature dependence of the


magnetization of a Ni49.7Mn24.1Ga26.2 alloy
quenched from 1173K and heated up to 673K.
Inset shows detail of the magnetization
anomalies associated to the premartensitic
transition.

4.1 Premartensitic transition. It is worth noting that not only the MT but also the premartensitic
transition is affected by the atomic order. This can be seen in the inset of Figure 17, where the small
magnetization anomalies associated to a premartenstic transition, which was previously determined
both from ultrasonic and magnetic susceptibility measurements [66], are shown in detail. The post-

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quench heating treatment increases the premartensitic transformation temperature (TI) from 193K,
in the as-quenched alloy, to 213K in the ordered one. In this case, the increase of the magnetic
moment associated to the post-quench ordering process modifies the magnetoelastic coupling on the
alloy, which is responsible of the appearance of the intermediate phase through the premartensitic
transformation, in such a way that the premartensitic transition takes place at higher temperatures.
It is interesting to note that, in spite of the different nature of the martensitic and the premartensitic
transformations [67], both of them are highly affected by the magnetism of the alloy.
5. Summary
The effect of long-range atomic order on the structural and magnetic properties of Ni-Mn-Ga
ferromagnetic shape memory alloy has been reviewed. It is shown that a quantitative correlation
between LRO and the martensitic and Curie temperatures can be established from the analysis of
the modification of both transformation temperatures and the atomic order under high and low
temperature thermal treatments. On one hand, the effect of thermal treatment on the long-range
atomic order has been determined from neutron diffraction measurements. Some L21 atomic
disorder is retained by quenching from high temperatures, but it may evolve to the equilibrium
value through post-quenched aging treatments. On the other hand, the evolution of the MT and
Curie temperatures and the magnetic properties has been determined from calorimetric and
magnetometry measurements. It is shown that, irrespectively of the thermal treatment, the
transformation temperatures increase with the increasing L21 atomic order degree, showing the
same linear dependence on the next-nearest-neighbors atomic order parameter. From the equation
of the linear trend, the effect of the atomic order on the relative stability between austenite and
martensite has been quantitatively determined. Such effect is mainly attributed to the influence of
atomic order on the magnetic moment of the alloy. In fact, the martensitic transformation
temperature taking place between two paramagnetic phases is unaffected by the variation of the
atomic order. Finally, it is shown that the atomic order affects not only the martensitic but also the
premartensitic transition.
Acknowledgments
This work was carried out with the financial support of the Spanish Ministerio de Ciencia e
Innovacin (projec no. MAT2009-07928). The Institute Laue-Langevin D1B installation and the
Spanish CRG D15 installation are acknowledged for the allocated neutron beamtime (Exp. 5-24262 and CRG-D15-08-118). The authors acknowledge C. Gmez-Polo and J.A. RodrguezVelamazn for helpful discussions and technical assistance.
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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.105

Crystal Structures of Modulated Martensitic Phases of FSM Heusler


Alloys
Lara Righi1,a, Franca Albertini2, Simone Fabbrici2, Antonio Paoluzi2
1

Dipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Universit


di Parma, Viale G. Usberti 17/A, I-43124 Parma, Italy

IMEM, Consiglio Nazionale delle Ricerche, Parco Area delle Scienze 37/A, I-43124 Parma, Italy
a

lara.righi@unipr.it

Key words: martensitic structure; incommensurate modulation; powder diffraction.

Abstract. Multifunctional ferromagnetic shape memory Heusler alloys are frequently characterized
by structural modulation in martensitic phases. In particular, modulated martensitic phases, showing
the higher magnetic field induced strain (MFIS) performance, are the most promising candidates for
technological applications. Depending on the composition, as well as pressure and temperature
conditions, this periodic structural distortion, consisting of shuffling of atomic layers along defined
crystallographic directions, accompanies the martensitic transformation. Over the years, different
Ni-Mn-Ga modulated martensitic structures have been observed and classified depending upon the
periodicity of corresponding ideal nM superstructure (where n indicates the number of basic unit
cells constituting the superlattices). On the other hand, it has been demonstrated that in most cases
such structural modulation is incommensurate and the crystal structure has been fully determined by
applying superspace formalism. The results, obtained by structure refinements on powder diffraction
data, suggest a unified crystallographic description of the modulated martensitic structures, here
presented, where every different nM periodicity can be straightforwardly represented.

Martensitic transformation in ferromagnetic Heusler alloys


The stoichiometric Ni2MnGa alloy belongs to the family of intermetallic compounds with general
formula X2YM, called Heusler alloys. The austenitic phase of Ni2MnGa stable at room temperature
is defined by the cubic L21 superstructure displayed in Fig. 1. This type of lattice is common to the
family of Heusler alloys, being the L21 superstructure able to accommodate different metallic
elements within a wide range of compositions. This family of compounds were discovered by
Heusler in the nineteenth century and possess the remarkable property to be ferromagnetic despite
the fact that the constituents itself are non-ferromagnetic (as in the case of Cu2MnAl). The large
interest on these particular alloys is mainly due to the presence of a ferromagnetic state; different
compositions such as Cu2MnIn Cu2MnGa are isostructural and show ferromagnetic properties. On
the other hand, Heusler alloys like Cu2NiAl and Zn2CuAu are characterized by thermo-elastic
martensitic transformations. These two properties are simultaneously present in Ni2MnGa. Ni-MnGa Heusler alloys represent the most interesting and promising ferromagnetic shape memory
materials for technological applications [1]. The main physical properties at the basis of the giant
MFIS are the ferromagnetic state with a Curie temperature (TC) exceeding 300K, the thermoelastic
martensitic transformation (MT) generally below TC, and the presence of a high magnetocrystalline
anisotropy in the martensitic phase [2-4]. The reciprocal ratio of atomic species defining the offstoichiometric Ni-Mn-Ga Heusler alloy determine the MT temperature and martensitic crystal
structure as well [4].

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A structural description of the phases involved in the martensitic transformation was firstly reported
by Webster et al. in 1984 on the basis of neutron diffraction studies [5]. The parent cubic phase
stable at high temperature was found to belong to the Fm-3m space group, having a lattice
parameter aa= 5.833 . On cooling below 220K a reversible transformation takes place giving rise
to a martensitic phase. The cubic structure is distorted by a contraction of the c axis accompanied by
an elongation of the two remaining lattice vectors giving rise to a low-symmetry lattice. The
martensitic transformation is generally defined as Bain strain. Such distortion is represented by
the tetragonality parameter c/a, that in case of Ni2MnGa martensite, is approximately 0.94<1. The
c/a parameter is of fundamental importance in determining the maximum possible strain achieved
by magnetic-induced shape memory effect. The symmetry of the product phase is properly described
with a I-centred unit cell having the fundamental axes coinciding with the [10 1 ] , [101] and [010]
directions of the parent L21 superstructure (Fig. 1).

Figure 1. Prospective view of the L21 cubic structure of Ni2MnGa austenite (straight line). The
dotted line shows the axes defining, after distortion, the martensitic body centred unit cell.,
Long-period structural distortions in martensitic Ni-Mn-Ga phases
Several diffraction experiments [5-8] demonstrated the presence of additional weak reflections
indicating that, in some cases, the martensitic structures are characterized by structural modulation.
Neutron and X-ray experiments have demonstrated that the structure of martensite of the
stoichiometric compound Ni2MnGa is more complex. Extra reflections in the X-ray diffraction
pattern of Ni2MnGa martensite have been interpreted in terms of a superstructure constituted by 5
unit cells (five-fold modulation, 5M) along the [001]m /[-110]a direction, by considering the
presence of periodical shuffling of the (100)m/(110)a atomic layers [6-8]. The nature of this
structural modulation on Ni2MnGa martensite will be discussed in section 2.2.
Different martensitic structures of shape memory alloys exhibit structural modulation, as reported in
several publications. Ni-Al [9] and Ni-Ti [10] martensites exhibit, as a function of the composition,
a variety of structural modulations, which are generally viewed as periodical stacking faults of
{110}a atomic planes along determined crystallographic directions. The formation of such structural
modulations is in agreement with C. Zener et al. [11] who suggested the centred lattice of the
austenite to be unstable with respect the shear/shuffle motion of the {110}a planes. This instability
is manifested by the softening of the TA2 phonon mode, observed when the martensitic transition is
approached on cooling [12]. In addition, the austenite/martensite evolution can also be promoted by
mechanical load. The martensite phase above TM is formed by mechanical stress loaded along
specific crystallographic directions on single crystals. Intermartensitic transformations may be
favoured by an increase of the strength of an applied tension or compression [6].

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Figure 2. Graphical representation of the nM=s+1 relationship. Top: schematic reproduction of the
typical sequences of satellites observed in single crystal diffraction patterns for martensitic
modulated phases. Bottom: ideal periodicity of commensurate supercells for 5M and 7M
martensites (modulation of atomic positions is not represented).
In the case of Ni2MnGa a compression along [100]a induces at 290K the same 5-fold modulation
stable below 200K, whereas a further increase of the load gives rise to a 7-fold modulated structure
with an orthorhombic distortion of parent lattice [6]. Thus, the evolution of martensitic
transformation is conditioned by experimental conditions and the presence of mechanical stress can
induce intermartensitic structural changes not observed by variations of temperature. Afterwards
several investigations on Ni-Mn-Ga alloys have described a variety of different modulated
structures [8]. The number of observed satellites (s) between the main reflections, is directly
associated to superstructures constituted by 5, 6, 7, 10 or even 12 unit cells and commonly indicated
as 5M, 6M, 7M, 10M and 12M [7,8,13], where nM is referred to the relationship n=s+1. This
classification excludes the occurrence of incommensurate modulation. In spite of the intense
research dealing with the study of the magnetic and structural properties of the Ni-Mn-Ga system,
the structural characterization of modulated martensites is still a controversial matter. A series of
different models and approaches have been suggested in order to describe such a structural
distortion. Hereafter, the most important models developed to account displacive distortions of
martensitic phases are briefly presented.
Zhdanov description of distorted stacking sequences in close packed crystals. The symmetry
of close packed crystal structures can be described with different notations and symbolisms
following different interpretations [14-19]. The most important and used notations employed to
distinguish the different ABC close-packed structures have been described in detail by A.R. Verma
and P. Krishna [14]. Close packed or layered structures tend to form polytypes characterized by
different sequences (ordered or disordered) of stacking modes. In such a type of layered structures it
is particularly helpful the so-called Zhdanov notation [18] and long-period martensitic structures are
frequently designated by this compact schematic representation. The periodic shuffling can be
viewed as a zig-zag sequence of layers codified with Zhdanov symbols: a series of numbers
indicates the atomic layers related to a periodical shift corresponding to a fundamental lattice vector,
the opposite shift direction of the next block of planes is indicated by a sign. The suffix means the
total number of zig-zag motifs constituting the periodic crystal lattice. In Fig. 3 some examples of
this notation are illustrated.

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Figure 3. Three examples of Zhdanov sequences of martensitic layered structures. The two
structures on the left are referred to an hypothetical commensurate 7M modulation; the structure on
the right corresponds to the commensurate 5M modulation. The related symbol for each model is
indicated at the bottom

Nano-twinning. This original interpretation has been introduced by A.G. Khachaturyan et al.
[20] where a Ni-Al 7M monoclinic martensite has been treated as a nano-twinned adaptive phase.
Martensitic transformation is a diffusionless process involving large strains [21]. Alongside the
invariant plane, besides the Bain strain generating the martensitic lattice, a further invariant lattice
deformation process involving multi-variant twinning is indicated as the origin of structural
distortion. In particular for 7M modulation, in order to preserve the structural constraint of the
invariant plane strain, the mesoscale martensitic twinning develops into an adaptive nanostructure
having the size of the individual twin variants comparable with interatomic distances. The crystal
structure is therefore generated by the ordered sequence of nanocrystals of tetragonal martensitic
phase being the 7M modulation considered as the intermediate adaptive mode across the cubic
(austenite) to tetragonal (martensite) lattice transformation. The volume fraction of each nanovariant is related to:

= d 1 / d 2 (d1=nat , d2 = mat)
1

(1)

wherein at is the unit cell parameter of tetragonal phase and d1 and d2 are the thickness of the two
lamellae. This relationship is derived from the lattice constraints conditioned by the invariant plane
strain [21].
This theoretical analysis interprets the 7M type modulated Ni-Al martensite as nano-twinned phase
corresponding to the classical (5, 2 ) periodical stacking. Also in this case this approach does not
take into account the frequent observation of incommensurate periodicity of structural distortions.
A. G. Khachaturyan [20] suggests the presence of structural disorder such as stacking fault
determining the shift of diffraction spots from calculated positions referred to the commensurate
n/m ratio. Indeed, the sequence of nano-twinned domains is simplified to only two segments (m and
n) having a fixed thickness. More complex distributions of nano-variants with variable thickness are
not taken into account and the final interpretation of structural distortion is virtually equivalent to

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(5, 2 )2 Zhdanov model. In the last years, nano-twinning model have attracted a new interest for the
interpretation of the structural modulation for Ni-Mn-Ga martensitic phases showing classical 7M
type of diffraction pattern [22,23]. On the other hand this original point of view, as already pointed
out, does not supply an exhaustive and precise description of the structural distortion specially in the
case of incommensurate modulation.
Crystallographic description of incommensurate modulated structures: the superspace
approach. The literature, dealing with modulated martensitic structures of several ternary or binary
alloys, demonstrated that the modulation is frequently incommensurate [12,24-26]. Over the years,
the structural analysis of incommensurate structures has been developed on the basis of the
superspace formalism. Hereafter, the theoretical background of superspace approach necessary to
correctly interpret the next structural results is provided. A more comprehensive description of this
theory can be found in Ref.[27].
The diffraction pattern of incommensurate crystal is composed by two distinct set of reflections.
The first group is composed by strong diffraction peaks (main reflections) defining by a*, b* and c*
a conventional lattice. The second set of reflections (satellites), usually weaker, is not indexed on
the basis of the former vectors group. The indexing of the whole diffraction pattern requires
supplementary vectors and, as a result, the generic diffraction vector H assumes the form (in the
case of mono-dimensional modulation):
H=ha*+kb*+lc*+mq

(2)

where the q vector is usually written as:


q= a*+b*+c*

(3)

Therefore each Bragg reflection has four indexes hklm corresponding to the three basic vector a*,
b*, c* and to the modulation vector q. Depending on , and coefficients it is possible to
individuate two main classes of modulated structures. If these coefficients correspond to a rational
number the modulation is defined commensurate, otherwise, an irrational number determines an
incommensurate modulation. The commensurate modulation can be always expressed in terms of a
three-dimensional superstructure. On the contrary, the crystallographic description of an
incommensurate modulated crystal requires the introduction of the superspace.
The structural modulation is derived by a periodic deviation involving atomic positions which are
referred to the basic lattice defined by a, b and c principal vectors. In the incommensurate
modulated crystal the generic position is converted in:

xi = xi + ui ( x4 )

(4)

The xi indicates the atomic position of the i-th atom in the unit cell (expressed by x, y and z
fractional coordinates). The superspace enables to express all the periodicities present in the
structure, included that related to the modulation showing a periodic length not commensurate to the
three-dimensional basic lattice. The function ui ( x4 ) depends on the superspace coordinate x4 and it
is periodic with respect to the translation along the fourth axis. Accordingly to incommensurateness
of the modulated structure the factor ui ( x 4 ) added to the un-distorted position of a specific atom is
different for each adjacent unit cell removing the three-dimensional translational symmetry of the
crystal. The modulation function is generally expanded into a Fourier series:

u ( x4 ) = An sin(2nx4 ) + Bn cos(2nx4 )
n =1

(5)

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The amplitudes An and Bn are the unknown parameters to be determined. The general atomic
position xi ( xi , x4 ) depends on a couple of parameters, one derived from the average basic structure
(external space), the second referred to the additional dimension of the superspace (internal space).
The superspace permits a crystallographic description of the modulated crystal and consequently the
whole symmetry of the system is expressed by superspace groups [27].

The 5M family of modulated martensitic phases


The typical diffraction pattern of stoichiometric Ni2MnGa thermally induced martensitic structure is
characterized by four distinct satellites and therefore this phase has been generally indicated as 5M
modulated [6,7]. Further single crystal neutron scattering experiments performed by A. Zheludev et
al. [12], revealed that modulation periodicity was not commensurate to the martensitic basic lattice.
The structure determination of the incommensurate modulated structure of stoichiometric
martensitic phase has been achieved by applying the superspace formalism [25]. The powder X-ray
diffraction pattern collected at 100K on a polycrystalline specimen of Ni2MnGa has been indexed
with the orthorhombic body-centred lattice having constants a=4.2187(1), b=5.5534(1),
c=4.1899(1). The remaining weak reflections were associated to a single component modulation
vector q=0.43c*. The analysis, based on the set of reflections obtained by a full-profile fitting of the
PXRD pattern, indicated the presence of translational symmetry fulfilled by the superspace group
Immm(00)s00. Main reflections and satellites are used in the Rietveld refinement of the (3+1)dimensional model.
The design of structural modulation is based on the first interpretation given by V. V. Martinov et
al.[6,7]. To the distorted martensitic lattice, the authors applied a sinusoidal function alongside the
fundamental c lattice vector with a five-fold periodicity. The best agreement with the observed
intensities of satellites was achieved with the function:
j = A sin(2 / 5) + B sin(4 / 5) + C sin(6 / 5)

(6)

where A, and B parameters, as reported in Ref. [6,7], are written in Table1.


This imply that the modulation function could be applied not on the single atomic site but on the
(00l)m layers taken as a rigid unit. This simple representation of the displacive distortion is therefore
transferred in the (3+1)-dimensional model by imposing the following constraints:
1) The modulation involves the periodic transversal shift of the (00l) atomic layers,
consequently, the Ain amplitudes are constrained to assume the same value for all the atomic
sites.
2) The shift is mostly alongside the x axis perpendicular to the fundamental direction of the
modulation vector. Therefore, the y component of the modulation function is fixed to zero.
As a result the Eq. 5 is converted into:
3

ui ( x4 ) = Ain sin( 2nx4 )

(7)

n =1

During Rietveld refinement the atomic displacement parameters (ADP) are calculated as isotropic.
The modulated interatomic distances, are consistent with the typical bond lengths for such type of
atoms in intermetallic compounds [28].

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Table1 Summary of the structural modulation parameters found for different martensitic phases of
Heusler FSMA The An(x) coefficients are related to Eq.7. The nM Mart. type is referred to the
coefficients of Eq. 6 for Ni2MnGa as reported in Ref. [6]
Alloy

Type

A1(x)

A2(x)

A3(x)

A1(z)

A2(z)

Ni2MnGa

5M (IC)

0.4248(2)

0.0700(2)

--

--

--

--

Ni2MnGa

5M Mart.

2/5

-0.06

0.002

0.008

--

--

Ni1.95Mn1.19Ga0.86 5M(C)

0.3991(2)

0.0677(8)

-0.002(3)

--

--

--

Ni2Mn1.2Ga0.8

7M(IC)

0.30814(4)

0.090(1)

0.033(1)

--

0.003(1)

-0.002(2)

Ni2.15Mn0.85Ga

7M(IC)

0.307(4)

0.069(1)

0.048(2)

--

0.001(3)

-0.003(6)

Ni2MnGa*

7M Mart.

2/7

0.083

-0.027

0.0

--

--

Ni2.4Fe0.6Ga

6M(IC)

0.3513(5)

0.088(1)

0.043(2)

--

0.001(1)

-0.002(2)

From q= c*
* The stress-induced 7M modulation for single crystal of Ni2MnGa at room temperature.

From the Rietveld refinement the modulation vector is actually q= 0.452c* which is close to
3/7c*(=0.428c*). If this approximation is taken into account it is possible to derive from the (3+1)dimensional structure a seven-fold 3-dimensional model consisting of seven unit cells along the
fundamental c axis. The superstructure, described by the non standard Pnmn space group, has 4
independent atomic positions for Mn, Ga and Ni. The graphical representation of this supercell
reveals the perfect sinusoidal wave of the shifted (001)m planes [25]. The calculated diffraction
pattern is characterized by the presence of 4 satellites in reciprocal space indicating the 5M nature
of the seven-fold superstructure. The modulation vector q slightly differs from commensurate
period 2/5c*. Indeed, the Ni2MnGa martensite is roughly five-fold modulated 5M having
q=(2/5+)c* where represents the degree of incommensurateness. To avoid inhomogeneous
notation with regard to the general notation of this type of distorted phases we indicate this
Ni2MnGa martensite as 5M (IC).

Figure 4. X-ray powder diffraction patterns from N2MnGa (up) and Ni2Mn1.15Ga0.85 (down)
martensites showing the same fingerprint for both modulated phases.
The structural investigations of off-stoichiometric Ni-Mn-Ga alloys demonstrated the occurrence of
the commensurate form of martensitic 5M modulation [29]. A polycrystalline sample of

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composition Ni1.95Mn1.19Ga0.86 has been studied by X-ray powder diffraction at room temperature. As
it is shown in Fig. 4, the comparison with the PXRD pattern collected for Ni2MnGa at 100K (well
above TM) indicates the close structural analogy of the two martensitic phases. The splitting of some
fundamental reflection revealed a tiny monoclinic distortion of the orthorhombic martensitic lattice.
The superspace model of Ni2MnGa has been therefore adapted to redefine such a monoclinic
symmetry, which is described with the superspace group I2/m(0)00. The Rietveld refinement
[27] has been successfully carried out giving final unit cell constants am=4.2283(2),
bm=5.5752(2), cm=4.2003(2), =90.325(6) and q=0.3991(2)c*. The refined modulation vector
q, coincident with 0.4c*=2/5c*, demonstrates the commensurateness of the modulation. Hence Mnrich martensite shows a five-fold superstructure having lattice parameters: a=am, b=bm, c=5*cm. As
shown in Table 1, the modulation function assumed refined parameters very similar to those found
for Ni2MnGa. However, having recorded for Ni1.95Mn1.19Ga0.86 additional weak satellites belonging to
second order, A2(x) term of modulation function (Eq.7) is refined during least-square fitting.
Despite to the commensurate periodicity of the system, the structural refinement has been performed
with the monoclinic (3+1)-dimensional model. For instance, within n-dimensional approach, the
structural modulation is correctly obtained by the refinement of few parameters, otherwise in order
to solve the crystal structure of the five-fold supercell nine independent atomic positions are
required to be determined. From the superspace description, a classical 3-dimensional structure is
straightforwardly obtained (for details see Ref. [29]). In this case, analogously to the 5M(IC)
structure found for Ni2MnGa, this second commensurate type generates 4 equi-spaced satellites in
the calculated diffraction pattern. Although 5M modulation has been always related to a single
crystal structure, in some cases Ni-Mn-Ga 5M martensites were reported to have a monoclinic
structure with close to 90.3 [24] whereas for closely stoichiometric Ni2MnGa alloys the basic
structure is claimed to assume orthorhombic symmetry [30]. We have demonstrated that for Ni-MnGa Heusler alloys there are at least two different kinds of 5M modulation: monoclinic
commensurate (C) and orthorhombic incommensurate (IC). At low temperature (83K) the 5M(C)
modulation for Ni1.95Mn1.19Ga0.86 becomes incommensurate. As the temperature decreases the
periodicity of the modulation gradually varies from 2/5 ratio. On the other side, in the studied
temperature range, the basic structure is characterized by small changes, whilst the structural
modulation remarkably evolves from commensurate to incommensurate.

The 7M family of modulated martensitic phases


The martensitic structure of Ni-Mn-Ga 7M type is related to the presence of six satellites between
the main reflections of distorted basic structure [6,8,31]. The martensitic lattice is usually described
as an orthorhombic distortion of the original parent L21 structure with a>b>c [6,32,33]. However
the corresponding I-centred unit cell (see Fig. 1) shows a strong monoclinic distortion with 93.
Several investigations evidenced the occurrence of temperature-induced 7M-modulated martensite
in Mn-rich [33,34] and Ni-rich [35] Ni-Mn-Ga alloys. Furthermore, this type of structure has been
reported in an experiment where a stoichiometric Ni2MnGa single crystal was subjected to external
tensile or compression loads along the cubic <100> or <110> crystallographic directions
respectively, at room temperature [6]. Such a Ni-Mn-Ga martensite displays some analogies with
the Ni-Al layered martensitic structure. The Ni-rich binary Ni-Al alloys shows a 7M martensitic
phase [8, 9], with a monoclinic structure having a seven-layered modulation. This structure has been
described in terms of a (5, 2 ) stacking sequence of the (110)A nearly close-packed atomic planes.
The same model has been applied to Ni-rich martensitic phase on the basis of TEM analysis [35].
However these studies supplied a qualitative description of the structural modulation, and in order
to study this new modulated martensitic structure it has been followed the same procedure
established for 5M family. Some off-stoichiometric 7M Ni-Mn-Ga samples (see Table 1) were
analyzed by powder X-ray and neutron diffraction [36].

V.A. Chernenko

113

Figure 5. Bottom: The 10-fold superstructure related to the incommensurate 7M structure showing
the zig-zag distortion of the atomic layers perpendicular to c axis. Top: corresponding diffraction
pattern along [012] fundamental projection. The dashed box evidences the six satellites located
between main reflections.
In particular, the sample with composition Ni2Mn1.2Ga0.8 is found to have a monoclinic unit cell
a=4.222 b=5.507 c=4.267 with =93.3 at room temperature. The refined modulation vector,
q=0.308c*, indicates that the structural modulation is not commensurate to a seven-fold layered
structure being variable (see Eq.3) significantly different from 2/7. The monoclinic (3+1)dimensional model chosen for the Rietveld refinement of the powder diffraction pattern is the same
obtained for the 5M commensurate structure [36]. The modelling of the periodic displacive
distortion, involving the (00l)M atomic layers along the c fundamental axis, requires the introduction
of first and second order of Fourier series of Eq.7. The resulting modulation parameters reported in
Table 1 define a modulation function rather similar to a smoothed zig-zag stacking. If the
modulation vector q is regarded as approximately equal to 3/10c*, the modulated structure of
Ni2Mn1.2Ga0.8 can be described with a 10-fold superstructure having monoclinic P2/m symmetry
and unit cell dimensions: a=aM, b=bM c=10cM and =M. Within Zhdanovs notation the layers
sequence forming the ten-fold superstructure is (4 2 5 2 4 3 ) for a total of 20 layers as schematically
shown in Fig.5. For instance, the incommensurate periodicity of the displacive shift of atomic layers
breaks the simple stacking (5, 2 )2 corresponding to a commensurate seven-fold superstructure. So
far, it is important to underline that a commensurate form of 7M modulation for Ni-Mn-Ga
system is still not observed. The reciprocal space, calculated from the 10-fold superstructure,
reflects the typical sequence of satellites associated to the 7M modulation (see top of Fig.5).
Interestingly, a similar incommensurate 7M modulated structure with almost unvaried q vector and
modulation function has been found for Ni2.15Mn0.85Ga composition at room temperature [36]. For
this second composition, the Rietveld refinement performed on powder neutron diffraction data

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reveals a modulation function with a smoothed zig-zag shape very similar to that found for the first
structure.
In the frame of nano-twinning modelling the authors of Ref. [20] analysed the 7M martensitic
modulation of binary Ni-Al alloy. The corresponding calculated volume fraction 0 of variants (see
Eq. 1) was found to be 0.31 and this value has been interpreted as related to the ratio 2/(2+5).
Therefore it is concluded that the atomic structure was generated by micro-twins of 2 and 5 atomic
layers (e.g. Zhdanov 5 2 sequence). On the other hand, the obtained 0 is much closer to 3/10 which
recalls the parameter determined by the application of superspace model for Ni-Mn-Ga 7M (IC)
modulation. For instance, this parallelism could indicate that also the investigated Ni-Al martensite
shows an incommensurate modulation.
Nowadays, the structural modelling of 7M modulation obtained from structural refinement of (3+1)dimensional structures is the most reliable and correct. This is also confirmed by a recent structural
investigation, through electron backscattering diffraction (EBSD), dealing with the morphological
analysis and precise determination of twin interfaces of a polycrystalline sample of 7M Ni-Mn-Ga
[37]. It is important to recall that EBSD measurements require a correct and detailed
crystallographic description of the studied crystal. In this work the authors successfully indexed the
Kikuchi line pattern of one variant by using the ten-fold superstructure derived from (3+1)dimensional model, confirming that also in this case the 7M modulation occurs with
incommensurate periodicity. In addition it was possible to give a reliable labelling of all the
twinning boundaries, giving a detailed picture of the twin types constituting the studied sample [36].
The 7M monoclinic (3+1)-dimensional structure has been also exploited to solve the martensitic
crystal structure of FSMA with composition Ni2.4Fe0.6Ga [38]. Although this monoclinic structure,
refined on the basis of powder neutron diffraction data, shows all the main structural characteristics
of 7M modulation the most interesting difference regards the periodicity of the modulation. The
structural refinement of the incommensurate Ni2.4Fe0.6Ga martensitic phase determines a
modulation vector q=0.3521*c. Such a periodic length is not pseudo-commensurate to a ten-fold or
seven-fold superstructure but, on the contrary, it is necessary to represent a large sequence of (00l)
atomic layers involving 17 adjacent unit cells.

Figure 6. Sketch of the periodicity ratio between modulation function and corresponding
superstructure obtained from the pseudo-commensurate approximation.

V.A. Chernenko

115

Surprisingly, the single crystal diffraction pattern calculated on the basis of this large superstructure
shows 5, instead of 6, satellites between main reflections. Previous TEM investigations on Ni-Fe-Ga
martensitic phase with similar composition show the presence of a new modulated structure
characterized by five satellites and called 6M [13]. Hence, the investigated polycrystalline sample
exhibits 6M(IC) modulated structure representing, within the frame of (3+1)-dimensional space, a
new form of monoclinic martensitic FSMA.
Summary
We have summarized a series of structural analysis of different modulated Ni-Mn-Ga martensitic
phases of ferromagnetic shape memory Heusler alloys. It has been found that the structural
modulation is frequently incommensurate and in few cases commensurate. For instance, the
occurrence of incommensurate modulation necessarily requires the reconsideration of the structural
description based on nM superstructures. In particular, it has been demonstrated that the number
observed satellites and the corresponding periodicity of the commensurate models are not
correlated. The simple criterion, generally adopted up to now, is not sufficiently accurate to describe
the wide panorama of martensitic modulated structures. The correct determination of the pseudocommensurate superstructures is, on the contrary, related to the periodical relationship between
modulation function and unit cell spatial dimensions (see Fig. 6). In this frame the superspace
approach represents an useful instrument able to define the modulation vector as not constrained to
the basic structure. The results, obtained from systematic structural study of different modulated
martensitic phases of FSMA, are also fundamental for a unified description of martensitic structures
in the superspace where every different periodicity can be straightforwardly represented.
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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.117

Magnetic Microstructure Analysis of Ferromagnetic Shape Memory


Alloys and Related Compounds
Y. Murakami1,a, R. Kainuma2,b, D. Shindo1,c and A. Tonomura3,4,d
1

IMRAM, Tohoku University, Sendai 980-8577, Japan


Graduate School of Engineering, Tohoku University, Sendai 980-8579, Japan
3
Advanced Research Laboratory, Hitachi, Hatoyama 350-0395, Japan
4
Advanced Science Institute, RIKEN, Wako 351-0198, Japan
a

murakami@tagen.tohoku.ac.jp, kainuma@material.tohoku.ac.jp,
c
shindo@tagen.tohoku.ac.jp, d akira.tonomura.zk@hitachi.com

Key words: magnetic domain, domain wall, antiphase boundary, martensite, transmission electron
microscopy, Lorentz microscopy, electron holography

Abstract. We performed magnetic imaging of Ni-based ferromagnetic shape memory alloys. The
magnetic microstructure was revealed by Lorentz microscopy and electron holography, which are
powerful tools based on transmission electron microscopy. Observations of Ni51Fe22Ga27 and
Ni50Mn25Al12.5Ga12.5 alloys, both of which have an L21-ordered structure in the parent phase,
demonstrated that the antiphase boundaries (i.e., a type of planer defects) caused significant changes
in the magnetization distribution due to depression of the atomic orderactually, the magnetization
in these alloys depends upon the degree of chemical order. We propose a method which estimates the
important magnetic parameters (the magnetocrystalline anisotropy constant and exchange stiffness
constant) based on transmission electron microscopy observations. This method should be useful in
magnetic measurements of nanometer-scale areas, for which conventional techniques cannot be
applied.
Introduction
Since the discovery of giant strain in a Ni2MnGa alloy [1], which was induced by the application of a
magnetic field, ferromagnetic shape memory alloys (SMAs) have attracted considerable attention in
the field of materials science. Researchers continued their efforts in both developing new
ferromagnetic SMAs [110] and understanding the extraordinary phenomena observed in these alloys
[1119]. For industrial application, ferromagnetic SMAs have several advantages over conventional
nonmagnetic alloys, such as a quick response to applied magnetic fields and operation without
touching the specimens. A key point in explaining the magnetic-field-driven shape deformation is the
high magnetocrystalline anisotropy of martensites [1,14,20], which is typically on the order of 105
J/m3. Because of this significant magnetic anisotropy, the martensite variants show one-to-one
correspondence to their magnetic domains, i.e., the magnetization vectors in all of the martensite
variants are aligned to the easy magnetization axis. This peculiar magnetic domain structure in
martensites was revealed by using microscopic methods such as magnetic force microscopy [21], a
colloidal method [22], magneto-optical method [23,24], Lorentz microscopy [13,25], and electron
holography [26,27]. Among these methods of magnetic imaging, Lorentz microscopy and electron
holography (both of which are based on transmission electron microscopy (TEM)) can provide useful
information on the magnetization distribution, which is the focus of this review paper.
We here review topical observations on the ferromagnetic SMAs and related compounds,
which were recently studies by the authors. In magnetic domain analysis of the ferromagnetic SMAs,
an important problem is the effect of antiphase boundaries (APBs), which are planar defects produced
in the atomic ordering during heat treatment [28,29]. As demonstrated in the later sections of this
report, APBs cause several anomalies in the observations, not only in the local magnetization

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distribution but also in the macroscopic thermomagnetization curve (temperature vs. magnetization
curve). Here we show the results of Lorentz microscopy and electron holography performed on the
Ni-based ferromagnetic SMAs Ni51Fe22Ga27 and Ni50Mn25Al12.5Ga12.5, which reveal the effect of
APBs on the magnetic microstructure [28,30,31]. In addition, we report a method that estimates the
principal magnetic parameters (the magnetocrystalline anisotropy constant Ku and the exchange
stiffness constant A) using only TEM-based observations [32].
Experimental Procedure
A Ni51Fe22Ga27 alloy [6] was heat treated at 1473 K for 24 h to obtain a homogeneous single phase,
followed by quenching in ice water. The parent phase is L21-ordered, and transforms to the
monoclinic martensite (10M-type or 14M-type structure) near 141 K. The Curie temperature (TC) is
approximately 310 K. A Ni50Mn25Al12.5Ga12.5 alloy [33] was annealed at 1273 K for 3 days, followed
by quenching in ice water. This ingot was subsequently heated up to 1073 K, followed by slow
cooling to 673 K over 1 h. The ingot was finally quenched in ice water. Although the
Ni50Mn25Al12.5Ga12.5 alloy, which had a stoichiometric composition, did not undergo a martensitic
transformation upon cooling, the L21-ordered parent phase provided sufficiently large antiphase
domains (of the order of 100 nm) to enable in-depth examination of the correlation with magnetic
domains. TC in the Ni50Mn25Al12.5Ga12.5 alloy is approximately 373 K. In order to determine the
magnetic parameters Ku and A by TEM observation, we used a model specimen of perovskite-type
manganite La0.25Pr0.375Ca0.375MnO3 [34], which undergoes a first-order magnetic phase
transformation at approximately 50 K. Because of the character of the first-order transformation, it is
possible to observe an isolated ferromagnetic region (low-temperature phase) that was formed in the
nonmagnetic parent phase. A single crystal of the manganite was fabricated by the floating-zone
method.
There are two popular TEM-based methods of observing magnetic domains. One is Lorentz
microscopy [35,36], which provides easy visualization of magnetic domain walls as bright or dark
lines in defocused conditions, as shown in Fig. 1(b). This imaging technique is based on the deflection
of electron beams by the Lorentz force of a magnetic specimen (Fig. 1(a)). The other method is
electron holography [36,37], which can be used to visualize the distribution of magnetic flux, as
shown in Fig. 2(d). Let us imagine two sorts of electron waves, i.e., an object wave passing through a
specimen and a reference wave in vacuum (Fig. 2(a)). The phase of the object wave is modified
relative to the reference wave because of the magnetic (or electric) field of the specimen. This phase
information can be stored in a hologram (Fig. 2(b)) as an interference fringe between the object and
reference waves, which can be generated using a biprism. It is possible to extract the phase
information using the Fourier transform of digitized holograms (Figs. 2(b) and (c)). This process
causes a reconstructed phase image, as shown in Fig. 2(d), in which the contour lines can be
regarded as the distribution of an in-plane component of the magnetic flux.

Fig. 1 Principle of Lorentz


microscopy. The thin-foil specimen
contains two types of magnetic
domains, A and B, separated by a
180 wall.

V.A. Chernenko

119

Fig. 2 Principle of electron holography.


Magnetic domain observations of the Ni-based ferromagnetic SMAs were carried out using a
300 kV transmission electron microscope, a JEM-3000F, in which a magnetically shielded objective
lens was installed [38]. The residual magnetic field at the specimen position was reduced to 0.04 mT.
The observation of the manganite was carried out using another 300 kV electron microscope, an
HF-3300X [39].
Impact of Antiphase Boundaries in the Magnetic Domain Structure
The Ni51Fe22Ga27 alloy has several advantages [6]. For example, both TC and MS (martensitic
transformation start temperature) can be controlled by heat treatment of the quenched specimen, via
enhancement of the L21 order, as well as by the choice of an appropriate composition. Moreover, the
ductility of the polycrystalline state can be improved dramatically by introduction of the phase into
the grain boundaries. In addition to these practical advantages, the alloy exhibits a curious
phenomenon, as shown in Fig. 3. In the temperature range between 400 K and Ta (temperature at
which the anomaly begins to occur), the magnetization in the parent phase monotonically increases
with decreasing temperature, as observed in other ferromagnetic SMAs. However, the observed
magnetization decreases over a wide temperature range between Ta and MS, although the specimen
has not yet transformed to the martensitic phase. From an engineering viewpoint, what happens in this
temperature range is an essential issue in the materials design of ferromagnetic SMAs. Therefore, we
investigated the underlying mechanism by performing TEM observations.

Fig. 3 Thermomagnetization curve observed in a


Ni51Fe22Ga27 alloy subjected to heat treatment at
773 K for 1 h. The magnetization was measured in
an applied magnetic field of 1 kOe.

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Figure 4 shows the changes in a Lorentz microscope image of a Ni51Fe22Ga27 alloy upon
cooling [26]. The magnetic domain walls appear as dark and bright lines in this mode of observation.
At 296 K, at which the anomaly in the thermomagnetization curve is negligible, the specimen shows
micrometer-sized magnetic domains (Fig. 4(a)). It is likely that the micrometer-sized magnetic
domains are common in the parent phase of SMAs. However, in the temperature window between Ta
and MS, the magnetic domain structure in the parent phase dramatically changes. As shown in Figs.
4(b) and 4(c), the population of the magnetic domain walls markedly increases upon cooling, and all
of the magnetic domain walls are highly curved. As a result, the Lorentz micrograph exhibited a
peculiar spotty contrast, as can be seen in Fig. 4(c). This anomalous magnetic domain structure was
observed until the martensitic transformation was complete. As shown in Fig. 4(d), the martensitic
phase showed a distinct form of plate-like magnetic domains due to the large magnetocrystalline
anisotropy. Our TEM studies have indicated that the anomalous magnetic domain structure in the
parent phase (Figs. 4(b) and 4(c)) was due to interaction with APBs, which strongly attracted the
magnetic domain walls. However, because the antiphase domains (i.e., highly ordered portions
enclosed by APBs) were small in the Ni51Fe22Ga27 alloy, it was not easy to obtain in-depth
information regarding the magnetization distribution near an APB. Therefore, we used a different
alloy system, Ni50Mn25Al12.5Ga12.5, which provides sufficiently large antiphase domains, on the order
of 100 nm, after an appropriate heat treatment. As mentioned later in detail, the magnetization in the
Ni50Mn25Al12.5Ga12.5 alloy is highly sensitive to the degree of chemical order [33]. As a result, the
interaction between the magnetic domain walls and APBs is significant.

Fig. 4 Changes in the Lorentz microscope images of a Ni51Fe22Ga27 alloy upon cooling.
Reprinted with permission from [26].
Figure 5(a) shows a dark-field image of the Ni50Mn25Al12.5Ga12.5 alloy, which was obtained by
using the 111 reflection in the L21-ordered parent phase [31]. The highly curved gray lines represent
APBs in this viewing field. Figure 5(b) shows a Lorentz micrograph of the same viewing field, in
which the magnetic domain walls appear as bright or dark lines. These observations indicate that the
magnetic domain walls trace the positions of the APBs. For example, we have indicated several APBs
using arrows labeled 16. As shown in Fig. 5(b), the magnetic domain walls are located at exactly

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these APB positions. This observation indicates that the magnetic domain walls are strongly attracted
by APBs.
Figure 6(a) provides another Lorentz microscope image of the parent phase of a
Ni50Mn25Al12.5Ga12.5 alloy [31]. The magnetic domain walls are located at the same positions as the
APBs, as was the case in Fig. 5. Figure 6(b) shows a magnetic flux map based on electron holography.
The flux map was observed in the same area as shown in Fig. 6(a). The contour lines represent the
in-plane component of magnetic flux in the thin-foil specimen. Remarkably, there were many vortices
in the magnetic flux, as indicated by the arrowheads. In order to characterize these vortices in greater
detail, the reconstructed phase image was superimposed with the Lorentz micrograph, as shown in
Fig. 6(c), wherein the small arrows represent the direction of magnetic flux. It is clear that the
magnetic vortices formed within closed and/or highly curved magnetic domain walls, in the presence
of the strong interaction with APBs. Because of these closed patterns of magnetization, which were
developed by cooling the parent phase, the observed magnetization in an applied magnetic field
should be reduced. Thus, the anomalous drop in the thermomagnetization curve, such as shown in Fig.
3, can be explained by the significant change in the magnetic domain structure due to the strong
interaction with APBs.

Fig. 5 Correspondence between APBs and magnetic domain walls in the Ni50Mn25Al12.5Ga12.5
alloy. (a) Dark-field image and (b) Lorentz microscope image of the parent phase (L21 phase).
Reprinted with permission from [31].

Fig. 6 Magnetic vortices formed in a


Ni50Mn25Al12.5Ga12.5 alloy. (a) Lorentz
microscope image and (b)
reconstructed phase image
representing the lines of magnetic flux
in the parent phase. (c) Superimposed
images of (a) and (b). The small arrows
indicate the direction of the lines of
magnetic flux. Reprinted with
permission from [31].

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From an engineering point of view, the strong interaction with APBs appears to provide a
significant pinning force that hampers the motion of magnetic domain walls. This idea was
substantiated by in situ Lorentz microscopy observations. In order to apply a magnetic field to the
thin-foil specimen inside the electron microscope, we used a magnetizing stage which employed a
small electromagnet [40]. The magnetic field was applied in a direction parallel to the foil plane.
Figure 7(a) shows a Lorentz micrograph taken in a negligible magnetic field [28]. We shall focus on
the magnetic contrast indicated by the arrows, which represent the magnetic vortices as revealed by
the magnetic flux map in Fig. 6(b). There were two types of patterns in the magnetic vortices shown in
Fig. 7(a), depending on the chirality. The arrows labeled V1, V3, and V5 indicate clockwise vortices,
which have a central bright spot (vortex core) and an outer dark frame (domain wall). The other type
of vortices is counterclockwise, which is indicated by the arrows labeled V2 and V4. The
counterclockwise vortices are characterized by a central dark spot and an outer bright frame. Refer to
the upper panels in Fig. 7(c) to distinguish these vortices patterns. When a magnetic field (H) of 60 Oe
was applied along the white arrow, the vortex cores moved to the left (for bright spots) or to the right
(for dark spots), depending on their chirality (Fig. 7(b)). This motion was attributed to an increase in
the magnetic component (within the closed APBs) that was aligned to the applied magnetic field, as
illustrated in the lower panels of Fig. 7(c). Despite this change in the inner magnetization distribution,
the magnetic domain walls remained unmoved due to the significant pinning effect of the APBs.

Fig. 7 In situ Lorentz microscopy observations that demonstrate the pinning of magnetic
domain walls by APBs in Ni50Mn25Al12.5Ga12.5. Lorentz micrographs obtained (a) before
applying a magnetic field and (b) when a magnetic field of 60 Oe is applied. (c) A schematic
representation of the change in the vortex-like patterns caused by applying a magnetic field.
Reprinted with permission from [28].

Magnetic imaging with TEM is useful in determining the thickness of magnetic domain walls
[30]. We examined the width of magnetic domain walls located at the APBs. In order to determine the
domain wall thickness in the Ni50Mn25Al12.5Ga12.5 alloy, we employed Lorentz microscopy [30,36],
although electron holography offers an alternative method of accurate measurement, as discussed in a
later section. We focused on a dark line (i.e., a low intensity line representing a magnetic domain

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123

wall) that traced the APB position (Fig. 8(a)). This wall was identified to be a 180 wall, based on
magnetic flux observation by electron holography [30]. The full width at half maximum W in the
intensity profile (from the Lorentz microscopy) was obtained along the line AB crossing the 180 wall
to measure the wall width, as shown in Fig. 8(b). The background was determined by taking a line that
intersects the intensity maxima at X1 and X2. When the defocus value Z was not extremely large, it
was a reasonable approximation to consider that W linearly increased with increasing defocus value Z.
Assuming this linear relationship, the width of a magnetic domain wall can be determined by plotting
W as a function of Z, and extrapolating it to zero defocus. If the plane of APBs and magnetic domain
walls is tilted away from the direction of the incident electrons, this plot will overestimate the width.
To minimize this overestimation, we selected a region in which the observed APB width was narrow.
Least-squares fitting of the plots yielded a wall width of 10 nm (Fig. 8(c)). Interestingly, this wall
width was considerably lower than that of 180 walls in other cubic systems. Therefore, the width of
domain walls near APBs (10 nm) was dominated by a different mechanism than that of conventional
180 walls.
It appears that the unexpectedly narrow magnetic domain wall shown in Fig. 8(c) is due to the
chemical disorder that must occur in APBs. As mentioned earlier, APBs are a type of structural defect,
which is thermally formed in the chemical ordering from the B2 disordered state to the L21 ordered
state. In order to reduce the boundary energy of the APBs, the chemical order parameter must change
gradually, rather than discretely, at the boundary position. As a result, thermally-produced APBs have
a finite width (typically on the order of nanometers [41,42]), within which the atomic order may be
close to that of the B2 disordered state, rather than the L21 ordered state. In addition, we should be
aware of the peculiar magnetism of the Ni50Mn25Al12.5Ga12.5 alloy, which is ferromagnetic in the L21
ordered state but antiferromagnetic in the disordered B2 state [33]. Therefore, the magnetization
appears to be considerably depressed at the APBs, as shown schematically in Fig. 9(b). The
depression of ferromagnetism will change the magnetic parameters responsible for the thickness of
the magnetic domain walls. Consequently, the wall thickness is effectively reduced at the APBs. In
other words, the spin twisting may be different from that observed in a conventional Bloch wall
produced in a region with uniform magnetization (Fig. 9(a)). It is plausible that the energy of the
magnetic domain walls is minimized at the APBs, which could explain the significant pinning force
inhibiting domain wall motion.

Fig. 8 Determination of the width of the 180 wall located at an APB in Ni50Mn25Al12.5Ga12.5. (a)
Lorentz microscope image showing a 180 wall (dark line). (b) Intensity profile measured along
line AB in (a). (c) Full width at half maximum (FWHM) of the intensity profile plotted as a
function of the defocus value Z. Reprinted with permission from [30].

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Fig. 9 Schematic illustrations of the structure of 180 walls. (a) Typical case of a Bloch wall
formed in a ferromagnetic matrix. (b) Magnetic domain wall formed at an APB (gray portion) in
Ni50Mn25Al12.5Ga12.5.

Estimation of Magnetic Parameters Based on TEM Observations


As mentioned in the previous section, the magnetic parameters Ku and A are important in the study of
magnetic compounds. For example, as mentioned in the previous section, the width of a magnetic
domain wall depends on these parameters. However, we do not have a comprehensive database of Ku
and A (particularly A), because complex experiments must be carried out to determine these
parameters. In order to evaluate Ku, for instance, magnetization curves should be obtained for
magnetic fields applied in both the easy and hard magnetization axes of a single crystal. To measure A,
we usually acquire magnon dispersion curves by neutron scattering. Here, we propose a method of
determining both Ku and A using TEM observations.
Estimation of the magnetic parameters was carried out using a model specimen of
La0.25Pr0.375Ca0.375MnO3. As shown in the Lorentz microscope image of Fig. 10(a), a magnetic
contrast was produced in a nonmagnetic parent phase. This contrast (i.e., pair of the bright dot and the
white dot) indicates that the ferromagnetic phase was formed as a single domain containing no
magnetic domain wall; refer to the schematic illustration shown in the inset [32]. The ferromagnetic
domain grew during the subsequent cooling to 46.8 K, and changed to a double domain, as shown in
Fig. 10(b).

Fig. 10 Change in the Lorentz microscope image of a manganite La0.25Pr0.375Ca0.375MnO3 sample


upon cooling. Reprinted with permission from [32].

V.A. Chernenko

125

Based on TEM observations, we can measure the magnetic domain wall energy per unit area d
and the magnetic domain wall width (180 wall) Wd. Both of these parameters can be expressed using
Ku and A, in which we are interested.

d = 4 AK u ,
Wd = = A K u ,

(1)
(2)

where represents the magnetic exchange length [43]. Thus, we have two equations with two
unknown parameters. Solving these equations yields A and Ku.
The parameter d can be evaluated in the following manner. Lorentz microscopy observations,
such as those shown in Fig. 10, indicate that the critical radius (rc: half the domain size) at which a
single domain changes into a double domain is approximately 39 nm. We assume that the domain is
spherical, and that at the point rc the domain wall formation energy (drc2) equals the reduction in the
demagnetization energy resulting from the conversion to the double domain form. The reduction in
the demagnetization energy is approximately I s 2rc 3 9 0 (i.e., half of the original demagnetization
energy), where Is is the saturation magnetization and 0 is the permeability of vacuum. These results
lead to an estimation of d to be 1.8 103 J/m2.
The parameter Wd can be determined from electron holography as well. Figure 11(a) shows a
reconstructed phase image observed in La0.25Pr0.375Ca0.375MnO3 at 40.3 K. The contour lines represent
the in-plane component of the magnetic flux. We focus on the 180 wall, which is indicated by the
dotted line. This wall separated the large ferromagnetic domains A and B. Figure 11(b) is a plot of the
phase shift (x) of electrons measured along the line XY across the 180 domain wall, where x
indicates the position along the line XY. The sign of (x) changed from positive to negative at the
180 domain wall (refer to the transient area in the plot of Fig. 11(b)). Using a classical approximation
of spin twisting near the domain wall [43,44], the distribution of the in-plane magnetic flux
component can be approximated by ctanh{x/()}, where c is a constant. Since the derivative of (x)
is related to the in-plane magnetic flux component, the parameter can be determined by curve fitting
d(x)/dx (Fig. 11(c)). Thus, the domain wall width was determined to be 39 nm.

Figure 11 Determination of the width of the 180 wall in La0.25Pr0.375Ca0.375MnO3. (a)


Magnetic flux distribution determined by electron holography. Arrows indicate the direction of
the lines of magnetic flux. (b) Phase shift of the electron wave plotted along the line XY in (a).
(c) Derivative of the phase shift shown in (b). The gray line in (c) represents the curve fitting
result. Mother phase represents the nonmagnetic parent phase. Reprinted with permission
from [32].

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By substituting the values of d and Wd into equations (1) and (2), the unknown parameters were
estimated to be Ku = 3.6 104 J/m3 and A = 5.6 1012 J/m. Although these results are obtained using
a thin-foil specimen of La0.25Pr0.375Ca0.375MnO3, they are in good agreement with the Ku value
determined from a magnetic torque measurement of a single-crystalline film (3.6 104 J/m3,
La0.7Ca0.3MnO3 at 77 K [44]) and the A value deduced from a magnon measurement by neutron
scattering (3.3 1012 J/m, La0.67Ca0.33MnO3 at 50 K [45]).
Summary
Electron holography and Lorentz microscopy both provide useful information regarding the magnetic
microstructure in ferromagnetic SMAs and related compounds. Since these methods are based on
TEM techniques, we were able to reveal the correlation between magnetism and lattice (including the
impact of structural imperfections), based on direct observation of the magnetization distribution and
other crystallographic features. Using peripheral TEM techniques (e.g., equipment to control
temperature, magnetic field, and pressure), the entire phase transformation process can be observed in
situ. The Lorentz microscopy images in Fig. 10 provide a typical result of in situ observation of the
nucleation and growth of a first order magnetic phase transformation. Furthermore, the important
magnetic parameters Ku and A can be estimated from these TEM observations. We expect that these
techniques can be widely applied to the investigation of magnetic functional materials.
Acknowledgments
The study of the Ni-based ferromagnetic SMAs was conducted in collaboration with Professors K.
Oikawa, K. Ishida, and Dr. T. Yano at Tohoku University. The study of the manganite was carried out
as a research project of Okinawa Institute of Science and Technology, in collaboration with Dr. J. J.
Kim, Mr. H. Kasai, Mr. S. Mamishin, and Professor S. Mori (Osaka Prefecture University). The
authors wish to thank all of the collaborators for their advice and assistance. The study of the
Ni-based alloys was supported by Grant-in-Aid for Scientific Research (S) and Grant-in-Aid for
Scientific Research (B) from JSPS.

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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.129

Polycrystalline Ni-Mn-Ga as a Potential Material for Magnetically Driven


Actuators
Martin Ptschke1,a, Stefan Roth1,b, Uwe Gaitzsch1,c, Claudia Hrrich1,d,
Andrea Bhm2,e and Ludwig Schultz1,3,f
1
2
3

IFW Dresden, Helmholtzstr. 20, D-01069, Dresden, Germany

Fraunhofer-IWU, Reichenhainer Str. 88, D-09126 Chemnitz, Germany

Dresden University of Technology, Department of Mechanical Engineering, Institute for Materials


Science, D-01062 Dresden, Germany
a

m.poetschke@ifw-dresden.de, bs.roth@ifw-dresden.de, cu.gaitzsch@ifw-dresden.de,


c.huerrich@ifw-dresden.de, eandrea.boehm@iwu.fraunhofer.de, fl.schultz@ifw-dresden.de

Key words: Ni-Mn-Ga, polycrystal, training, texture, magnetic-field-induced strain, MFIS

Abstract. Textured polycrystalline Ni-Mn-Ga alloys were prepared by directional solidification.


Alloys were chosen to have the 5M modulated martensitic structure after proper heat treatment. A
two-side mechanical training decreased the twin boundary pinning stress. The stress-strain
behaviour for the training process and the magnetically induced stress depends on the training
direction. Magnetic field induced strain was demonstrated in samples with a plate-like geometry.
The influence of the microstructure on the magneto-mechanical behaviour is discussed.
Introduction
Single crystals of Ni-Mn-Ga show magnetic-field-induced strain (MFIS) due to twin boundary
motion [1]. This effect is found in low temperature martensites which form around room
temperature from an austenite which is a cubic L21 phase arising upon cooling at around 750 C.
Prerequisites for MFIS are a uniaxial magnetic anisotropy and highly mobile twin boundaries [2].
Both features are found in Ni50Mn29Ga21 after annealing for homogenisation and stress relief [3]. Its
structure is a modulated martensite with five unit cells modulation length (5M), with tetragonal
symmetry and with c/a<1 [4]. Here we use the lattice parameters of a martensitic unit cell, which is
described in the austenite coordinate system (index A) [5].
Since the preparation of single crystals is time consuming and expensive there is a great interest
in polycrystals which are easier to produce and therefore cheaper.
There is little information of the influence of microstructure of polycrystals on the behaviour of
Ni-Mn-Ga on MFIS. Ullakko et al. report on magnetic-field-induced strains in polycrystalline NiMn-Ga at room temperature. But, they give very little information about the microstructure of their
alloys. It was an oriented crystal structure with columnar grains. No information on length and
diameter of the grains was given [6]. The strain vs. magnetic-field curves in that paper are very
similar to those given for single crystals elsewhere [7]. Liang et al. [8] report on reversible MFIS of
about 1150 ppm in zone melted Ni50.5Mn24Ga25.5 at -50 C. The microstructure is described as
oriented and textured. No information about the morphology of the grains is given. One conclusion
from these papers is that an orientation of the grains and a texture is beneficial to achieve MFIS by
twin boundary motion in polycrystalline Ni-Mn-Ga.
A possible approach to prepare textured material is by directional solidification. Another route is
plastic deformation, but the brittleness of the alloy is well known. Hot rolling [9], rod extrusion [10]
and high-pressure torsion [11] at a temperature of about 1000 C is reported to be possible, but the

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overall degree of texture which can be achieved this way is low because of dynamic
recrystallisation.
Recently we could show that it is possible to achieve magnetic-field-induced strain caused by
twin boundary motion in textured polycrystalline Ni50Mn29Ga21 after mechanical training [5,12,13].
In this paper we report on the preparation of textured samples by a directional solidification
technique. The influence of the directionally solidified microstructure and the sample shape on the
mechanical properties and the MFIS are discussed. Furthermore, MFIS is measured in samples with
a plate-like geometry.
Experimental
Directional solidification was performed by a hot mould technique [14]. The principle of the
experimental set up is displayed in
Fig. 1. A hot mould is mounted on a cooling copper plate. To avoid heating of the cooling plate by
the hot mould, an insulation ring is placed between the mould and the plate. When the melt is cast
into the mould, a temperature gradient and, thereby, a heat flow through the melt towards the
bottom is generated, which causes a directional solidification in opposite direction. The texture is
supposed to occur along the direction of the heat flow.
After the casting, the samples of 10 x 50 mm were subjected to successive annealings in an
Ar/5 % H2 atmosphere, first at 1000 C for 48 h for homogenisation and then at 600 C for 14 h to
relax stresses [15]. The transformation temperatures were measured with a Perkin Elmer DSC,
using a scan rate of 10 K/min. TMart = 55 C was derived from the average of the peak-temperatures
of the cooling and the heating curves. The grain orientations were investigated with electron
backscatter diffraction (EBSD) in a scanning electron microscope (SEM).
The cubes (5 x 5 x 5 mm) and plates (10 x 6 x 1.8 mm) for the mechanical training were spark
cut from the textured part of the directionally solidified ingot. One edge of the cube and the length
of the plates were oriented along the direction of solidification. The samples were ground and
polished in order to achieve plane and parallel surfaces. The training was performed by alternative
compression along two perpendicular directions in order to favour only one twin system. Such
experiments were performed at room temperature in an Instron 8562 testing machine equipped with
a load cell with a capacity of 20 kN and the cross-head speed was 0.1 mm/min. The trained sample
was glued on a holder and placed in the yoke of an electromagnet. A magnetic field up to 1 T was
applied, which was measured with a Hall-probe. The strain was measured in length direction by a
polychromatic light beam (sensor Micro Epsilon optoNCDT 2402/90-4, resolution 100 nm).

q ds
preheated
mold
liquid
insulation
solid
chill
Fig. 1: Principle of hot mould casting to achieve a directional solidification. The heat flow q is
antiparallel to the direction of solidification dS.

V.A. Chernenko

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Results
Microstructure by directional solidification. The typical microstructure of an as-cast sample
(in the austenitic state) with optimized casting parameters is displayed in Fig 2. The microstructure
can be divided into four zones. In the first very narrow zone at the bottom fine almost globular
grains are observed. This is due to the close contact to the cooling plate and the resulting high
cooling rate. In this region, also a grain selection takes place. In the second zone, columnar grains
can be seen. The length of this zone depends on the casting parameters, especially on the mould
temperature. With increasing mould temperature the area of elongated grains becomes larger. An
optimal mold temperature was 1200 C at the start of the casting. At the top of the second zone a
conical region can be seen, where in the center still columnar grains can be observed in contrast to
the globular grains on the rim of the sample. Here the solidification direction changes gradually
from unidirectional (to the copper plate) to radial (to the mould). Above this cone all the grains are
globular, which we call zone 3. In the fourth region sink holes and other cavities due to melt
shrinkage can be seen.
The pole figure of zone 2 (Fig 2) shows that the columnar grains have a <100>A fibre texture
parallel to the solidification direction. The preferred growth direction along the direction of heat

Deviation of <100>A from dS (X-direction)

4
{100}A

3
Y

Z
5 mm

min

max
intensity

Polefigure of zone 2

Fig 2: The EBSD-mapping shows the typical as-cast microstructure of a directionally solidified
sample with the four zones. The pole figure of zone 2 reveals the <100>A fibre texture. The Xdirection is parallel to the direction of solidification dS.
flow is the <100>A-direction, which corresponds with literature [16]. The length of the columnar
grains is up to 20 mm and the diameter is in the millimetre range. Zone 2 shows the desired texture
and so the samples for further characterization were taken from this zone.

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Mechanical training of polycrystalline Ni-Mn-Ga cubes with a <100>A fibre texture. The
aim of the training is to reduce the stress which is necessary to move the twin boundaries (so called
twinning stress) below the magnetically inducible stress (so called magneto stress). The training is
performed by compressing the samples consecutively from different sides. In order to use such a
material in an actuator a two-side mechanical training is necessary. One training direction is
specified by the texture and lies along the fibre direction (X-direction). The second training
direction is perpendicular to the fibre direction. When using a cubic sample there are two possible
directions for the second training direction. By using another sample shape (plates) one of these
directions can be distinguished for mechanical training. For the technical realisation of the
mechanical training of a cube the direction which shows larger strain when compressing along the
fibre texture is chosen as the second training direction (here called Y-direction).
By mechanical training, the twinning stress can be reduced and the strain is increased. This is due
to a simplification of the initially complicated twin-microstructure. The two-side mechanical
training leads to one type of twin or even a single variant state in the individual grains [17]. After
some training cycles, the stress-strain curves do not change anymore. The stress-strain curves for
compression along the two training directions show a different behaviour (see Fig. 3). Along the
fibre direction (X-direction) the curve shows a single-crystal-like behaviour with a stress plateau.
The movable twin boundaries, which are {110}A planes, all have the maximum Schmid-factor of
m = 0.5 for motion. The Schmid-factor is a geometrical criterion, which describes the projection of
a normal stress on the slip-direction in the slip-plane. For the tetragonal martensite these are the
<11;0>A direction and the {110}A-plane [18]. If a critical stress is exceeded all the twin boundaries
in the different grains start to move at the same time. This causes the stress-plateau. Since
theoretically the a-axes can directly change to c-axes the maximum possible strain of 6 % could be
reached by compression along the fibre direction. In the polycrystal this maximum strain is not
reached because of deviations of the grains from the <100>A texture and constraints at the grain
boundaries.
The curve for compression along the second training direction (Y-direction, perpendicular to the
fibre texture) shows an increasing slope. Here, the Schmid-factor depends on the angle of rotation of
the grains around the X-axis, and is reduced. This means that the critical stress to move the twin
boundaries is reached at differing and higher stress levels. The maximum achievable strain is
reduced because of the deviation of the a- and c-axes from the compression direction.
Also the magneto stress is different for the two directions. Here the magneto stress was measured
while compressing the sample and turning on a magnetic field perpendicular to the load direction at
various strain levels. When applying the magnetic field parallel to the fibre direction all the movable
twin boundaries experience the maximum possible shear stress since they all have a maximum
Schmid-factor of 0.5. For 5M Ni-Mn-Ga the maximum normal stress a magnetic field can exert on a
twin boundary is 2.6 MPa. The measured magneto stress perpendicular to the magnetic field is a
little bit lower (only 2.5 MPa, see Fig. 3) because of the geometrical projection of the maximum
force of 2.6 MPa in the Y-direction. If the magnetic field is applied perpendicular to the fibre
direction (Y-direction) then not all the twin boundaries experience the critical shear stress for
motion because of their smaller Schmid-factors. This leads to a much smaller measured magneto
stress of only 1.7 MPa in the fibre direction (X-direction).
The expected magnetic-field-induced strain of such a fibre textured sample is different for the
two training directions because of the different shape of the curves and the different magneto
stresses. Furthermore, the strain, which is resettable by a magnetic field, is limited by the lower of
the two magnetic-field-induced strains.

V.A. Chernenko

133

Fig. 3: Stress-strain curves for two-side mechanical training of a cube with a fibre-texture.
Influence of sample shape. In order to further decrease the twinning stress and to improve MFIS
a plate-like sample geometry was chosen. The plates were cut from the textured area of the
directionally solidified sample with the length along the columnar grains. The thickness of the plates
was in the range of the diameter of the columnar grains, so there are only 1-2 grains across the
thickness. Thus, besides the direction of solidification a second direction (i.e. the thickness
direction) is distinguished for mechanical training. Across the thickness and the length, very little
grain boundaries are expected to be perpendicular to the stress direction. For investigations of
different training processes two plates (plate A and B) were cut parallel to each other from the same
ingot to ensure the same microstructure.
Plate A was trained by compression along the length direction and the thickness direction
alternately. After some training cycles the initially hard behaviour is changed and the curves showed
higher strain at lower stress levels. This behaviour is again due to simplification of the initially
complicated twin-microstructure. Fig. 4 shows the stress-strain curves for the 13th (t-13) and 15th (t15) compression along thickness and the 12th (l-12) and 14th (l-14) compression along length. The
difference in the shape of the curves for compression along the length and the thickness is already
known from the training of the cubic samples and due to the <100>A fibre texture. Further training
cycles did not change the curves remarkably, so the training was stopped. No compression was
applied along the width direction of the plate and the width did not change remarkably after the 1st
training cycle. This implies that after the 1st training cycle the a-axis is fixed along the width of the
plate. Consequently the c-axes alternates between the trained directions.

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Fig. 4: Stress-strain curves for plate A after several training cycles along thickness and length. t13 (t-15) means 13th (15th) compression along thickness and l-12 (l-14) means 12th (14th)
compression along length.
Plate B was trained in length and width direction, to investigate the influence of the grain
boundaries. In width direction there are at least 8 grains (see inset in Fig. 5). The stress-strain curve
(see Fig. 5) for compression in length direction during the 14th compression (l-14) is comparable to
the curve measured in length direction of plate A and shows again the single-crystal-like behaviour.
In contrast, along the width direction the curve has a very steep slope at the beginning. Compared to
the stress-strain curve for compression along the thickness direction, the curve for compression
along the width direction is shifted to much higher stress values. This is because in the former case
there are very few or no grain boundaries perpendicular to the stress direction, while in the latter
case the grain boundaries are assumed to be perpendicular to the stress direction, which hinders twin
boundary motion. Further training did not significantly change the stress-strain behaviour. The
absence of grain boundaries perpendicular to the stress direction significantly decreases the
twinning stress. Therefore the plate-geometry can improve the MFIS.

V.A. Chernenko

135

Fig. 5: Stress strain-curves for plate B after several training cycles along width and length. w-13
means 13th compression along width and l-14 means 14th compression along length.
Free strain due to MFIS. The free strain due to MFIS was examined at room temperature. Plate
A which was trained along length and thickness was glued on a sample holder and set in an
electromagnet. The strain was always measured in length direction. It was found that the sample
showed strain starting at a low magnetic field and saturating at around 600 mT. The curve for the
18th cycle of MFIS in Fig. 6 shows the elongation of the plate in length direction when the magnetic
field is applied in thickness direction. Upon the application of the magnetic field, the magnetically
easy c-axis aligns in the field direction and the a-axes align in the other two directions. Since the caxis is the short axis compared to the a-axes the length of the plate increases (red curve in Fig. 6).
The maximum strain is 0.16 % above 600 mT. When the magnetic field is turned off the strain
slightly decreases to a value of 0.15 %. This is due to internal stress which set back the strain. The
curve for the opposite magnetic field direction is symmetric. In the 19th cycle the magnetic field was
aligned parallel to the sample length, so the short c-axis aligns in the field direction and the samplelength shrinks (black curve in Fig. 6). The strain of the 18th cycle is fully reset to zero. This
behaviour is repeatable for more than 20 times. This results show, that it is possible to achieve
magnetically resettable strain in polycrystalline Ni-Mn-Ga alloys. This opens new opportunity for
using polycrystalline material showing MFIS in actuators.

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Fig. 6: Strain vs. magnetic field for the 18th and 19th cycle of MFIS. The strain is measured in length
direction and is fully resettable by the magnetic field.
Summary
Directionally solidified polycrystalline Ni-Mn-Ga was prepared by a technologically simple hot
mould casting process. The samples show a <100>A fibre texture. A two-side mechanical training
decreased the twinning stress. Due to the microstructure there is a difference in the stress-strain
behaviour and magneto stresses for the two training directions. This leads to a smaller resettable
MFIS compared to single crystals. The influence of the grain boundaries was investigated by using a
plate-like sample geometry, with nearly no grain boundaries existing perpendicular to the thickness
an length of the plate. The absence of grain boundaries improved the stress-strain behaviour. A
resettable free MFIS was measured in such plates.
This work was carried out within the priority program SPP 1239 of the German Research Society
(DFG). The authors would like to thank A. Phl and H. Klau for technical assistance.

V.A. Chernenko

137

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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.139

Metamagnetic Shape Memory Effect and Magnetic Properties


of Ni-Mn Based Heusler Alloys
R. Kainuma1, a, W. Ito1, b, R.Y. Umetsu2, c, V. V. Khovaylo3, d, T. Kanomata4, e
1

Department of Materials Science, Tohoku University, Sendai 980-8579, Japan

Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

National University of Science and Technology MISiS, Moscow 119049, Russia


4

Faculty of Engineering, Tohoku Gakuin University, Tagajo 985-8537, Japan.

kainuma@material.tohoku.ac.jp, bw-ito@material.tohoku.ac.jp, crieume@imr.tohoku.ac.jp,


d

khovaylo@misis.ru, ekanomata@tjcc.tohoku-gakuin.ac.jp

Key words: metamagnetic shape memory, metamagnetic phase transition, martensitic


transformation, magnetic field-induced strain, layered structure, magnetic property, Ni-Mn-In,
Ni-Mn-Sn

Abstract. In some Ni-Mn-In- and Ni-Mn-Sn-based Heusler-type alloys, martensitic transformation


from the ferromagnetic parent phase to the paramagnetic martensite phase appears and magnetic
field-induced reverse transformation, namely, metamagnetic phase transition, is detected. In this
paper, the metamagnetic shape memory effect due to the metamagnetic phase transition and the
magnetostress effect in the Ni-Co-Mn-In alloys are introduced and the phase diagrams of
Ni50Mn50-yXy (X: In, Sn, Sb) alloys are shown as basic information. Furthermore, the magnetic
properties of both the parent and martensite phases in the Ni-Mn-In- and Ni-Mn-Sn-based
metamagnetic shape memory alloys are also reviewed.
Introduction
Shape memory alloys (SMAs) with applications in various fields, such as medical guidewires,
cellar-phones antennas, and smart actuators, are also potential candidates for actuators such as motors
and supersonic oscillators, because of the extremely large strain and stress generated by the shape
memory effect (SME) as compared to those generated in piezoelectric and magnetostrictive
materials. However, it is not easy to obtain a rapid response to the input signal because the thermal
conductivity of the alloys is a rate determining factor of the response [1]. This drawback is one of the
factors that limits the application of SMAs as actuators. Magnetic shape memory alloys (MSMAs),
in which a rapid output strain is achieved through the application of a magnetic field, have been
developed to overcome this obstacle.
In 1996 Ullakko et al. [2] first reported the magnetic field-induced strain (MFIS) in a
ferromagnetic Ni2MnGa single crystal and stimulated research on MSMAs. The MFIS obtained in a
ferromagnetic Ni2MnGa single crystal is explained by the rearrangement of martensite (M) variants
due to an external field. When the crystalline magnetic anisotropy energy of the M phase is larger
than the driving force required for the variant boundary-migration, the variant rearrangement occurs
and yields the MFIS, which is consistent with the twin-deformation strain induced by the monoaxial
stress, instead of the magnetic field. Details on the MFIS in the Ni2MnGa alloys have recently been
reviewed by Marioni et al. [3]. Although large output strain greater than 9% [4] and rapid response
can be confirmed in the Ni2MnGa alloy, the output stress is principally lower than about 5 MPa [5].
Although attemptes have been made to obtain MFIS due to phase transformation in Ni2MnGa alloys
[6-8], no satisfactory result has been obtained because of the small magnetization change between
the parent (P) and M phases [9].

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In 2004, Sutou et al. [10] found that some non-stoichiometric ferromagnetic alloys in Ni-Mn-X
(X: In, Sn and Sb) systems show martensitic transformation and reported the phase diagrams of the
Ni50Mn50-yXy systems. Although stoichiometric Ni2MnX Heusler alloys with bcc-based (L21) crystal
structures are known to exhibit ferromagnetism [11,12], martensitic transformation in these alloys
had not yet been reported until that time. Subsequently, especially in the Ni-Mn-In and Ni-Mn-Sn
alloys, an unusual transformation from the ferromagnetic P phase to the weak magnetic M phase,
which exhibits behaviors completely different from those of the previous MSMAs, have been
reported [13] and the magnetic-field-induced SME, namely, metamagnetic shape memory effect
(MMSME), has been confirmed in the Ni-Co-Mn-In and Ni-Co-Mn-Sn alloys [14,15]. Moreover,
since the report on the metamagnetic shape memory alloy (MMSMA), many investigations have been
performed and some unique physical properties such as giant magnetoresistance [16,17], giant
magnetothermal conductivity [18], and the inverse magnetocaloric effect [19,20] have been reported.
Details of these properties appearing in the Ni-Mn-based alloys have recently been reviewded by
Planes et al. [21].
In this paper, the MMSME, the phase diagrams and the magnetic properties of the P and M
phases, mainly in the Ni-Mn-In and Ni-Mn-Sn based alloys, are reviewed.
Metamagnetic shape memory effect [14]
Figures 1(a) and (b) show the thermomagnetization (M(T)) curves in the magnetic fields of 0.5,
20 and 70 kOe and the magnetization curves at 200, 270, 290, and 320 K in the Ni45Co5Mn36.6In13.4
alloy, respectively [14]. In the M(T) curve of 0.5 kOe, the Curie temperature TC of the P phase is
detected at around 380 K, and the martensitic transformation starting temperature TMs appears at
around 300 K. The magnetization is observed to drastically decrease with decreasing temperature
from the TMs to the martensitic transformation finishing temperature TMf and that the thermal
hysteresis is approximately 10 K. It is also observed that the difference in the magnetization between
the P and M phases is approximately 100 emu/g and that the TMs and TMf temperatures and the
temperatures TAs and TAf at which the reverse transformation starts and ends, respectively, decrease
by 25 K due to the increase of the magnetic field from 0.5 to 70 kOe. This result suggests that at
temperatures between 270 and 290 K, the M phase transforms to the P phase due to application of the
magnetic field of 70 kOe. This behavior, i.e., the magnetic field-induced reverse transformation
(MFIRT), was actually confirmed in the magnetization curves at 270 and 290 K, as shown in Fig.
1(b). This indicates that this quaternary alloy shows a magnetic field-induced SME due to this
metamagnetic phase transition at room temperature.
As shown in Fig. 1, the TMs and TMf temperatures decrease with the increase of the magnetic field.
The degree of the decrease T, however, differs in the alloy systems. For instance, the decrease in the

Fig. 1 Thermomagnetization curves in magnetic fields of H = 0.5, 20 and 70 kOe (a) and
magnetization curves at various temperatures (b) in the Ni45Co5Mn36.6In13.4 alloy [14].

V.A. Chernenko

141

value of TMs for a magnetic field of 70 kOe is approximately 50 K in Ni46Mn41In13 [13] but
approximately 25 K in Ni45Co5Mn36.6In13.4. Since the T determines the temperature range showing
the MFIRT, a large T is required to induce the MFIRT in a larger temperature range. The T,
namely, transformation temperature change, induced by the magnetic field change, H, is
approximately given by the Clausius-Clapeyron relation in the magnetic phase diagram:
dH
S
=
,
dT
M
M
T
H ,
S

(1)

where T and H denote the absolute temperature and applied magnetic field, and M and S, the
differences in magnetization and entropy between the P and M phases, respectively. According to
Eq. 1, the decrease in the value of TMs induced by the magnetic field is proportional to the value of H
when M/S is constant. In the Ni-Co-Mn-In alloy shown in Fig 1, the value of S experimentally
determined by DSC measurement is 27.0 J/Kkg [14], and the T estimated by Eq. 1 on the basis of
the experimental values of M (= 100 emu /g) and H (= 70 kOe) is 26 K, which is in good agreement
with the experimental value [14]. On the other hand, the T estimated in the Ni46Mn41In13 alloy with
a smaller S (=17.1 J/Kkg) and almost the same M compared with those in the Ni-Co-Mn-In alloy,
is about 41 K [13]. These results support the relationship given by Eq. 1 and imply that a large value
of M and a small value of S must accompany the martensitic transformation if a large variation in
TMs is desired.
The shape recovery induced by the magnetic field was examined by a three-terminal capacitance
method with the Ni45Co5Mn36.7In13.3 specimen [14]. Figure 2 shows the recovery strain induced by
the magnetic field at 298 K, at which a compressive pre-strain of approximately 3% was applied in
the direction plotted with a filled circle in the stereographic triangle shown in the inset of Fig. 2 and
the magnetic field was applied vertically to the compressive axis of the specimen. The recovery
strain started to increase at approximately 20 kOe and rose sharply at approximately 36 kOe and then
gradually increased to 80 kOe with increasing the magnetic field. A recovery strain of approximately
2.9%, almost equal to the pre-strain of 3%, was obtained with a magnetic field of 80 kOe.

Fig. 2 Recovery strain at 298 K induced by a


magnetic field for the Ni45Co5Mn36.7In13.3 alloy in
which a compressive pre-strain of about 3% was
applied, where the magnetic field was applied
vertically to the compressive axis of the specimen and
the length change parallel to the compressive axis was
measured [14].

Fig. 3 Magnetostress effect detected in the


superelastic Ni45Co5Mn36.5In13.5 alloy. Critical
stress of stress-induced martensitic
transformation increases with increasing
applied magnetic field [22].

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In contrast with the conventional MSMAs such as Ni2MnGa and Fe-Pd, this MMSMA system
has many advantages for practical applications. The most important advantage may be that the
present MFIS can yield a high work output stress due to the magnetic field, i.e., magnetostress. The
Clausius-Clapeyron relation on the critical stress for the stress-induced martensitic transformation is
given by
d c
S
=
,
dT
Vm

(2)

where denotes the difference in the lattice strain between the P and M phases in a corresponding
direction and Vm denotes the molar volume of the alloy. The magnetic field-induced change in the
critical stress corresponds to the output stress obtained by the combination with Eq. 1, as follows:
c

S
M
T
H .
Vm
Vm

(3)

This equation shows that the magnetostress is approximately proportional to the magnetic field. In
Eq. 3, the fact that c is inversely proportional to may be one of the most important points. This
suggests that the value of c can be varied by the selection of the deformation direction in a single
crystal. Recently, Karaca et al. have experimentally confirmed that a Ni45Co5Mn36.7In13.3 specimen
shows a magnetostress effect of about c =30 MPa for H=16 kOe in the <100> p direction, as
shown in Fig. 3 [22]. Furthermore, by using Eq. 3 they evaluated the c for a magnetic field of 10
kOe in the compressive deformation mode approximately 27 and 143 MPa along the <100>p and
<111>p directions with = 6.61% and 1.22%, respectively [22]. Thus, in NiCoMnIn alloys, the work
output stress is greater than that ( 5 MPa) in NiMnGa alloys, whereas the output strain is relatively
smaller than that ( TD 9 % [3]) in the Ni-Mn-Ga alloys.
In the MMSME, a rapid response to an input signal with a magnetic field is expected. Sakon et
al. [23] have reported that a Ni45Co5Mn36.7In13.3 single crystal exhibited an almost perfect MMSME
for a single magnetic field pulse of 200 Hz, whose characteristic features are similar to that in a static
magnetic field. The MMSME has recently also been confirmed in polycrystalline and sintered
Ni-Co-Mn-Sn alloys [24,25].
Phase diagrams of Ni50Mn50-yXy base alloy systems [10,26]
The phase diagrams of Ni50Mn50-yXy (X: In, Sn, Sb) alloys reported by Sutou et al. [10] and Ito et
al. [26] are shown in Fig. 4. It is seen that the martensitic transformation temperatures decrease with
increasing y, while the TC temperature in the P phase slightly increases. It is very interesting to note
that the gradients of both the TMs and TC drastically change at the cross point in every alloy system and
that the degree of change of cocentration dependence after the crossing-over increases with the order
of X = In > Sn > Sb. The interaction between the structural and magnetic transformations has recently
been analyzed by Kataoka et al. [27], whose theory is introduced by Kanomata et al. with a case of
Ni-Mn-Ga-Cu alloys in this book. This suggests that the transformation strain and the magnetic
properties are strongly correlated with each other.
In order to increase the TC, the addition of Co for Ni is known to be very effective. Figure 5
shows the TMs and TC for the Ni45Co5Mn50-yIny (5Co-yIn) and the Ni42.5Co7.5Mn50-yIny (7.5Co-yIn)
alloys [26]. It is seen that in the whole region, whereas the TMs of the alloy with the same In
composition decreases, the TC of the P phase significantly increases by doping Co. Similar
tendencies have also been reported in the Ni-Co-Mn-Sn alloys [28]. It is apparent that the decrease
of the TMs temperature in the ferromagnetic region after crossing with the TC line is gradual in the
beginning and accelerated with further cooling. This behavior has been considered to be due to the
thermodynamic contribution of the second order magnetic transformation in the P phase [26].

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143

It has been reported that the order-disorder phase transformation from the B2 to the L21 Heusler
structure occurs in the Ni50Mn50-yIny alloys and that the critical temperature, TtB2/L21 , shows a convex
curve in this concentration section as shown in Fig. 6 [29]. The values of TtB2/L21 are located in the
temperature region from 800 K to 1100 K, which almost coincides with those of the Ni50Mn50-yGay
alloys, as shown in Fig. 6 [30]. The maximum temperature of TtB2/L21 in the Ni50Mn50-yIny alloys is
located at 22.5 In, and deviates from the stoichiometric composition of Ni2MnIn. It is not clear why
such a difference in the maximum point of TtB2/L21 appears in these systems. As well as in the
Ni-Mn-Ga alloys, the magnetic and martensitic transformation behaviors in the Ni-Mn-In based
alloys are affected by the degree of order that is a function of the annealing condition [31,32].

Fig. 5 Magnetic phase diagrams of Ni50-xCox


Mn50-yIny alloy systems. Substitution of Co for Ni
results in increase of TC of P phase and decrease of
TMs [26].

Fig. 4 Magnetic phase diagrams of


Ni50Mn50-yXy (X: In, Sn, Sb) alloy systems
[10, 26].

Fig. 6 B2/L21 order-disorder transformation


temperatures of Ni50Mn50-yIny and Ni50Mn50-yGay
alloys [29,30].

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Magnetic properties of P phase [33]


As shown in the above phase diagrams, the concentration dependence of the TC in the P phase is
not so stong in all the alloy systems. The concentration dependence of spontaneous magnetization,
however, is very complicated, especially in the Ni-Mn-Sn alloys. Figure 7 shows the total magnetic
moment for formula unit, total, estimated from the spontaneous magnetization at 4.2 K for the
Ni50Mn50-yIny and Ni50-xCoxMn50-ySny (xCo-ySn) alloys, respectively. In the case of the In alloys, the
magnetic moments monotonically increase with decreasing In content [29]. This result means that
the magnetic coupling between the Mn atoms at Mn and In sites is always ferromagnetic. On the
other hand, for the 0Co-ySn specimens, the dependence of Sn content on magnetic moment shows a
concave curve with a minimum of about y = 20 at.% Sn, deviating from the theoretical straight line
drawn on the assumption that the Mn atoms at Mn(4b) sites are antiferromagnetically coupled with
the Mn atoms at Sn(4d) sites. Furthermore, due to substitution of Co for Ni, all the total drastically
increase and those for 8Co specimens simply linearly increase with decreasing Sn content. Here, it
should be noted that this line for the 8Co specimens is almost parallel to the straight line theoretically
given in the case that the Mn atoms at the Mn(4b) sites are ferromagnetically coupled with those on
the Sn(4d) sites for the 0Co-ySn alloys. Furthermore, for the 5Co specimens, while still retaining the
concave behavior in high Sn content region of over y = 16, the dependence of Sn content on magnetic
moment almost coincides with the straight line of 8Co specimens in the low Sn content region. This
suggests that also in the low Sn content region of the 0Co-ySn specimens, the concave curve connects
to a linear line based on the ferromagnetic coupling, as shown in the 5Co specimens.

Fig. 7 Magnetic moment of P phase in


Ni50Mn50-yIny and Ni50-xCoxMn50-ySny alloys
[29,33,35].

Fig. 8 Lattice parameters of P phase in


Ni50Mn50-yIny and Ni50-xCoxMn50-ySny alloys
[33,34,35].

Thus, two kinds of interesting behaviors, i.e., concave behavior in Sn concentration dependence
of magnetic moment in the ternary Ni50Mn50-ySny and disappearance of the concave behavior due to
the substitution of Co for Ni, are detected in the Ni-Mn-Sn-based alloys. Figure 8 shows the lattice
constants for the 0Co-ySn and 8Co-ySn specimens determined by XRD [33,34,35]. It can be seen
that while being almost linear in the Ni-Mn-In, the composition dependence of the lattice constant
apparently shows a convexity in the high Sn region of 0Co-ySn. The origin of the convex behavior on
the lattice constant appearing only in the 0Co-ySn alloys is unknown, but this may be related to the
concave behavior on the magnetic moment demonstrated in Fig. 7. On the other hand, the Sn
composition dependence of the lattice constant for the 8Co-ySn specimens becomes almost linear,
and the lattice constants are basically smaller than those for the 0Co-ySn specimens, as shown in Fig.
8. These results suggest that some correlation exists between the magnetic configuration and the
lattice constant. It is known that the magnetic exchange interaction in the Ni-Mn based Heusler
alloys mainly originates from the Ni(8a)-Mn(4b or 4d) and Mn(4b)-Mn(4d) pair interactions.

V.A. Chernenko

145

aolu et al. [36] have recently reported that the Ni-Mn exchange interaction in the first nearest
neighbor (FNN) in the Ni-Mn based Heusler alloys is ferromagnetic and depends on the lattice
constant, increasing with decreasing lattice constant. The concave behavior may be brought about by
the increase of the ferromagnetic exchange interaction in the FNN Ni-Mn pairs induced by decrease
of the lattice parameter. On the other hand, it has been reported that the Co(8a)-Mn(4b or 4d)
ferromagnetic exchange interaction in Co2MnSn Heusler alloy is about several times larger than the
Ni-Mn exchange interaction in Ni2MnSn alloy [37,38]. These reports support our experimental result
showing the increase of the magnetic moment as exhibited in Fig. 7.
Magnetic properties and crystal structures of M phase [39]
Because the M phase in the binary NiMn alloy with L10 structure is antiferromagnetic [40], the
magnetic property of the M phase had been expected to be antiferromagnetic. However, we have
recently confirmed that the M phase with a very low magnetization existing at temperatures just
below the TMf in the Ni-Mn-In and Ni-Mn-Sn alloys is paramagnetic, but not antiferromagnetic
[39,41]. Figure 9 shows the thermomagnetization curve obtained from the Ni50Mn34.357Fe0.5In15.2
alloy [39] that exhibits almost the same M(T) curves as the Ni50Mn35In15 alloy [26, 42]. Since the TMs
is very close to the TC, in the cooling process the magnetization increasing at the TC immediately
decreases at the TMs of 300 K, remains almost zero and then starts to increase again at around 200 K.
The field-cooling effect is clearly detected, as shown in Fig. 9. Figure 10 shows the Mssbauer
spectra at 200, 303 and 352 K obtained from the Ni50Mn34.357Fe0.5In15.2 alloy [39]. It is apparent that
the spectra of the M and the P phases with a low magnetization taken at 200 K and 352 K, respectively,
show a single peak with a very narrow half width, while the spectrum obtained at 303 K located at just
below the TC in the P phase includes some ferromagnetic component that makes the half width thick.
This means that the M phase with a low magnetization at temperatures ranging from 200 to 300 K is
paramagnetic and that the martensitic transformation in this specimen shows an abnormal magnetic
transformation sequence from the ferromagnetic P phase to the paramagnetic M phase.

Fig. 9 Thermomagnetization curve obtained from the


Ni50Mn34.357Fe0.5In15.2 alloy under a magnetic field of
0.5 kOe [39].

Fig. 10 Mssbauer spectra at 200, 303


and 352 K obtained from the
Ni50Mn34.357Fe0.5In15.2 alloy [39].

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A similar Mssbauer examination has also been carried out in the Ni-Mn-Sn(-57Fe) alloy, and the
same result on the magnetic property of the M phase has been confirmed [41]. Recently, Aksoy et al.
have performed a neutron diffraction examination for the Ni-Mn-Sn alloy and reported that the
antiferromagnetic interaction exists in the whole M phase region [43]. Actually, the field-cooling
effect appearing in the low temperature region showing some magnetization suggests that the
magnetic condition in the M phase is complicated. The magnetic property of the M phase in the low
temperature region is still under discussion.
In Ni-Mn-In and Ni-Co-Mn-In alloys, a mixture of 10- and 14-layered monoclinic martensitic
phases, i.e., the 10M and the 14M phases, has been reported [13,26,42]. The layered structures, such
as the 10M- and 14M-type structures expressed with ( 3 2 )2 and ( 5 2 )2 in Zhdanov notation,
respectively, are sometimes considered to be a tetragonal structure with a high density of ordered
nano-twins [44]. If the 10M- and 14M-type structures have the same stacking unit composed of the
distorted L21 phase denoted as a face-centered tetragonal (fct) structure, the lattice parameters for the
10M- and 14M-type structures can be easily evaluated on the basis of the 2M structure possessing a
lattice correspondence with the fct structure as a2M = c2M = ( a fct + c fct )/2 and b2M = afct (Fig. 11).
2

For the Ni50Mn34.357Fe0.5In15.2 alloy with the M(T) curves shown in Fig. 9, the lattice parameters of
the 2M structure, a2M = 0.4377, b2M = 0.5654 and c2M = 0.4377 nm and 2M = 99.54, which
correspond to afct = 0.5654 and cfct = 0.6684 nm for the fct structure, were determined by using some
peaks independent of the layered structures in the experimental X-ray diffraction pattern. This result
means that the basic tetragonal distortions from the L21 phase due to the martensitic transformation
are about -6% along the a-axis and about +11% along the c-axis, and that the volume change is about
-1%. The X-ray diffraction patterns calculated for 10M and 14M are shown in Fig. 12, together with
the experimental one [39]. The experimental pattern can be indexed as a mixture of the 10M- and
14M-type structures with the lattice parameters, a10M = 0.4377 nm, b10M = 0.5654 nm, c10M = 2.1594
nm and 10M = 91.93; and a14M = 0.4377 nm, b14M = 0.5654 nm, c14M = 3.0302 nm and 14M = 94.35,
respectively, obtained based on the experimental data for the 2M structure.

Fig. 11 Projections of the face-centered


tetragonal (a), 2M (b), 10M(c), and 14M (d)
structures on the b axis [39].

Fig. 12 X-ray powder diffraction pattern at room


temperature taken from the M phase of
Ni50Mn34.357Fe0.5In15.2 alloy and calculated
patterns estimated on the basis of some
fundamental lines appearing in the experimental
pattern [39].

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147

As listed in Table 1, in the Heusler P phase of Ni50Mn34.357Fe0.5In15.2 alloy at T = 320 K, the


distances between Ni and Mn(4b and 4d) positions in the first NN, between Mn(4b) and Mn(4d)
positions in the second NN, and between Mn(4b) and Mn(4b) positions in the third NN are rAfnn =
0.2597 nm, rAsnn = 0.2999 nm, and rAtnn = 0.4241 nm, respectively. If the presence of the nano-twin
boundaries in the layered structures can be neglected, these atomic distances are affected by the
simple tetragonal distortion from the cubic structure. As compared with the P phase, the rMfnn of
Ni-Mn(4b) and Ni-Mn(4d) pairs in the first NN of the M phase are 0.3% larger than that (rAfnn) of the
P phase, and both rAsnn and rAtnn are split by the structural distortions into the two inequivalent
distances (rMsnn and rMtnn) listed in Table 1.
The observed abnormal magnetic phase transition sequence from paramagnetic M to
ferromagnetic P phase seems to be due to a strong dependence of the exchange interactions on
interatomic distances [36-38,45,46] as well as to the magnetic coupling of Ni(8a)-Mn(4b or 4d) and
Mn(4b)-Mn(4d) pairs in the P phase as discussed in the previous section. In the M phase, two sets of
Mn-Mn distances [i.e., Mn(4b)-Mn(4b) and Mn(4b)-Mn(4d)] in the P phase are split into four sets
due to the structural distortions of the cubic lattice, as shown in Table 1. Taking into account the
coordination number, the effective changes of the exchange interactions may result from the decrease
(from rAsnn = 0.2999 to rMsnn = 0.2827 nm) of the Mn(4b)-Mn(4d) distance and the increase (from rAtnn
= 0.4241 to rMtnn = 0.4377 nm) of the Mn(4b)-Mn(4b) distance of the major pairs in the M phase.
Assuming that the Mn-Mn exchange interaction curve for the M phase is the same as that for the P
phase, it is strongly suggested that at least the Mn(4b)-Mn(4d) interactions in the c plane of the fct M
phase, where their atomic distance decreases about 5.7% by martensitic transformation, must be
antiferromagnetic, as schematically illustrated in Fig. 13. Furthermore, the increase in distance of the
Ni-Mn pairs also might result in a decrease of strength in their ferromagnetic coupling.
Thus, it is suggested that the magnetic properties of both the P and M phases in the MMSMAs are
related to the dependence of the exchange interactions on the interatomic distances of the Ni-Mn and
Mn-Mn pairs. Further experimental and theoretical investigations are required to clarify the origin of
such complicated magnetic behaviors.

Table 1 Coordination number and distances between Ni-Mn and Mn-Mn pairs
in the high-temperature L21 phase and the low-temperature fct phase of Ni50Mn34.357Fe0.5In15.2 [39].

Pair
Ni-Mn(4b)
in first NN
Ni-Mn(4d)
in first NN

L21 (a = 0.5998 [nm])


Distance, Coordination
rAinn [nm]
number

fct (a = 0.5654, c = 0.6684 [nm])


Ratio,
Distance,
Coordination
(dM - dA)/dA [%]
rMinn [nm]
number

0.2597

0.2605

0.3

0.2597

0.2605

0.3

Mn(4b)-Mn(4d)
in second NN

0.2999

0.2827
0.3342

4
2

-5.7
11.4

Mn(4b)-Mn(4b)
in third NN

0.4241

12

0.3998
0.4377

4
8

-5.7
3.2

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Fig. 13 Sketch of Mn-Mn exchange interaction curve in Ni2MnIn-based Heusler alloys [39].
Summary
The characteristics of the metamagnetic phase transition and metamagnetic shape memory effect
in the Ni-Mn based Heusler-type alloys were introduced, and the phase diagrams and the magnetic
properties of both the P and M phases mainly in the Ni-Mn-Sn and Ni-Mn-In alloys with 50% Ni were
reviewed. In the phase diagrams of Ni50Mn50-yXy (X: In, Sn, Sb) alloys, an apparent interaction
between the magnetic and martensitic transformations was detected and the concentration
dependences of both the Curie temperature of the P phase and the martentistic transformation
temperatures drastically changed at the crossing point. In the P phase, while the concentratioin
dependence of the Curie temperature is very small, that of the spontaneous magnetization is large and
complicated. That is, in the Ni50Mn50-yIny alloys, the spontaneous magnetization monotonically
increases with decreasing y from y = 25. In the Ni50Mn50-ySny alloys, however, the magnetization
decreases with decreasing y in the concentration region from y = 25 to 20 and then starts to increase at
around y = 20. On the other hand, it was confirmed by the Mssbauer examination that the magnetic
property of the M phase with a very low magnetization in the Ni-Mn-In and Ni-Mn-Sn alloys is
paramagnetic and that the martensitic transformation is the ferromagnetic P phase from the
paramagnetic M phase. Thus, the metamagnetic shape memory alloys show some complicated
magnetic behaviors that maight be related to the dependence of the exchange interactions on the
interatomic distances of Ni-Mn and Mn-Mn pairs.
Acknowledgements
The authors are grateful to Mr. T. Miyamoto, Profs. K. Ishida, K. Oikawa and A. Fujita, Tohoku
University, and Prof. Y. Amako, Shinsyu University, for their assistance with the experiments. This
study was supported by Grant-in-Aids for Scientific Research and Japan - Russia Cooperative
Science Program from the Japan Society for the Promotion of Science (JSPS), Japan, and by Global
COE Project.

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149

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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.151

Reverse Magnetostructural Transitions by Co and In Doping NiMnGa


Alloys:
Structural, Magnetic, and Magnetoelastic Properties
Franca Albertini1,a, Simone Fabbrici1,b, Antonio Paoluzi1, Jiri Kamarad2,
Zdenek Arnold2, Lara Righi3, Massimo Solzi4, Giacomo Porcari4,
Chiara Pernechele4, David Serrate5 and Pedro Algarabel5
1

IMEM-CNR Parma, Italy

Institute of Physics AS CR, Prague, Czech Republic

Dipartimento di Chimica GIAF, Universit di Parma, Parma, Italy

Dipartimento di Fisica, Universit di Parma & CNISM, Parma, Italy

Facultad de Ciencias, Universidad de Zaragoza & INA, ICMA-CSIC, Zaragoza, Spain


a

franca.albertini@imem.cnr.it, bfabbrici@imem.cnr.it

Key words: Martensitic transformation, Heulser alloys, NiMnGa, superelastic alloys, magnetic
shape memory, reverse transformation

Abstract.
We review the composition dependence of the structural and magnetic properties of the Co-doped
NiMnGa Ferromagnetic Shape Memory Alloy around the Mn-rich composition Ni50Mn30Ga20.
The presence of Co affects the critical temperatures and alters the exchange interactions of
martensite and austenite to different extents; by varying the composition it is possible to tune the
critical temperatures and to induce a paramagnetic gap between the magnetically ordered
martensite and magnetic austenite, thus giving rise to a reverse magnetostructural transformation.
The magnetic and structural properties display noticeable discontinuities across the martensitic
transformation: remarkable values of the saturation magnetization jump at the transformation (M),
of the field dependence of the martensitic transformation temperature (dTM/dH), and of the
crystalline volume change (V/V) are reported, and are considerably enhanced by additional Indoping of the quaternary alloy.
These properties give rise to a remarkable phenomenology which is of interest for multifunctional
applications; magnetic superelasticity and high values of reversible strain are found.
Introduction
Ni-Nn-X alloys, X being a group IIIA-VA element, have drawn a lot of interest in recent years for
their multifunctional behavior [1]: giant effects can be induced by the application of a magnetic
field, such as magnetocaloric [2], magnetoelastic [3, 4] and magnetoresistive effects [4, 5].
Moreover they are ferromagnetic and show remarkable properties induced by temperature, applied
pressure and stress (e.g. shape memory [6], barocaloric effect [7]) that can be exploited and
combined [8] in new-concept systems and smart devices based both on bulk and nanostructured
materials. The interplay between structure and magnetism is at the origin of their extraordinary
phenomenology: a martensitic transformation between two phases, a low symmetry martensite and
a cubic austenite occurs [9-10], also involving a change in the magnetic properties [1]. Associated
with the magnetostructural transition huge magnetic field induced strains have been obtained due to
two different mechanisms. One is the so called magnetic shape memory, as proposed by Ullakko
et al in 1996 [11]; it is due to field-induced twin boundary orientation in the martensitic phase. The
second is the magnetic super-elasticity; it is due to magnetic field-induced structural
transformation [4, 12]. The magnetic key property in the first case is the magnetocrystalline
anisotropy of martensite that make the twin boundary displacement more favorable than the

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magnetization rotation [13]. In the second case it is the magnetization variation (M) at the
transformation, and consequently the magnetic field dependence of the martensitic transformation
temperature. The same property is also crucial for the optimization of the magnetocaloric effect [1].
For this reason, it has been possible to obtain up to four-time increase of the magnetocaloric effect
in suitable Ni-rich composition ranges (e.g. Ni54.5Mn20.5Ga25) where Curie and martensitic
transitions merge [14, 15]. In this case the magnetization jump at the transition is maximized; in
fact the sample transformation is between a ferromagnetic austenite and a paramagnetic martensite.
In Ni50+vMn25+wGa25+z (v+w+z=0) alloys, for all studied compositions, a negative magnetic entropy
change has been obtained, giving rise to a direct magnetocaloric effect arising from a higher
saturation magnetization in the martensitic than in the austenitic phase. In these systems a positive
field dependence of the martensitic transformation temperature has been found [16].
On the contrary, Ni-Mn based Heuslers containing In, Sn and Sb show a so-called reverse
martensitic transformation where the low temperature phase presents a much lower magnetization
value with respect to the parent one [17]. In a narrow compositional range the structural
transformation is preceded by a Curie-like transition affecting the martensite (TCM), further
reducing the magnetization of the low temperature phase before the structural transformation [18,
19]. The temperature region between TCM and the martensitic transformation is characterized by a
very low magnetization value; for this reason it has been reported as paramagnetic gap. The
nature of the magnetic interactions ruling the temperature range between TCM and TM is still a
matter of debate; while some neutron polarization measurements performed in the gap of Sn and
Sb based alloys can be consistent with the presence of some antiferromagnetic interactions [20],
recent Mossbauer experiments performed on In based alloys seem to corroborate the paramagnetic
nature of the gap [21].
Such a reduced level of magnetization preceding the transformation to the ferromagnetic austenitic
phase (high moment), gives rise to high M values at the transformation. This fact is highly
favorable for driving the structural transformation by an external magnetic field, allowing the
magnetic super-elasticity [1]. Another consequence deriving from the reverse nature (from para to
ferro) of the magneto-structural transformation is that, differently from the ternary Ga based alloys,
the associated MCE is inverse [2], i.e. they show a positive magnetic entropy change, and cooling
is attained when the magnetic field is applied.
It has been recently found that it is possible to induce a reverse martensitic transformation also in
NiMnGa alloys by proper Co doping. The presence of Co enhances the stability of the magnetically
ordered austenite and weakens the magnetic interactions and the structural stability of martensite:
the Curie transition of austenite is shifted to higher temperatures while the martensitic
transformation and the Curie temperature of martensite are shifted to far lower temperatures. Also,
contrary to the Co-free compositions, the magnetic moment of austenite is higher than the
martensitic one [22, 23, 24]. We have recently identified a Mn-rich region of Co-doped alloys,
showing the so-called paramagnetic gap also in the Ga based alloys [24], leading to high values of
the inverse magnetocaloric effect [25, 26]. The discussion of the magnetocaloric effect is beyond
the scope of the present paper. Here we will focus on the effects of Co substitutions on transitions,
structure, and magnetism in the compositional range (5xCo9 and 30yMn 32) in order to deepen
the critical behavior of this class of materials and to tune the main properties.
Finally, we will show how the additional doping of In to a selected quaternary alloy composition
results in further improvement of the aforementioned functional properties and in noticeable
magnetoelastic effects, pushing these materials among the most promising candidates for
multifunctional applications.
Experimental
Samples of compositions Ni50xCoxMnyGa50y with 5x13 and 30y32, and Ni41Co9Mn32Ga16In2
were prepared by arc melting technique followed by annealing.
The critical temperatures were measured by Thermo-Magnetic Analysis (TMA), which consists in
measuring the temperature dependence of the initial ac susceptibility in an applied field of few Oe

V.A. Chernenko

153

in a temperature range between 4 and 1000 K. TMA is an effective way to measure the temperature
of the structural and magnetic transitions; in the NiMnGa system, the martensite and austenite
phases have different magnetic anisotropy [27] and therefore the susceptibility signal intensity
changes across the transition. In TMA the Curie temperature is usually taken as the inflection of the
ac susceptibility. The isothermal and isofield magnetic properties were measured in SQUID
magnetometers (max field 5T, temperature range 5-500 K). Unit cell volumes of the parent and
product phases were evaluated by X-ray diffraction at the transformation temperatures using a
Thermo ARL Xtra diffractometer equipped a solid-state Si(Li) Peltier detector and an
environmental chamber.
The thermal expansion and magnetostriction were measured in fields up to 5T by exploiting the
strain-gauge technique; the measures were collected with the strain sensing direction both parallel
and perpendicular to the applied magnetic field.
Structural and magnetic transition temperatures
Structural and magnetic transition temperatures of the Ni50-xCoxMnyGa50-y alloys are strongly
affected by composition, as summarized in Table 1 and Fig. 1. The Curie transitions show a linear
dependence on Co and Mn content. For several 3d-metal alloys, an increase of the Curie
temperature is generally found by increasing the Co content. In the present series such an increase is
only found in the austenitic phase (TCA/xCo=+12 K). On the other hand, the martensitic Curie
temperature TCM (where it is measurable) is found to decrease both by increasing Co and Mn
content. Moreover by increasing Mn content, a linear decrease of the austenitic Curie temperature is
observed (TCA/yMn=-8 K). The temperature shift of the martensitic transformation, although
mostly dependent on the Mn content, cannot be referred to a simple variation of just one species in
the composition. In fact, independently from the Mn composition the Co dependence is always
TM-A/ xCo15 K, while Mn dependence is influenced by the Co content
TM-A/yMn 55 K for xCo=5 and TM-A/yMn200 K the for xCo=7.
The occurrence of such a behavior is due to the presence of an antiferromagnetic alignment in the
Mn sublattices in Mn-rich NiMnGa alloys, and to a Co-induced modification of the exchange
interactions among Mn atoms, affecting in a different way the exchange coupling in martensitic and
austenitic phases [28, 29]. This fact originates a unique phenomenology that can be described by a
phase diagram where different regimes are found. In Fig. 2 we report the TMA plots as a function
of Co and Mn concentration.
Five different regimes have been found: they are characterized by a different number of first and/or
second order transitions evidenced by the TMA analysis, easily identifiable by the presence/absence
of thermal hysteresis. For the parent, Co-free sample (i.e. xCo=0, yMn=30) the Curie (TCA) and
martensitic transformation (TM-A) co-occur (one first order transition, Fig. 2a); for low Co and Mn
content the martensitic transformation occur at a much lower temperature than the austenitic Curie
transition (one first order and one second order transition, Fig. 2b); for high Co and low Mn content
the martensitic transformation is suppressed and the sample is cubic at all temperatures (one second
order transition, TCA, Fig. 2c); for xCo=5 and , yMn=32 ferromagnetism is present only in the
martensitic phase (only one second order transition in the TMA plot, TCM, Fig. 2d).
For xCo7 and yMn 31 two second order and one first order transitions occur (Fig. 2e). In this
region the samples show a complex susceptibility behavior as a function of temperature: a second
order critical temperature well below TM-A (the Curie temperature of martensite, TCM) defines a
region where the a.c. susceptibility is null, i.e. the material is paramagnetic; however, since the
austenitic Curie temperature, TCA, is far higher, by heating beyond this region the structural
transformation re-introduces a magnetic character in the material before the last drop to zero of the
a.c. susceptibility signal determined by TCA. In this configuration the martensite to austenite
transformation is concurrent with a reverse magnetic transition ( i.e. a the paramagnetic martensite
turns into magnetically ordered austenite). The proposed interpretation of this complex series of
critical temperatures has been confirmed by a structural study as a function of temperature (see [25]
and below).

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Table 1. Nominal compositions, and magnetic and structural critical temperatures of the presented
samples.
TCM [K]
TM-A [K]
TA-M [K]
TCA [K]
Ni50Mn30Ga20
376
372
374
Ni45Co5Mn30Ga20
337
327
420
Ni43Co7Mn30Ga20
182
163
450
Ni45Co5Mn31Ga19
353
341
420
Ni43Co7Mn31Ga19
323
385
372
436
Ni45Co5Mn32Ga18
300
408
406
408
Ni43Co7Mn32Ga18
295
426
420
433
Ni41Co9Mn32Ga18
257
436
421
456
Ni41Co9Mn32Ga16 In2
245
343
321
446

Figure 1. Curie (TCA and TCM) and martensitic (TM-A and TA-M) transition temperatures as a
function of the Co content in Ni50xCoxMnyGa50y. Crossed symbols refer to the Mn composition
y=30 series, solid symbols stand for y=31, open symbols stand for y=32 while half-solid symbols
stand for the In-doped Ni41Co9Mn32Ga16In2 sample.
In order to improve the figures readability, the two right panels report the same critical
temperatures for just the y=30 (top) and y=32 (bottom) series; the arrows emphasize the region of
existence of the magnetically ordered austenite. The barber poles depicted in the lower right panel
highlight the region of existence of the paramagnetic gap shown in the y=32 series.

The presence of Co plays a different role in the magnetic interactions of austenite and martensite, as
it promotes ferromagnetic ordering in austenite while weakening the exchange interactions in
martensite. In fact, the paramagnetic gap is realized by the abrupt decrease in the Curie temperature
of the martensite, TCM, which is shifted by the presence of Co to far lower temperatures than TM.
By playing with the relative amount of Co and Mn it is possible to tune the temperature range of
existence of the paramagnetic gap and of the martensitic phase transformation temperature. No
paramagnetic gap is present in the yMn=30 series, while it has been found in yMn=31 (xCo=7) and
yMn=32 (xCo=7, 9) samples. In this last series the widest gap is found at the highest Co content
(xCo=9) due to the contemporary TCM decrease and TM-A and TA-M increase. In contrast, at low Co
content (xCo=5), due to the different TCA dependence on Co with respect to TM-A, the martensitic
transformation and the austenitic Curie transition merge, leading to the disappearance of the
magnetically ordered austenite. The inset of Fig. 2d highlights the magnetic signatures of such
nearly coincident critical temperatures.

V.A. Chernenko

155

Figure 2. TMA plots of the presented samples arranged as a function of the Co (increasing from top
to bottom) and Mn (increasing from left to right) contents. The different colors highlight the
different regimes of the magnetic and structural critical temperatures. (a), green panel:
transformation from ferromagnetic martensite to paramagnetic austenite. (b), cyan panel:
transformation between ferromagnetic austenite and ferromagnetic martensite followed (by
increasing T) by Curie transition from ferromagnetic austenite to paramagnetic austenite. (c), white
panel: Curie transition between ferromagnetic austenite and paramagnetic austenite. (d), yellow
panel: Curie transition between ferromagnetic martensite and paramagnetic martensite and
concurrent structural transformation and austenitic Curie temperature (inset). (e), light red panel:
Curie transition from ferromagnetic martensite to paramagnetic martensite followed by reverse
transformation between paramagnetic martensite and ferromagnetic austenite.

Magnetic behavior and magnetic field dependence of martensitic transformation


The Co dual effect leading to a strengthening of the magnetic interactions in austenite and a
concurrent weakening in martensite is evidenced by the composition dependence of MS in the two
phases. The saturation magnetization values in the martensitic phase at T=5 K, are reported in Table
2. For Mn content yMn31 MS is drastically reduced by Co down to -38.5% for the sample with the
highest Mn and Co content (i.e. xCo=9, yMn=32). The aforementioned reduction of the magnetic
interactions due to Co doping is triggered by a Mn content exceeding yMn=30. In fact, at that Mn
composition MS is slightly increased by Co (up to +7% for xCo=7) with respect to the undoped
sample.
The interpretation of the different martensitic MS dependence on Co triggered by the Mn content is
not simple and many factors should be taken into account, first of all the site occupancy by the
atomic species.
In a fully ordered structure, Ni and Co are expected to occupy (in the cubic reference) the same 8c
site while Mn and Ga the 4a and 4b site, respectively [1, 9, 29, 30]. In a localized description of NiMn-X alloys, with the magnetic moment mostly confined on Mn atoms, ferromagnetic interactions
between Mn can be inferred to be positive for Ni50Mn25Ga25 and for off-stoichiometric alloys with
Mn content not exceeding the stoichiometric quantity (yMn25). Moving into the Mn-rich region,

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Advances in Magnetic Shape Memory Materials

the extra Mn atoms occupy some of the 4b sites left by the Ga deficiency, thus promoting the onset
of antiferromagnetic interactions [28, 31]. The distribution of extra Mn atoms increases by
increasing Mn content, affecting more and more unit cells. The compositional limit at which every
unit cell statistically contains one extra Mn is yMn=31; above that amount Co was found to induce a
decrease of martensitic MS.
Moreover, a possible atomic disorder, eventually enhanced by the off-stoichiometry, is also
expected to play a very important role both on the magnetic and on the martensitic properties, as
recently shown in [33].
Table 2. Saturation magnetization measured for martensite (at 5K) and austenite (at a reduced
temperature T*=T/TC). Isothermal magnetization jump at the transformation (Miso). field
dependence of the martensitic temperature (dTM/dH). Relative volume discontinuity at the
transformation deduced from diffraction measurements (V/V).
MSM
dTM/dH [K/T]
MSA
Miso
V/V
2
2
2
[Am /Kg]
[Am /Kg] [Am /Kg]
Ni50Mn30Ga20
66.6 0.4
-5.20.8
+0.570.20
0.2%
Ni45Co5Mn30Ga20
69.60.4
59.50.4 15.40.8
-1.040.14
0.45%
Ni43Co7Mn30Ga20
72.60.4
62.50.4 32.60.8
-2.780.26
0.6%
Ni45Co5Mn31Ga19
66.50.4
58.50.3 14.90.7
-1.250.25
0.55%
Ni43Co7Mn31Ga19
57.80.3
59.20.3 39.20.7
-2.950.26
0.65%
Ni45Co5Mn32Ga18
49.050.3
Ni43Co7Mn32Ga18
45.70.3
Ni41Co9Mn32Ga18
410.2
53.32.3 49.32.5
-2.80.4
0.8%
Ni41Co9Mn32Ga16 In2
37.20.3
79.10.7 73.51.0
-5.00.2
0.9%

It is also worth noting that Mn composition yMn=31 seems also to be involved in a change of the
electronic structure of the system. In fact, by plotting the transformation temperatures TM-A as a
function of the outer electrons (Fig. 3) a substantially different behavior is shown for yMn=30 and
yMn31 series. In the first case, a positive dependence of
TM-A is found, as generally for NiMnX Heuslers [1, 32]; the observed trend is non linear, possibly
due also to a change in the martensitic structure from 7M-orthorhombic (at xCo=0, yMn=30) [34] to
tetragonal at higher Co contents. In the second case (all tetragonal structures), a linear but negative
dependence of the martensitic temperature on e/a is obtained.

Figure 3. Martensitic transformation temperatures on heating reported vs. the number of valence
electrons per atom. The y = 30 series shows a positive dependence of TM-A vs. e/a, contrary to the y
= 31 and 32 series. The lines are guides to the eye.

V.A. Chernenko

157

On the contrary, the main Co effect on the austenitic phase consists in promoting the ferromagnetic
interactions: a large increase in the saturation magnetization values is produced for all doped
compositions. The values have been reported in Table 2 at a fixed reduced temperature
T*=T/TCA=0.86 in order to be comparable along the series. A slight increases with Co content and a
slight decrease with Mn are observed, but changes limited to a maximum spread of 5%.
In order to understand the physical origin of the above described phenomenology, measurements of
atomic and magnetic ordering, and band structure and electronic properties calculations are highly
desirable.
For all the Co doped alloys, in contrast with the undoped series, at the structural transformation the
magnetization of the austenitic phase is higher than the martensitic one. The isothermal differences
Miso between the saturation magnetization of the parent and product phase, measured in a
magnetic field oH=5T, are reported in Fig. 4 and Table 2. Noticeably, by Co doping, two
remarkable effects are induced: very high values of Miso, and its change of sign. As a
consequence, the possibility to drive the magnetic transition by field, represented by the parameter
|dTM/dH| is strongly enhanced (Fig. 4, Table 2), and the martensitic transformation temperature is
decreased by the application of a magnetic field, as shown by metamagnetic Ni-Mn based Heuslers
containing In, Sn and Sb.
Miso increases by increasing both Co and Mn up to 49.5 2.5 Am2/kg for sample xCo=9, yMn=32;
the highest values are associated with the samples showing the paramagnetic
gap. The dTM/dH parameter turns from weak and positive values of the parent sample dTM/dH=
+0.570.2 K/T to dTM/dH -30.3 K/T for samples showing the paramagnetic gap.

Figure 4. Magnetization jump at the transformation Miso (left panel) and dependence of the
structural transformation to the applied magnetic field dTM/dH (right panel). The labels report the
sample compositions in the xCo-yMn notation. The dashed lines are visual guides separating positive
and negative values.

Effects of the homovalent substitution of Ga


The finding of new alloys showing high values of |dTM/dH| is of great importance, not only from
the magnetocaloric point of view, but also for the possibility to drive the martensitic transformation
by field and to induce other related giant-effects (e.g. magnetic superelasticity, barocaloric,
magnetoresistive) [3-5, 7].
Moreover, in order to develop materials suitable for application in cyclic operation devices, it is
important to exploit high dTM/dH values to obtain martensitic temperature variations that exceed
the thermal hysteresis affecting the magnetostructural transformation.
With the aim to lower TM while preserving the noticeable magnetostructural properties shown by
sample Ni41Co9Mn32Ga18, an homovalent partial substitution of the sp element was performed, as
proposed in [35]. The obtained sample, of composition Ni41Co9Mn32Ga16In2 shows the
paramagnetic gap. While the austenitic and martensitic Curie temperatures are maintained, the

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substitution of just 2% Ga with In lowers the martensitic transformation temperature of about 90K;
for example, TM-A shifts from 436K of sample Ni41Co9Mn32Ga18 to 343K, (Table 1, Fig. 5).
Remarkably, due to the increased distance between the onset of the austenitic phase and its Curie
transition temperature the Miso and dTM/dH values (Table 2) are about 33% and 40% higher than
the quaternary In-free composition.

Figure 5. Comparison of the magnetic and structural critical temperatures in Ni41Co9Mn32Ga18 (top)
and Ni41Co9Mn32Ga16In2 (bottom)

Structural properties and volume variation at the martensitic transformation


The remarkable modifications of the magnetic properties and of the critical behavior, including the
occurrence of the paramagnetic gap, may be dependent, among other factors, from the structural
modifications induced across the martensitic transformation.
In order to investigate these features, X-ray diffraction patterns on crystalline powders were
collected varying the temperature. The evolution of the crystal structures across the transformation
has been analyzed by structural refinement analysis, returning the lattice parameters and the crystal
volumes of the two phases at different temperatures.
The measurements point out that the martensitic transformation in these samples is a complex
many-step process realizing in a consistent temperature span; many features, like the role of defects,
the strain energy between the two phases and the blocking effect shown by the smaller grains,
concur to the depicted behavior. Thus, the measured volume difference (V/V) between martensite
and austenite shows scattered values at different temperatures, also due to the different thermal
expansions of the two lattices.
In order to provide a consistent outline we considered the mean values of the V/V data in a
restricted range of the transformation, i.e. by taking into consideration the diffraction patterns which
returned a refined phase fraction in the range 15-85%.
This procedure allowed us to observe a general trend of the volume differences as a function of
stoichiometry which noticeably mimics the already described composition dependence of the
magnetic properties.
A common feature involving the measured samples is the bigger volume of austenite compared to
the martensitic one. The sign of the V/V parameter is always positive when transforming from the
low temperature phase to the high temperature one; also, while the ternary Co-free composition
martensite shows a 7M modulated structure [10], by introducing Co the crystal structure of
martensite turns to tetragonal non-modulated symmetry.

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The volume difference is enhanced by Co, and increases by increasing both Co and Mn. In the
parent samples V/V0.2%; by adding Co V/V increases between 0.45% of sample 5-30 up to
0.8% of sample 9-32, as reported in Table 2. The trend mimics the dependence of the saturation
magnetization jump with composition: the highest values are reported for samples with highest Co
content (x>7) and in particular for samples showing the paramagnetic gap. The reported values are
comparable and, for certain compositions, even exceed previous results reported in literature for
other Ni-Mn-X (X=In, Sn and Sb) FSMAs [36], qualifying the quaternary alloy NiCoMnGa among
the most promising Ni-Mn based Heusler alloys for magneto-elastic applications.
As already observed for the magnetic properties, the additional doping with In emphasizes also the
structural discontinuity at the transformation. As expected, the XRD analysis points out that by
introducing an element with a bigger atomic radius the lattice parameters of both phases generally
increase; for instance, the lattice parameters of martensite at room temperature are a=3.863 ,
c=6.604 (Vol=197.107 3) in Ni41Co9Mn32Ga18 and a=3.886 , c=6.612 (Vol=199.657 3) in
Ni41Co9Mn32Ga16In2. Noticeably, also the volume difference is enhanced, providing a mean V/V
value comprised between 0.9% and 1%.
By following the temperature evolution of the two phases, some features concerning the martensitic
transformation can be highlighted.

Figure 6. Portion of the X-ray diffraction patterns for sample Ni41Co9Mn32Ga16In2 at different
temperatures.

Fig. 6 shows the evolution of the XRD pattern of the In-doped sample with temperature in the range
comprising the (112) and (200) tetragonal reflections of martensite and the (220) austenitic one; as
it is clearly visible from the absence of thermal drift, in these samples the (112) reflection appears
as the invariant direction of the martensitic transformation.
The adaptive nature of martensite is suggested by the temperature dependence of the tetragonal
distortion c/a, which shows different values depending on the thermal history of the material (Fig.
7, left panel); in fact, the tetragonal distortion at a given temperature is always lower when the
sample is transforming on cooling from the cubic parent phase. On the contrary, the transformation
on heating involves a more distorted martensite.
The variation of the tetragonal distortion during the transformation originates from the highly
anisotropic thermal expansion of martensite; while the basal plane expands on heating, the
tetragonal axis shrinks. Given the different multiplicity of the two directions, the tetragonal
shrinking is faster than the planar expansion (Fig. 7, left panel): in the shown temperature range the
tetragonal c axis variation is approximately -0.08 , while the planar a axis varies about +0.04 .
Moreover, it is possible to appreciate that the origin of the thermal history dependence of the c/a
parameter relies on the remarkable difference between the cooling and heating measurements of the

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tetragonal axis c, as shown in the left panel of Fig. 7.


By comparing the above mentioned quantities as a function of the austenitic weight fraction, it is
found that this behavior seems not connected either to the weight fraction of the two phases or the
thermal hysteresis.
The overall consequence of this complex situation, together with the isotropic thermal expansion of
austenite occurring at a different slope, gives rise to a certain degree of scattering of the V/V data
with temperature (Fig. 8); nevertheless, a mean V/V value (being for this sample slightly higher
than 0.9%) can still be reliably estimated.

Figure 7. (left) c/a ratio calculated for the martensitic phase of sample Ni41Co9Mn32Ga16In2 at
different temperatures. (right) Thermal expansion of the martensitic lattice parameters. The label
c marks the values calculated from the cooling branch of the transformation. Unmarked values
are calculated from heating measurements.

Figure 8. Relative volume change at the transformation estimated by structural analysis of the Xray diffraction patterns at different temperatures for sample Ni41Co9Mn32Ga16In2. The label c
marks the values measured on cooling.

Superelastic behavior and magnetic field induced strain in Ni41Co9Mn32Ga16In2.


Additional magneto-strain measures performed on bulk samples by exploiting the strain-gauge in
parallel and perpendicular configurations pointed out a superelastic behavior characterized by
remarkable strain of these alloys. Fig. 9 reports the temperature dependence of the relative linear
deformation measured by the strain-gauge technique, collected at different magnetic fields in the
parallel configuration. The relative length change l/l shows at TM a sudden jump of 0.35%. The
applied magnetic field slightly enhances the isothermal value of l/l (about 13% increase of l/l
measured at 5T with respect to the 0T curve), with the parallel and perpendicular configurations
showing similar strain values. Given the isotropic response of this material, the occurrence of the

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magnetic field driven selection of twin-variants seems unlikely, contrary to the NiMnGa alloys [27].
The observed enhancement of the l/l values should probably be ascribed to the different slope of
the thermal expansion of martensite and austenite; such difference is in fact amplified by the high
dTM/dH values, which shifts the critical temperature up to 40K when changing the applied field
between 5T and 0T.
The measured l/l values provide also a further corroboration of the reliability of the structural
estimations discussed above, as the V/V values, estimated as 3*l/l (i.e. 0.9% - 1%) are
consistent with the reported structural analysis.
Concerning the superelastic character of these alloys, we show in Fig. 10 the isothermal field
induced strain measured in the perpendicular configuration by applying a magnetic field of 5T at
320K, close to the critical temperature on heating. The field induced transformation is fully
reversible; also, the martensitic phase transforms almost completely in the given field range, as
testified by the value of the induced linear deformation (up to 0.3%), close to full transformation
value reported above.

Figure 9. Temperature dependence of the strain at different applied fields for sample
Ni41Co9Mn32Ga16In2; the huge reversible deformation is associated to the martensitic
transformation.

Figure 10. Isothermal field induced strain (squares) and magnetization (circles) cycles measured
concurrently in the field range 0-5T for sample Ni41Co9Mn32Ga16In2.

Summary
In the present paper we have presented a thorough magnetic and structural study of Co-doped NiMn-Ga Heusler alloys. By changing Mn and Co content five different regimes, characterized by a
different sequences of magnetic and structural transformation, can be obtained. High values of M
(up to 49.3 Am2/Kg) at the martensitic transformation in samples showing the paramagnetic gap

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have been obtained, assuring the possibility to strongly drive the transformation by applying an
external magnetic field (|dT/dH| up to ~3K/T). Moreover very high values of V/V at the
transformation have been found. These noticeable properties have been further enhanced by a 2%
In- doping of the quaternary alloy (M up to 73.5 Am2/Kg, (|dT/dH| up to ~5K/T) also associated to
a high decrease (closer to RT) of the martensitic transformation temperature. Moreover, magnetic
superelasticity was observed to occur by applying a 5T field at 320 K, characterized by V/V
values of about 0.9%. For these properties, as well as for their giant magnetocaloric effect, Co and
In doped NiMnGa alloys can be considered a very promising class of materials for multifunctional
applications.

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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.165

Magnetic phase diagram of the ferromagnetic shape memory alloys


Ni2MnGa1xCux
K. Endo1, a, T. Kanomata1, b, A. Kimura1, c, M. Kataoka2, d, H. Nishihara3, e,
R. Y. Umetsu4, f, K. Obara4, g, T. Shishido4, h, M. Nagasako5, i, R. Kainuma5, j,
K. R. A. Ziebeck6, k
1

Faculty of Engineering, Tohoku Gakuin University, Tagajo 985-8537, Japan.

Department of Basic Sciences, Faculty of Science and Engineering, Ishinomaki Senshu University,
Ishinomaki 986-8580, Japan
3

Faculty of Science and Technology, Ryukoku University, Otsu 520-2194, Japan


4

Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Department of Materials Science, Tohoku University, Sendai 980-8579, Japan

Department of Physics, Cavendish Laboratory, University of Cambridge, CB3, 0HE, UK


a

s0994301@tjcc.tohoku-gakuin.ac.jp, bkanomata@tjcc.tohoku-gakuin.ac.jp,

b0641153@tohoku-gakuin.ac.jp, dkataokam@kxe.biglobe.ne.jp, enishihara@rins.ryukoku.ac.jp,


f

rieume@imr.tohoku.ac.jp, gobara@imr.tohoku.ac.jp, hshishido@imr.tohoku.ac.jp,

nagasako@material.tohoku.ac.jp, jkainuma@material.tohoku.ac.jp, kkraz2@cam.ac.uk

Key words: Heusler alloy, phase transition, phase diagram.

Abstract. X-ray powder diffraction, permeability, magnetization and differential scanning


calorimetry measurements were carried out on the magnetic shape memory alloys Ni2MnGa1xCux
(0 x 0.25). On the basis of the experimental results, the phase diagram in the
temperatureconcentration plane was determined for this alloy system. The determined phase
diagram is spanned by the paramagnetic austenite phase (Para-A), paramagnetic martensite phase
(Para-M), ferromagnetic austenite phase (Ferro-A), ferromagnetic martensite phase (Ferro-M) and
the premartensite phase. It was found that the magnetostructural transition between the phases
Para-A and Ferro-M can occur in the concentration region 0.12 < x 0.14 and that Ni2MnGa1xCux
has the characteristics of the phase diagram similar to those of the phase diagrams of Ni2+xMn1xGa
and Ni2Mn1xCuxGa. In order to understand the phase diagram, the phenomenological free energy as
a function of the martensitic distortion and magnetization was constructed and analyzed.
Introduction
Recently, much activity has been devoted to the development of ferromagnetic shape memory
alloys (FSMAs) [1]. FSMAs are potential materials for use as magneto-mechanical actuators
because they show a large magnetic-field-induced strain by the rearrangement of twin variants in
the martensite phase [2]. Until now, several candidates for FSMAs have been reported. Among
them, the stoichiometric Heusler alloy Ni2MnGa was mostly studied. This alloy has the cubic L21
Heusler structure at room temperature with the lattice parameter ac = 5.825 , and orders
ferromagnetically at the Curie temperature TC 365 K. On cooling below a martensitic transition
temperature TM 200 K, a superstructure forms [3].
Beside the magnetic shape memory effect as mentioned above, the magnetocaloric effect
observed in Ni-Mn-Ga alloys is of technological interest. An enhanced magnetocaloric effect was
observed in the vicinity of the combined magnetostructural transition from the ferromagnetic
martensite phase to the ferromagnetic austenite phase for Ni-Mn-Ga alloys [4-7]. Among Ni-Mn-Ga

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alloys, the Ni-rich Ni2+xMn1xGa FSMAs were mostly studied [8-14]. Vasil'ev et al. [15] and
Khovaylo et al. [16] studied the structural and magnetic phase transitions in the FSMAs
Ni2+xMn1-xGa. The experimental phase diagram of Ni2+xMn1xGa, constructed from differential
scanning calorimetry (DSC), transport and magnetic measurements, exhibits distinctive feature in a
compositional interval 0.18 x 0.27, where martensitic and magnetic transitions merge in a
first-order magnetostructural phase transition from the ferromagnetic martensite phase to the
paramagnetic austenite phase. Experimental values of the magnetic entropy change regarding the
magnetocaloric effect of Ni2+xMn1xGa with coupled magnetostructural transitions are about 30
J/kgK [8, 9, 13, 14]. These values are of the same order as in the so-called giant magnetocaloric
materials, such as La(Fe,Si)13 [17, 18].
More recently, magnetization, initial permeability and DSC measurements were done on the
FSMAs Ni2Mn1xCuxGa [19]. On the basis of the results, the phase diagram in the
temperature-concentration plane was determined for this alloy system. The phase diagram of
Ni2Mn1xCuxGa (0 x 0.4) is very similar to that of Ni2+xMn1xGa (0 x 0.36). Both martensitic
transition temperature and Curie temperature of Ni2Mn1xCuxGa (0 x 0.4) merge together in
samples with 0.23 x 0.30. Stadler et al. reported the magnetocaloric properties of
Ni2Mn1xCuxGa, which showed a maximum magnetic entropy change of Sm ~ 64 J/kgK at 308 K
under a magnetic field change H = 50 kOe for the sample with x = 0.25 [20]. The dependence of
Sm on H was approximately linear and did not reach saturation at 50 kOe. They demonstrated
that the temperature at which Sm occurs can be tuned through subtle variations in composition.
Continuous, measurements of the magnetocaloric effect for Ni2Mn1xCuxGa system have been given
by many authors [2125]. Thus, Cu-substituted Ni-Mn-Ga alloys are powerful candidates of the
room temperature magnetocaloric materials because they exhibit the first-order transition from the
paramagnetic austenite phase to the ferromagnetic martensite phase under field. As far as we know,
there is no data on the structural and magnetic phase transitions in the Cu-substituted FSMAs
Ni2MnGa1xCux except for the paper reported by Jiang et al.[26]. In this paper, the structural and
magnetic properties of Ni2MnGa1xCux (0 x 0.4) are examined experimentally and theoretically
to gain deeper insight into the phase transitions of these materials.
Experiment
The polycrystalline Ni2MnGa1xCux (0 x 0.25) were prepared by repeated arc melting of the
constituent elements, namely 99.99 % pure Ni, 99.99 % pure Mn, 99.99 % pure Cu and 99.9999 %
pure Ga, in argon atmosphere. All reaction products were sealed in the evacuated silica tubes,
heated at 850 C for 3 days and then 600 C for 1day before being quenched into water. The phase
characterizations of the samples were carried out by X-ray powder diffraction measurements using
CuK radiation.
The Curie, premartensitic and martensitic transition temperatures were determined by an ac
transformer method. The primary and secondary coils were wound on the sample rod with about
1mm in diameter and about 10 mm in length. An ac current of constant amplitude was applied in
the primary coil and the secondary voltage, which is directly proportional to initial permeability ,
was recorded as a function of temperature. The frequency of the ac magnetic field is 1 kHz. The
measurements were done after the samples were demagnetized. The magnetization M data were
collected using a commercial superconducting quantum interference device (SQUID)
magnetometer. Thermal analysis was carried out by DSC measurements, where the heating and
cooling temperature rate was 10 K/min.
Results and discussion
Experimental results. The Heusler L21 structure (space group: Fm3 m ) showed in Fig. 1 is
comprised of four interpenetrating fcc lattices A, B, C and D with origins at (000), ( ), (
) and ( ), respectively. In Ni2MnGa, Ni atoms occupy the A and C sites, and Mn atoms and
Ga atoms the B and D sites, respectively. Figure 2(a) shows the observed X-ray powder diffraction

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167

pattern at room temperature of the sample with x = 0.02. All the diffraction lines can be indexed
with the cubic structure. The intensities of the superlattice line such as (111) and (200) agree well
with the results calculated by assuming the L21 structure. These results ensure that the sample with
x = 0.02 has a fully ordered L21 structure. The lattice parameter ac of the sample with x = 0.02 is
found to be 5.8206 . We observed similar X-ray powder diffraction patterns at room temperature
for samples with x = 0.01, 0.03, 0.05 and 0.07, indicating that the samples of Ni2MnGa1xCux with
the concentration range 0 x 0.07 crystallize in the L21 structure at room temperature. Figure 2(b)
shows the X-ray powder diffraction pattern of the sample with x = 0.12. As shown in Fig. 2(b),
most of main reflection can be indexed using a fourteen-layered monoclinic (14M) structure (space
group: P2/m). The tetragonal phase with D022-like
crystal structure coexists with the monoclinic phase
with the 14M structure at room temperature in the
sample with x = 0.12. In Fig. 2(b), (hkl)t and (hkl)m
indicate the Miller indexes for the D022-like and 14M
crystal structures, respectively. The lattice
parameters of this sample were determined as at =
3.8920 and ct = 6.5105 for the D022-like phase.
We could not estimate the exact values of the lattice
parameters and the unit cell volume for the 14M
structure because the strong diffraction lines from
the 14M structure overlap with the diffraction lines
from other structure. Similarly, the X-ray powder
diffraction patterns of the samples with x = 0.10 and
0.11 indicate that the 14M phase and the tetragonal
D022-like phase coexist at room temperature though
the fraction of the D022-like phase increases with
increasing the concentration x. The X-ray powder
Fig. 1
Unit cell of the Heusler-type
diffraction pattern at room temperature for the
structure. A, B, C and D denote each of
sample with x = 0.23 is shown in Figure 2(c). All the
the four different sites.
diffraction lines can be indexed with the tetragonal
structure, where the a-axis is chosen to be rotated in a c plane by 45 from a-axis in the L21
structure. The intensities of all diffraction lines agree well with the results calculated by assuming
the D022-like crystal structure (space group; P4/mmm) as shown in the inset in Fig. 2(c). The lattice
parameters of the sample were estimated to be at = 3.8348 and ct = 6.6650 , where at is shorter
by a factor 1 2 than ac of the L21 structure in the absence of lattice distortions. As the values of
the atomic scattering factor for Ni, Mn, Ga and Cu atoms are close, we could not determine which
site Cu atoms occupy preferentially. For all calculations of X-ray powder diffraction intensities, we

Fig. 2 X-ray powder diffraction patterns at room temperature of (a) Ni2MnGa0.98Cu0.02, (b)
Ni2MnGa0.88Cu0.12 and (c) Ni2MnGa0.77Cu0.23. The inset in (c) shows the D022-like crystal structure,
where the symbols represent the four different sites A, B, C and D as in Fig. 1.

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assumed that the Cu atoms occupy the Ga sites preferentially. X-ray data show that Ni2MnGa1xCux
within the concentration interval 0 x 0.25 are in single phase. A small amount of pure Cu
phase, which was estimated from the relative intensities of extra X-ray peaks, begins to appear at x
= 0.27 and becomes significant with increasing Cu concentration x. Figures 3(a) and (b) show the
concentration dependence of the lattice parameters and the cell volume per formula unit at room
temperature. The unit cell volume decreases with increasing x.

Fig. 3 Concentration dependence of (a) lattice constants and (b) unit cell volumes for each
structure of Ni2MnGa1-xCux (0 x 0.25). In Fig. 3 (b), the unit cell volume of the D022 -like
structure was converted to one of the L21 structure.
Figure 4(a) shows the temperature dependence of the initial permeability for the sample with x
= 0.02. The arrows along the curves in this figure show the heating and cooling processes. The
abrupt large increase of with decreasing temperature corresponds to the transition from the
paramagnetic state to the ferromagnetic state. The Curie temperature TC was defined as the cross
point of the linear extrapolation lines from higher and lower temperature ranges on the versus T
curve. The Curie temperature is estimated to be 365.6 K for the sample with x = 0.02. With further

Fig. 4 Temperature dependence of (a) the initial permeability and (b) the magnetization M at
1 kOe for Ni2MnGa0.98Cu0.02. The arrows along the curves in (a) show the cooling and heating
processes. TC is the Curie temperature. TMs and TMf mean the martensitic transition starting
temperature and the martensitic transition finishing temperature, respectively. TAs and TAf represent
the reverse martensitic transition starting temperature and the martensitic finishing temperature,
respectively. Tp and Tp' show the premartensitic transition temperatures for the cooling and heating
processes, respectively. The arrows with ZFC and FC along the curves in (b) show the zero-field
cooling and field cooling processes, respectively.

V.A. Chernenko

169

decrease of temperature, the abrupt decrease of is observed around 240 K. Furthermore, the
thermal hysteresis with the width of about 20 K is observed on the versus T curves in the cooling
and heating processes. These temperature variations of are similar to those of Ni2MnGa and
Ni2Mn1xCuxGa. Therefore, the abrupt changes of are thought to correspond to a martensitic
transition. The martensitic transition starting and finishing temperatures TMs and TMf and the reverse
martensitic transition starting and finishing temperatures TAs and TAf were also defined as the cross
points of the linear extrapolation lines from both higher and lower temperature ranges on the
versus T curves as shown in the figure. Moreover, an anomalous local dip is clearly observed above
TMs and TAf. This dip starts and finishes around Tp = 264 K on the versus T curves in both cooling
and heating processes, which corresponds to a premartensitic transition temperature. The thermal
hysteresis width at the premartensitic transition temperature is estimated to be about 2 K, indicating
that the premartenstic transition is of the first order.
Figure 4(b) shows the temperature dependence of the magnetization M measured in a
zero-field-cooling (ZFC) and a field-cooling (FC) processes at the applied field of 1 kOe for the

Fig. 5 Temperature dependence of (a) the initial permeability and (b) the magnetization M at
1 kOe for Ni2MnGa0.95Cu0.05. The arrows along the curves in (a) show the cooling and heating
processes. TC is the Curie temperature. TMs and TMf mean the martensitic transition starting
temperature and the martensitic transition finishing temperature, respectively. TAs and TAf
represent the reverse martensitic transition starting temperature and the martensitic finishing
temperature, respectively. The arrows with ZFC and FC along the curves in (b) show the
zero-field cooling and field cooling processes, respectively.
sample with x = 0.02. In the ZFC process, a sample was first cooled to 5 K from room temperature
under zero magnetic field; at this temperature the magnetic field (H = 1 kOe) was applied and the
magnetization was measured at this constant field with increasing temperature up to 375 K. Then,
without removing the external field, the magnetization measurement was made with decreasing
temperature, i.e., the FC process. As shown in Figs. 4(a) and (b), the martensitic transition is
accompanied by the abrupt changes of and M because the low symmetry of the martensite phase
enhances the magnetocrystalline anisotropy energy, which forces magnetizations in martensitic
variants to direct to their magnetic easy axes under the weak magnetic field 1 kOe. Similar versus
T and M versus T curves were observed for the sample with x = 0.03.
Figures 5(a) and (b) show the temperature dependence of and M at 1 kOe for the sample with x
= 0.05. The temperatures TMs, TMf, TAs and TAf of the sample with x = 0.05, which characterize the
martensitic transition, were determined as shown in Fig. 5(a). It should be noted that the anomalous
local dip as shown in Fig. 4(a) is not observed on the versus T curves for the sample with x = 0.05.
Similar versus T and M versus T curves were observed for the samples with x = 0.07, 0.10, 0.11
and 0.12. Figures 6(a) and (b) show the temperature dependence of and M at 1 kOe for the sample
with x = 0.13, respectively. As shown in Figs. 6(a) and (b), and M decrease sharply around 350 K
with increasing temperature, indicating that the magnetic transition from the ferromagnetic phase to

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the paramagnetic phase is of the first order. We did not observe any anomaly below TC on the
versus T and M versus T curves, so that TM is considered to coincide with TC. The Curie temperature
TC (= TM) was determined to be 362.3 K for the sample with x = 0.13, where TM was defined to be
TM = (TMs + TAf) / 2. As shown in Fig. 6(b), for the sample with x = 0.13 the curves cross around
330 K. The values of magnetization observed by the FC process are larger than those of the ZFC

Fig. 6 Temperature dependence of (a) the initial permeability and (b) the magnetization M at 1
kOe for Ni2MnGa0.87Cu0.13.The arrows along the curves in (a) show the cooling and heating
processes. TC is the Curie temperature. TMs and TMf mean the martensitic transition starting
temperature and the martensitic transition finishing temperature, respectively. TAs and TAf
represent the reverse martensitic transition starting temperature and the martensitic finishing
temperature, respectively. The arrows with ZFC and FC along the curves in (b) show the
zero-field cooling and field cooling processes, respectively.
process. This may be attributed to the pinning effect of the domain wall. The sample with x = 0.13
shows the first-order martensitic transition at TMs and TAf as mentioned above. The value of TAf is
higher than that of TMs. It means that the cross point appears on the M versus T curves for the ZFC
and the FC processes. Similar experimental results ware observed on the M versus T curves of
Ni2Mn0.77Cu0.23Ga [19]. Figures 7(a) and (b) show the temperature dependence of and M at 1 kOe
for the sample with x = 0.23. The versus T and M versus T curves in Figs. 7(a) and (b) are
characteristic of ferromagnets with the ferromagneticparamagnetic second order phase transition.
We observe an anomaly around 50 K on the M versus T curve for the ZFC process as shown in Fig.
7(b). Now it is not clear why the magnetization show the anomalous behavior at about 50 K for the
ZFC process. Figure 8 shows DSC curves of the sample with x = 0.23 for the heating and cooling
processes. As shown in Fig. 8, we can observe the exothermic and the endothermic heats due to the
martensitic transition. We determined TMs, TMf, TAs and TAf by using the intersection of the baseline
and the tangent lines with the largest slopes of the DSC peak as shown in Fig. 8. Similar DSC
curves were observed for the samples with x = 0.13, 0.16, 0.18, 0.20, 0.23 and 0.25.
The experimental Tx phase diagram of Ni2MnGa1xCux (0 x 0.25), which was constructed
from the measurements of the temperature dependence of and M, and DSC measurements, is
shown in Fig. 9. In the compositional interval 0 x 0.12, the Curie temperature decreases from TC
= 365 K at x = 0 to TC = 340 K at x = 0.12 with increasing the concentration x. On the other hand,
the martensitic transition temperature TM increases with increasing x for the samples with 0 x
0.12. As shown in Fig. 9, TM and TC merge together in the samples with 0.12 < x 0.14. With
further increase in x, TM increases with increasing x from 378.0 K at x = 0.14 to 611.9 K at x = 0.25.
On the other hand, in the compositional interval 0.14 x 0.25 TC decreases almost linearly with
increasing x. As shown in Fig. 9 the premartensitic transition is observed in the samples with 0 x
< 0.05. To sum up, the three distinct regions can be distinguished in the phase diagram shown in
~
Fig. 9. In the first region, characterized by the Cu concentration 0 x 0.12, TC > TM and

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martensitic transition takes place between two ferromagnetic phases. The second region with 0.12 <
x 0.14 is characterized by TM = TC, i.e., the coupled transitions of the martensite and
ferromagnetic phases. Finally, the third region with x > 0.14 is characterized by TC < TM, i.e, the

Fig. 7 Temperature dependence of (a) the initial permeability and (b) the magnetization M at 1
kOe for Ni2MnGa0.77Cu0.23. TC is the Curie temperature. The arrows with ZFC and FC along the curve
in (b) show the zero-field cooling and field cooling processes, respectively.
ferromagnetic transition in the martensite state. It is remarkable that the phase diagram of
Ni2MnGa1xCux presented here has the characteristics very similar to those of Ni2+xMn1xGa [16]
and Ni2Mn1xCuxGa [19].
Phenomenological analyses of the phase diagram. The common features of the phase diagrams of
Ni2+xMn1xGa, Ni2Mn1xCuxGa, and Ni2MnGa1xCux indicate that the origin of the appearances of
the observed phases and the order parameters in those phases are common to all these alloy
systems. Vasil'ev et al. [15] and Khovaylo et al. [16] first analyzed phenomenologically the phase

Fig. 8 DSC curves of Ni2MnGa0.77Cu0.23. The arrows along the curves mean the cooling and
heating processes. TMs and TMf mean the martensitic transition starting temperature and the
martensitic transition finishing temperature, respectively. TAs and TAf represent the reverse
martensitic transition starting temperature and the martensitic finishing temperature, respectively.
diagram of Ni2+xMn1xGa by introducing the tetragonal strain e3 and the magnetization M for the
order parameters in the martensite phase and in the ferromagnetic phase, respectively. In these
theories, magnetostrictions play an important role in the interplay between the martensitic and
ferromagnetic phases. Recently, Kataoka et al. [19] also analyzed the phase diagram of

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Ni2Mn1xCuxGa by assuming the same order parameters, and found that higher order couplings are
more important than magnetostriction. The latter theory is here applied to the present alloy system
Ni2MnGa1xCux to analyze its phase diagram. Since, however, the order parameter of the
premartensite phase has not yet been clarified, the study of this phase is out of the analyses in the
following.
We start with a phenomenological Landau free energy of a cubic crystal which has the positive
magnetic anisotropy constant K1 > 0. The crystal is assumed to be able to exhibit the spontaneous

Fig. 9 Phase diagram of Ni2MnGa1xCux (0 x 0.25). Para means paramagnetic state and
Ferro means ferromagnetic state. A and M represent the austenitic and martensitic states,
respectively. TC, TM and Tp are the Curie temperature, the martensitic transition temperature and
the premartensitic transition temperature, respectively. The data of the sample with x = 0 are
cited from Ref. 3. Solid lines in the figure are a guide for the eyes.
order parameters e3 = (2ezz exx eyy) / with the strain components eii and/or M = Mz, where x, y,
and z denote the crystal axes. The total free energy per unit volume as a function of e3 and M can
have the following form as
1
1
1
c 2 e32 + A3 e33 + I 4 e34
2
3
4
1
1
+ 1 M 2 + J 1 M 4
2
4
1
1
+ Ge32 M 2 + Pe33 M 2 .
2
3

Ftot =

(1)

In this equation, the coefficients c2, A3 and I4 (>0) can be expressed in terms of the second-, thirdand fourth-order elastic constants, 1 is the inverse of the magnetic susceptibility, J1 (> 0)
originates from the magnetic exchange energy, and G and P represent the coupling constants of M 2
to e32 and e33, respectively. It should be noted that the above Ftot does not contain the linear term of
e3, which plays only a minor role in the present theory. In order to obtain the phase diagram in the
temperature T and the concentration x plane, it is necessary to know the T- and x-dependence of the
coefficients in Eq. (1). As in the former theories [15, 16, 19], we assume that the coefficients except

V.A. Chernenko

173

for c2 and 1 are all independent of both T and x, but c2 and 1 depend on T and x linearly as
follows:

c2 =

cm
(T TM ( x)),
TM (1)

1 =

(2)

cf
(T TC ( x)),
TC (0)

(3)

with

TM ( x) = TM (0) + (TM (1) TM (0)) x ,

(4)

TC ( x) = TC (0) + (TC (1) TC (0)) x ,

(5)

where TM(x) and TC(x) are, respectively, the fictitious (or sometimes real) second order transition
temperatures of the martensite phase and the ferromagnetic phase, and cm and cf are new positive
constants independent of T and x.
An equilibrium state at any T and x is found by minimizing the free energy given by Eqs. (1)(5)
with respect to the order parameters e3 and M. It has been already shown [19] that the above free
energy can give the appearances of the Para-A, Para-M, Ferro-A, and Ferro-M phases in the T-x
plane and the phase diagram is characterized by the following parameters:
tc

TC (1)
T ( 0)
T ( )
, t m ( 0) M
, t m (1) M ,
TC (0)
TC (0)
TC (0)
2

c
r m
cf

J1
A3
, a
,
2 cm I 4
I4

c
g m
cf

G
P c 2
and p m .
cf I 4
I 4

(6)

The values of these parameters are chosen so that the theory may reproduce well the observed
phase diagram. By use of the observed x-dependence of the transition temperatures between the
Para-A and Para-M phases and between the Para-A and Ferro-M phases together with some other
characteristic points in the observed phase diagram, these parameter values are estimated as tc(1) =
0.174, tm(0) = 1.028, tm(1) = 4.977, r = 1.898, a = 0.520, g = 1.126, and p = 1.867. The negative
sign of a has been employed by taking into account the observed elongation of the crystals in the
martensite phase [19]. Then we calculate numerically the free energy with these parameter values to
find finally the boundary lines between various phases. The obtained phase diagram is shown in
Fig. 10 for comparison with the observation. As seen from this figure, the calculated phase diagram
agrees satisfactorily with the observed one except for the appearance of the premartensite phase.
From the above experimental and theoretical analyses, the following properties of the phase
transitions in Ni2MnGa1xCux are noticed. The martensite and ferromagnetic phases are attractive
since g < 0. This together with the non-vanishing lattice anharmonicity a 0 causes the
magnetostructural transition. This transition appears at lower concentrations than those in
Ni2+xMn1xGa and Ni2Mn1xCuxGa, since TM(x) in Ni2MnGa1xCux steeply increases with x
compared with the transition temperatures TM(x) in the latter alloy systems. The temperature of the
transition between the Para-M and Ferro-M phases decreases with x faster than that in
Ni2Mn1-xCuxGa. This result is understood as follows. With increasing x from the concentration at

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which the Para-M phase begins to appear, the martensitic distortion in the martensite phase
develops faster in Ni2MnGa1-xCux than in Ni2Mn1-xCuxGa. The distortion more developed at higher
concentrations suppresses more strongly the appearance of the Ferro-M phase for p > 0. Finally, we

Fig. 10 Calculated phase diagram in the temperature Tconcentration x plane of


Ni2MnGa1xCux with the experimental data. The solid lines are the calculated results obtained by
use of the parameter values given in the text. The symbols are the experimental values taken
from Fig. 9. A and M represent the austenite and martensite phases, respectively. TC, TM and Tp
are the Curie temperature, the martensitic transition temperature and the premartensitic
transition temperature, respectively. The phase boundary line between Ferro-A and Ferro-M
phases was obtained by neglecting the appearance of the premartensite phase at low
concentrations.
compare the above numerical values of r, a, g and p with those employed in the calculation of the
phase diagram of Ni2Mn1-xCuxGa [19]. Form the observed phase diagrams, TM(1) in Ni2MnGa1-xCux
is about twice as large as that in Ni2Mn1-xCuxGa, while c2 in Eq. (2) can be assumed to have similar
values for the two alloy systems. These suggest that cm in the former alloy system is also about
twice as large as that in the latter. After taking into account this difference of cm , the sets of the
parameter values in the two alloy systems become close to each other. This fact proves that the
parallel phenomena occur in both the alloy systems, only except for their large difference of TM.
Summary
X-ray powder diffraction, permeability, magnetization and differential scanning calorimetry
measurements ware carried out on the magnetic shape memory alloys Ni2MnGa1xCux (0 x
0.25). On the basis of the experimental results, the phase diagram in the temperatureconcentration
plane was determined for this alloy system. The determined phase diagram is spanned by the
paramagnetic austenite phase, paramagnetic martensite phase, ferromagnetic austenite phase,
ferromagnetic martensite phase and the premartensite phase. It was found that the overall feature of
this phase diagram is very similar to those of Ni2+xMn1xGa and Ni2Mn1xCuxGa. The observed
phase diagram was explained, except for the appearance of the premartensite phase, on the basis of
the phenomenological theory, where the higher order coupling between the strain and the
magnetization plays an essential role in the interplay of the martensitic and ferromagnetic states.

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175

Acknowledgements
This work was partly supported by a grant based on the High-Tech Research Center Program for
private universities from the Ministry of Education, Culture, Sports, Science and Technology
(MEXT), Japan. This was partly supported by a Grant-in-Aid for Scientific Research (Grant No.
21560693) from the Japan Society for the Promotion of Science (JSPS)/MEXT.
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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.177

Effects of Surface Pinning, Locking, and Adaption of Twins on the


Performance of Magnetic Shape-Memory Alloys
Markus Chmielus1,2,3,a and Peter Mllner1,b
1

Departement of Materials Science and Engineering, Boise State University, Boise, Idaho
83725, USA

Institute for Complex Magnetic Materials, Helmholtz Centre Berlin for Materials and Energy,
Hahn-Meitner-Platz 1, 14109 Berlin, Germany

Now at: Department of Materials Science and Engineering, Cornell University, 214 Bard Hall,
Ithaca, NY 14853-1501, USA
a

markuschmielus@cornell.edu, bpetermullner@boisestate.edu

Key words: constraints, surface treatment, magnetic shape-memory alloy, single crystal,
Ni-Mn-Ga, Heusler alloy, magneto-mechanical properties, MSMA, FSMA

Abstract
We study the effect of surface modifications and constraints on the mechanical properties of Ni-MnGa single crystals, which are imposed by (i) structural modifications near the surface, (ii) mounting
to a solid surface, and (iii) guiding the stroke. Spark eroded samples were electropolished and
characterized before and after each polishing treatment. Surface damage was then produced with
spark erosion and abrasive wearing. Surface damage stabilizes and pins a dense twin-microstructure
and prevents twins from coarsening. The density of twins increases with increasing degree of surface
deformation. Twinning stress and hardening rate during mechanical loading increase with increasing
surface damage and twin density. In contrast, when a damaged surface layer is removed, twinning
stresses, hardening rate, and twin density decrease. Constraining the sample by mounting and
guiding reduces the magnetic-field-induced strain by locking twins at the constrained surfaces. . For
single-domain crystals and for hard magnetic shape-memory alloys, external constraints strongly
reduce the magnetic-field-induced strain and the fatigue lifetime is short. In contrast, for selfaccommodated martensite and for soft magnetic shape-memory alloys, the twin-microstructure
adapts well to external constraints and the fatigue lifetime is long. The performance of devices with
MSMA transducers requires managing stress distributions through design and control of surface
properties, microstructure, and constraints.
Fatigue and fracture of magnetic shape-memory alloys
Consistent performance under dynamical actuation is a requirement for active materials to be
considered for commercial applications. This is also true for magnetic shape-memory alloys
(MSMAs) with potential applications including actuators (e.g. Refs. [1-6]), valves (e.g. Refs. [7,8],
flappers [e.g. 9]), and micro energy harvesting devices (e.g. Refs. [10-12]) in single crystalline bulk
form and also in form of thin films (e.g. Refs. [13-17]). The lack of repeatability and insufficient
resistance against fatigue damage are still hindering commercialization of MSMA technology.
Fatigue experiments have been performed using different setups and actuation mechanisms. Highcycle fatigue actuation of single crystalline MSMAs can be facilitated with a rotating magnetic field
[18-24], i.e. by controlling the magnetic field and free strain. Under mechanical actuation, the

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experiments can be performed load-controlled or strain-controlled, i.e. under a defined strain range
(e.g. 2% in [25]).
Rotating-field experiments showed a change in magnetic-field-induced strain (MFIS) over the
course of the fatigue tests. Samples which deformed well below their theoretical possible MFIS
when actuated by a magnetic field, did not fail by fracture [19,20,22-26] while samples deforming
at or close to maximum theoretical MFIS did fracture [18-20]. X-ray tomography of cracks of a
10M Ni-Mn-Ga actuated magnetically for 108 cycles indicated fatigue cracks parallel to the {110}
plane [24]. The fracture plane along {110} was confirmed by Aaltio et al. in magnetically actuated
high-cycle tests [26]. In Ref. [27], ten 10M samples have been purely mechanically actuated over
82 x 103 to 2 x 109 cycles. In three cases, the sample broke. In the other cases, the experiments were
stopped to allow for characterization of the twin-microstructure and of damage accumulation. The
mechanical actuation was performed under strain control with a maximum strain of 2% and 3%.
The three fractured samples show macroscopic fracture planes close to {111} with microscopic
terraces along {101} planes. A review on results about fatigue and fracture of Ni-Mn-Ga with a
focus on 10M martensite is given in this book by Aaltio et al. [28].
The dependence of MFIS on the actuation frequency was studied in Refs. [29,30]. Modeling and
experiments indicate that the MFIS stays constant until a particular threshold frequency is reached,
above which the MFIS decreases. MSMAs are not only susceptible to fracture during high strain
cycling but also during thermal cycling. During the martensite phase transformation, cracks
nucleate especially in regions with coexisting martensite variants, are self-propagating and form
along {110} twinning planes and between martensite variants [31,32] (in these Refs., the L10 axis
system is used, for which the twin boundaries are {112}), probably driven by the formation of
stress-induced martensite [33].
For polycrystalline MSMAs, fracture was studied with mechanical loading experiments. E.g. in
Ref. [34] it was found that sintered Ni-Mn-Ga has a nearly three times higher tensile fracture
strength than arc-melted Ni-Mn-Ga, while [35] found that grain boundaries are ductile and fracture
occurs at grain boundaries most likely through impurity segregation. In [36,37] the addition of Fe
was found to increase the fracture toughness of Ni-Mn-Ga polycrystals. While small grained
polycrystalline bulk MSMAs showed less than 0.01% MFIS due to neighboring grains constraining
each other [38-40], recovery strains of up to 1% were found in coarse grained, mechanically trained,
and strongly textured polycrystalline MSMA in an orthogonal magnetic bias field [41-42]. When
removing the internal constraints imposed by grain boundaries with porosity, MFIS of up to 8.7%
and good performance without fracture have been obtained for polycrystalline Ni-Mn-Ga foam [4347].
The effects on structure, thermal properties, and magnetic properties of Ni-Mn-Ga MSMAs are
very sensitive to variations of the alloy composition and have been determined in detail in various
studies [e.g. 48-55]. Similarly, the surface preparation procedures impact the magneto-mechanical
properties of these materials. However, information on the surface treatment and sample preparation
methods is often of qualitative nature and describes only the cutting and polishing itself [e.g.
48,54,56-64]. Thermo-mechanical and thermo-magnetic training increases the MFIS. Murray et al.
[65] and Sozinov et al. [66] applied a magnetic field and a mechanical load to create a single twin
domain specimen. This method was applied to achieve high MFIS [67]. The option of using several
mechanical treatments as training procedure to produce repeatable magneto-mechanical behavior
was mentioned in [68]. In [69], it was shown how variants are changing from a single variant state
to a two variants state after thermo-mechanical training, and how the variants rearrange due to
alternating straining in different directions and when exposed to a rotating magnetic field. If several
variants are present in a single crystalline sample, the application of a magnetic field favors the
variant with its c axis most closely parallel to the magnetic field direction. This variant grows at the
expense of the other variants, in the ideal case until a single variant state is attained. Rotating the
magnetic field to a different direction favors another variant, which has now the c direction most
closely parallel to the direction of the magnetic field causing this variant to nucleate and grow.
Rotating the magnetic field creates nearly single variant states and allows for easy switching

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between variants at reduced twinning stress. Additionally, in Refs. [19-21,23] it is described how
training impacts the MFIS at the beginning of a rotating magnetic field experiment and how the
MFIS evolves over a large number of magnetic field revolutions.
While thermo-mechanical training increased the MFIS at the beginning of the magnetomechanical cycling experiments in a rotating magnetic field to the theoretical maximum, it also
increased the susceptibility to failure by fracture [21,23]. Ineffectively trained samples (with selfaccommodated martensite) have a small MFIS at the beginning of the magneto-mechanical cycling
experiments. Due to the rearrangement of twin variants and the growth of favorable twin variants
during in-service training (i.e. while exposed to a rotating magnetic field), the MFIS increased
from 0.18% to above 2% for a 10M martensite sample without fracturing over 108actuation cycles
[23]. Straka et al. [70] generated a simple two variant state by repeated compressive straining. This
lead to a decrease of twinning stresses for a 10M martensite sample from 2.3 MPa directly after
thermo-mechanical training (cooling from austenite to martensite with applied stress) to 1.1 MPa in
a trained state and for a 14M martensite sample from 6.3 MPa to 2.9 MPa.
External constraints may reduce the MFIS [69,71]. Constraints stabilize a dense twinmicrostructure with thin twins in ineffectively trained samples exhibiting self-accommodated
martensite [21,23,24]. In contrast in effectively trained samples with a single martensite variant
state, constraints induce coarse twins which lead to crack nucleation. In effectively trained samples
(i.e. without twins), the macroscopic constraints hindered the microstructure from adapting to the
internal stresses which resulted in failure in high cycle dynamical experiments [23,27].
It is still difficult to reproduce single crystals with identical properties. To avoid artifacts
originating from crystal production, often samples are being tested repeatedly in different
conditions to study effects, which certain extrinsic parameters impose on the performance of
MSMAs. This approach, however, has the disadvantage of convoluting the targeted effects from
training effects, which are due to repeated testing [70]. In this article, we review recent progress on
effects of surface modifications and external constraints, with an attempt to separate effects of
training from those of external constraints, and surface properties. In the first part, it is shown that
different surface treatments in combination with repeated mechanical deformation experiments
significantly reduce the twinning stress. Furthermore, polishing reduces the twinning stresses
especially in the high strain regions where the rough surface layer causes hardening, and also leads
to serrated flow. Reversing this test in the second part, we show how the increase of surface
roughness and straining of samples with electropolished surfaces influences the twin-microstructure
as well as twinning stresses. In the third part, we study the influence of external constraints which
are imposed, e.g., by holding and guiding mechanisms as unavoidable components of MSMA
devices and experiments. We study the influence of constraints on one end or both ends of the
sample imposed by sample mounting on the magneto-mechanical properties of two Ni-Mn-Ga
samples with 10M and 14M martensite structure.
Removing a surface layer with a high defect concentration
Removing a damaged surface layer, which originated from spark erosion cutting, reduces the
twinning stresses of MSMAs [72]. The surfaces of six samples (A1 to A6) were electropolished
three times to receive different levels of surface roughness and to take off the deformed surface
layer. Before and after each polishing step, four of these samples were mechanically tested, to
receive information about their twinning stresses. One end of samples A was cut with a wire saw
and the change of surface roughness in relation to electropolishing steps was measured also on this
surface. A group of three control samples (B1 to B3) was not electropolished but received the same
amount of mechanical testing, to account for the effect of training without change in surface
deformation. After this series of mechanical tests, the rough surface layer was taken off by
mechanical polishing, without removing underlying material, as this was the case during
electropolishing of samples A.

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Scanning electron micrographs taken prior to the first polishing treatment show that the
topographies of the spark eroded surfaces and the wire cut surfaces were different and had distinct
features (Fig. 1). The spark eroded surfaces were densely covered with dents and bumps with no flat
surface regions between them. These surface features were between 20 and 80 m wide and had
height differences of over 12 m. The largest dents on the wire cut surfaces measured 5 m. No
salient features were found on these surfaces. The dents only covered a small percentage of the
entire surface area. In between the dents, there were flat regions with very small ridges not larger
than 1 m.

Figure 1: Scanning electron micrographs of as cut surfaces. (a) The spark eroded
surface showed very large, round surface features in the range of several 10 m in
diameter and depth of up to 12 m. (b) Features on the wire cut surface were
smaller than 5 m and had a depth of less than 1 m [72].
The images shown in Fig. 2 were taken with optical profilometry and illustrate qualitatively how
the surface roughness changed with each polishing treatment. After the first electropolishing
treatment, all coarse and rough surface features on surfaces of both cut types were mostly gone and
the surface appeared to be smooth. Additionally, straight valleys and ridges (indicated exemplarily
by black dashed lines in Fig. 2) appeared at a distance of 2 m to 20 m. These valleys and ridges
mark the traces of twin boundaries, which formed during deformation tests. After the third
electropolishing treatment, small cavities with 2 to 5 m diameter appeared on all surfaces,
probably due to pitting [72].
The effect of material removal on surface roughness is shown quantitatively in Fig. 3. The
average surface roughness, Ra, decreased to less than a third after the first electropolishing
treatment. After each following polishing treatment, the surface roughness decreased further,
however at a reduced rate. The average material removal during the first, second, and third
electropolishing treatment was 29, 14, and 27 m, i.e. 70 m was removed in total. This was about
6 times the highest surface feature of the unpolished spark eroded surface. Comparing the average
surface roughness of the spark eroded and wire cut surfaces, the latter had much lower initial
roughness values. The wire cut and spark eroded surfaces had average surface roughnesses of 0.4
m and 1.6 m, respectively. The surface roughness decreased with each polishing treatment and
converged to 0.09 m (wire cut) and 0.14 m (spark eroded).
The mechanical polishing of samples B1 to B3 that have not been electropolished during the
first four deformation cycles, resulted in an average material removal of 35 m for B1 and B3 and
51 m for B2.The average roughness after the mechanical polishing of these samples was 0.15 m
(B1), 0.07 m (B2), and 0.08 m (B3).

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All deformation experiments were evaluated regarding the 0.2% yield stress Y, and the stress
95 at 95% of total strain. During the deformation experiments, the sample were mechanically
loaded parallel to the samples axis, which are defined as x (parallel to shortest dimension), y
(parallel to intermediate dimension), and z (parallel to longest dimension) .The term twinning
stress is conventionally related to the macroscopic stress required to initiate twinning and is related
to a critical resolved shear stress [73]. The twinning stress, tw, is defined here as the mean value of
the stress within the defined strain range (i.e. between = 0.2% and = 0.95 max). The twinning
stress was evaluated by graphically integrating the stress values. The difference between the lowest
and highest applied stress within these two strain marks define the twinning stress range, tw.

Figure 2: Micrographs of sample A5 taken with an optical profilometer. Spark


eroded and wire cut surfaces are shown in the left and right columns, respectively.
The four micrographs in each column are representing the surfaces (A) initially
before the first deformation cycle, (B) after the first electropolishing treatment,
and (C) after the second electropolishing treatment. Each micrograph shows an
area of 121 m x 92 m. The dashed lines exemplarily indicate the direction of
straight ridges and valleys marking the traces of twin boundaries [72].

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Figure 3: Surface roughness, Ra, for areas of


92 m x 121 m of the spark eroded surface
(squares) and the wire cut surfaces (pentagons).
Capital letters indicate the polishing state: (A)
unpolished, (B) after 30 s, (C) after 60 s, (D) after
120 s [72].

The stress-strain curves for samples A1 and A3 for the first deformation under loading in z
direction (parallel to longest sample dimension) before the electropolishing and after each polishing
treatment are exemplarily given in Fig. 4. All specimens show a drastic decrease of the twinning
stress after the first polishing treatment. Further polishing treatments still reduced the twinning
stress albeit by a lesser degree. The stress-strain curves after the first, second, and third polishing
treatment were very flat (i.e. they showed little hardening) and all twinning stresses were below 5
MPa with lowest values at 0.8 MPa (A1).

Figure 4: Stress-strain curves of samples (a) A1 and (b) A3. The solid lines
indicate the loading curves before electropolishing, the dashed lines those after
electropolishing. In the inset in (b), all stress-strain curves are drawn with solid
lines to emphasize the serrated flow [72].
The stress-strain curves of the control samples B2 and B3, which were not electropolished are
shown in Fig. 5. The first stress-strain curves of each unpolished sample were similar to those of the
unpolished samples A1 to A4, i.e. they had a high twinning stress (between 7.4 and 14.6 MPa [72])
and a steep slope. After the first deformation test the twinning stresses dropped to values between
3.5 and 4.9 MPa. From the second deformation test on, the twinning stresses decreased only slightly
during the subsequent deformation experiment. Finally, the twinning stresses of all B-samples were
between 2.6 and 2.8 MPa. After the samples were mechanically polished, the average twinning
stresses dropped further to 1.8 and 1.9 MPa (curves 5 and 6 in Fig. 5). The twinning stress remained
low over the entire strain range where twinning occurred before it sharply increased when twinning
saturated. This is in contrast to the unpolished samples, for which the stress levels increased
constantly with increasing strain, and transitioned slowly to the elastic region. As result of the
nearly constant twinning stress of the mechanically polished sample, the twinning stress range, tw

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(indicated as error bar in Fig. 6), was reduced by half from 5.5 0.4 to 2.7 0.5 MPa. In contrast to
the electropolished samples which showed serrated flow (inset in Fig. 4b), the not electropolished
samples had very smooth stress-strain curves (inset in Fig. 5a).

Figure 5: Stress-strain curves of samples B2 (a) and B3 (b). While deformation


experiments 1 through 4 were performed with unpolished as-cut surfaces,
loading 5 and 6 were performed with mechanically polished surfaces. The inset in
(a) illustrates the smoothness of the stress strain curves as compared to the
serrated flow shown in the inset of Fig. 4b [72].

Figure 6: Twinning stresses, tw, of (a) the electropolished samples and (b) the
control samples. The bars indicate the twinning stress range, tw (not the
experimental error) [72].
To verify the structure of two samples (A3 and B3), by neutron diffraction experiments were
performed. The lattice parameters of A3 were a = b = 6.03 , c = 5.59 , and = 90.7 consistent
with the monoclinic 10M martensite. The sample B3 contained a mixture of the 10M and 14M
phases where the lattice parameters of the 14M phase were a = 6.50 , b = 6.02 , c = 5.77 [72].
Increasing the degree of damage at the surface
In a second test series, the mechanical properties were measured first at samples with perfect, i.e.
electropolished surfaces and surface damage was then successively introduced [74]. Samples A1
and A3 which have been electropolished in three steps were mechanically tested before and after

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their surface roughness was increased first by using mechanical polishing (9 m water based
diamond suspension) and second by mechanical grinding (1200 grid SiC paper).
The images shown in Fig. 7 were taken with optical profilometry and illustrate qualitatively how
the surface roughness changed with each surface treatment. The electropolished surface is very
smooth (Fig. 7a). After the sample was mechanically polished (Fig. 7b), the surface showed a few
shallow polishing marks in form of long scratches. The depth, width, and density of the scratches
increased significantly after the mechanical grinding treatment (Fig. 7c). The average surface
roughness, Ra, determined from optical profilometer line scans, increased from the electropolished
surface to the mechanically polished surface from 20 nm to 70 nm. With mechanical grinding, the
average surface roughness increased to 200 nm. Fig. 8 shows the stress-strain curves for samples
A1 (Fig. 8a) and A3 (Fig. 8b).

Figure 7: Micrographs of sample A3 taken with optical profilometry. The three


micrographs are representing the surfaces (a) after electropolishing treatments
(240 s) [72], (b) after mechanical polishing with a 9 m water based diamond
suspension, and (c) after mechanical grinding with a 1200 grit SiC paper. The
gray scaled bar next to each micrograph indicates the heights of each point [74].

Figure 8: Stress-strain behavior of initially electropolished crystals (a) A1with


14M martensite, and (b) A3 with 10M martensite, in the initially electropolished
condition (1), with subsequent mechanically polished (9 m diamond powder)
surfaces (2), and with subsequently grinded (1200 grit SiC paper) surfaces (3)
[74].
Figs. 9 and 10 show micrographs taken after each stress-strain test cycle. After these
micrographs were taken, the next surface treatment was performed. For sample A1 (Fig. 9),
micrographs are shown for (a) electropolished, (b) mechanically polished, and (c) mechanically

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grinded surfaces. Fig. 10 shows the micrographs of (a) mechanically polished and (b) mechanically
grinded surfaces of sample A3. While twins in the electropolished condition were rare and large (1
mm and larger), many finer twins appeared in the mechanically polished surfaces with a width
below 0.1 mm [74].

Figure 9: Optical micrographs of sample A1 (14M martensite) after stress-strain


experiments with the surfaces being (a) electropolished, (b) mechanically
polished (9 m diamond suspension), (c) subsequently grinded with 1200 grit SiC
paper [74].

Figure 10: Optical micrographs of sample A3 (10M martensite) after stress-strain


experiments with the surfaces being (a) mechanically polished (9 m diamond
suspension), (b) subsequently grinded with 1200 grit SiC paper [74].
Using x-ray diffraction, the full width at half maximum (FWHM) of the diffracted intensity
peaks (Fig. 11) was determined for different surface treatments [74,75]. For samples A1 and A3, the
2 FWHM increased slightly from mechanical polished (2) to mechanical grinded (3) surfaces from
0.56 to 0.57 and from 0.36 to 0.42 for sample A1 and A3, respectively. After the chemical
etching (4), the FWHM decreased to 0.52 (sample A1) and 0.22 (sample A3). The modulation
structure of the surface layer of A3 change from 10M to 14M after mechanical grinding (3) - as

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evidenced by the appearance of the (004)14M reflection - and back to 10M after additional etching
(4) - as evidenced by the disappearance of the (004)14M reflection. X-ray diffraction results of
samples A1 and A3 are given in Figs. 11a and 11b. X-ray diffraction data shown in Fig. 11 for
sample A1 and designated with 2 and 3 correspond to the optical micrographs b and c shown in Fig.
9 and to the increased surface deformation and the stress-strain curves 2 and 3 in Fig. 8. The
localized elastic strains, which are indicated by the enhanced XRD peak width, correlate with the
increase in twinning stress.

Figure 11: 2 x-ray diffraction data of (a) sample A1 and (b) sample A3 with
successive surface treatments. While the shape and position of the peaks of
sample A1 remained constant during successive surface treatments, a (004)14M
structure peak appeared for sample A3 after it was mechanically ground. This
peak disappeared after the following etching [74].
External constraints
To evaluate the influence of external constraints on the magneto-mechanical properties of
MSMA, samples had to be constrained in different ways. The setup of the rotating field experiment
was modified such that it was possible to test a sample while glued (i) on one end and (ii) on two
ends, without sacrificing accuracy of the MFIS measurement. The experiments were performed
with a hard sample C (with tw > 1 MPa,) and a soft sample D (with tw < 1 MPa) [76]. Sample
C had the 14M structure, while sample D had the 10M structure. Fig. 12 illustrates how the sliding
head (5) is pushed by spring (6) against the sample (2) to ensure proper contact. In Fig. 12a, the
sample is glued on both ends, while in Fig. 12b, the sample is glued only on the bottom end. Further
details of the experiment are given in [44,76].

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Figure 12: Schematic of the sample


holder with modifications for testing
the influence of external constraints
on a MSMA sample. The sample (2)
is glued to the sample
holder/chamber (1) and to a
stabilizing decoupler (4). The darker
gray regions (3) at the ends of the
sample indicate glue. When the
sample changes its shape in z
direction, the sliding head (5) moves
and redirects the deformation to the
extensometers. Spring (6) presses the
sliding head against the sample.
Setup (b) is similar to (a) but without
decoupler (4). In setup (b), one
sample end is not glued. The
dimensions of the sample are
indicated in (b) by w (width) and l
(length) [75].
Neutron and x-ray diffraction experiments were performed to identify the structure lattice
parameters ratio of samples C and D [76]. Sample C had the 14M structure with the lattice
parameter ratio, c/a = 0.907 0.005. Sample D had the c/a ratio of 0.961 0.005 which is taken as
a signature of the 10M martensite structure though the c/a ratio of most 10M crystals is closer to
0.94. The mechanical properties of samples C and D in the martensitic state are shown in Fig. 13a,
illustrating that the plastic strains of samples C and D were 10.5% and 3.6%, respectively. While
the stress-strain curve of sample C was strongly serrated with an average twinning stress of 1.1
MPa, the stress-strain curve of sample D was smooth with an average twinning stress of 0.8 MPa.
Before further high cycle tests were performed (results shown in Fig. 13b), samples C and D
were studied optically in-situ in a slowly rotating magnetic field. The samples were glued only on
the end of the sample holder (as in Fig. 12b). Sample C (Fig. 14a) started deforming very suddenly
when the angle between the samples z axis (parallel to the longest dimension of the sample) and
magnetic field direction reached approximately 60. One distinct twin boundary was visible which
is highlighted with a dashed line in the second image of Fig. 14a. Two more discrete jumps of this
twin boundary at the field angles of 65 and 90 resulted in the shapes shown in the third and fourth
images in Fig. 14a. In contrast to this discontinuous deformation behavior, sample D deformed very
smoothly over the entire volume of the sample. Deformation started shortly above 45. The
deformation states obtained for the field angles 0, 50, 55, and 90 are depicted in Fig. 14b. For
sample D, the top surface stayed parallel to the bottom plate at all magnetic field orientations. For
sample C the top surface was tilted by 4 at the two intermediate deformation states before it
became parallel again after the deformation was complete at a field angle of 90.

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Figure 13: Results of magneto-mechanical experiments. (a) Stress-strain curves


for compressive deformation of samples C and D. (b) MFIS of constrained
samples C and D glued on one end (C1,D1) and on two ends (C2,D2), according
to settings shown in Fig. 1 [76].
When glued on both ends (Fig. 12a), only sample D deformed in the rotating magnetic field (Fig.
14c), albeit with a reduced MFIS. Sample C, which deformed discontinuously when constrained at
one end, did not deform at all when constrained at both ends. The results of the high cycle
experiments confirm these observations. While sample C did not show MFIS when being
constrained on two ends (Fig. 13b, solid squares), it demonstrated 1.8% MFIS after 150 magnetomechanical cycles (MMCs) and then the MFIS slightly decreased to 1.55% after 500 MMCs when
it was constrained on one end only (Fig. 13b, open squares). In contrast, sample D showed MFIS of
0.6% even when constrained on two ends (Fig. 13b, full triangles). When only constrained on one
end, the MFIS increased from 2.1% over the first 300 MMCs to 2.7% and then decreased slightly to
2.6% at 500 MMCs (Fig. 13b, open triangles).
A similar variation in MFIS is not only observed over several hundred (Fig. 13) but also over
several tens of millions MMCs. By actuating a constrained sample over a larger amount of MMC,
the twins interact with each other in a way that increases twin boundary mobility and therefore
eventually increases MFIS. In Fig. 15, the development of the MFIS over 108 MMC of an initially
fine twinned 10M Ni-Mn-Ga single crystal is shown. The MFIS changed significantly during
cycling. Regions of fairly constant MFIS are marked A, B, and C and divided by jumps in the
MFIS.
External constraints initially hinder twin boundary motion of the fine twins. But with increasing
number of actuations, small twins in the center of the sample were able to merge and build larger
twins with more mobile twin boundaries. When the twins in the center had combined to one large
twin, the MFIS reached a maximum. The decline in region C was probably caused by the
introduction of cracks in the sample (Fig. 16), which were detected using x-ray microcomputer
tomography. During the last 3 x 107 MMC the MFIS was constant 1.2%. After 108 MMC, there
were no twin boundaries detected with atomic force microscopy in the center of the sample (Fig.
17a) while the corner of the sample contained fine twins as shown in Fig. 17b [23]. The noise in (a)
is due to polishing marks. Such marks are also present in (b). There, the marks are perpendicular to
the twin boundaries and parallel to the scanning direction.

V.A. Chernenko

Figure 14: Deformation of sample C (a), and sample D (b, c) in a rotating


magnetic field. In (a) and (b), the samples were glued on one end to the sample
holder only. In (c), the sample was glued on both ends. In (a), one single twin
boundary moved through the sample as visualized by the dashed line. This single
twin boundary divided the sample in two twin variants with differently aligned c
axes. This resulted in the tilting of the upper part of the sample. The top surface
was therefore not parallel to the bottom surface. In (b), twin boundaries were not
visible but the sample deformed in a more homogenous and permanent way
without tilting. In (c), at the field angle equal to 0, the sample was short and
slightly barreled. At the field angle of 90, the sample was long and no barreling
was visible [76].

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Figure 15: The development of the MFIS in a Ni-Mn-Ga single crystal. Long
periods (regions A, B, C) during which MFIS changed slowly were separated
from periods (gray vertical bars) over which MFIS increases rapidly. The MFIS
increased from 0.2% during the first 103 MMC to 2.15% at 6 x 105 MMC and
then decreased to 1.2% [23].

Figure 16: Microcomputer tomography micrographs of the Ni-Mn-Ga single


crystal after 108 MMC. The micrographs are slices in the y-z plane. Slice (a)
represents a cross section close to the surface of the sample, slice (b) a crosssection in the center of the sample, and slice (c) a cross-section at the side
opposite to slice (a). The bright areas are regions of low density [air in cracks or
pores marked with arrows in (a)], the black or dark-gray regions have a high
density. The variable gray contrast in the solid material is caused by beam
hardening due to the thickness of the sample. Most cracks form an angle of 45
with the lateral surfaces, or are connecting cracks running at a 45 angle [24].

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Figure 17: Atomic force microscopy results for (a) the center and (b) a
constrained corner of a Ni-Mn-Ga single crystal after 108 MMC. (I) are the
topography images and (II) are cross sections along the arrows in (I) after
averaging within the white box. In the center of the sample (a), there are no twin
structures visible, while there are many fine twins in the corners (b) [23]. The
noise in (a) is due to polishing marks. Such marks are also present in (b). There,
the polishing marks are perpendicular to the twin boundaries and parallel to the
scanning direction.
Mechanisms
The results presented here can be grouped according to three distinctly different mechanisms. We
term these mechanisms surface pinning of twins, locking of twin boundary motion, and twin
adaption.
Surface pinning of twins is related to the presence of the surface defects (or damage). The
defects may be introduced via deformation (e.g. by grinding, polishing, impacting), radiation (e.g.
by ion implantation) or by other means. The first two studies are complementary in the sense that
one study starts with deformed surfaces which get removed, while the other study starts with
polished surfaces that get deformed.
Reduction of surface damage by electropolishing results in a decreased twinning stress (see Fig.
4) and in broadening of twins. When the surface is undamaged, i.e. free of any surface defects such
as approximated by the electropolished state, the stress-strain curve has a flat slope (i.e. a small
twinning stress range), and the stress-strain curve is serrated (Fig. 4 lines 2 to 4 and line 1 in Figs.
8a and b). At an increased degree of surface damage, as produced with increasingly rougher
polishing tools, the twinning stress, tw, and the twinning stress range, tw, both increase (Fig. 4,
line 1 and Fig. 8, lines 2 and 3). Furthermore, the stress-strain curves are smoother at an increased
degree of surface damage (line 1 in Fig 4 and Fig. 5, line 3 in Figs. 8a and b). The opposite trend is
found upon removal of the defective surface layer. With increasing amount of removed material, the
twinning stress, tw, and the twinning stress range, tw, both decrease and the stress-strain curves
become serrated when electropolished (Fig. 4).
Repeated mechanical loading of samples that were not electropolished reduced twinning stresses
(Fig. 5, lines 1 to 4), similarly to but not as significantly as samples that had there damaged surface
layer removed. Thus, repeated mechanical loading constitutes a training effect [70]. When polished
after this mechanical training procedure, the twinning stress, tw, was further reduced (Fig. 5, lines 5
and 6). The reduction of the twinning stress obtained from removing a surface layer is the combined
effect of mechanical training (due to sequential testing) and removal of surface defects because

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these effects act additively. The situation is opposite for the experiments with increasing surface
damage. Here, introducing defects at the surface increases the twinning stress while the training
effect due to sequential testing reduces the twinning stress. Hence, the two effects are subtractive
and the measured increase of twinning stress provides a lower limit of the actual effect originating
from surface damage. The localized strains in the surface layer were confirmed by x-ray diffraction
experiments. The FWHM of the (004) peak broadens with increasing degree of surface deformation
(see Fig. 11). This indicates an increase of inhomogeneous elastic strain. The associated stress
concentrations pin the twin boundaries.
Fig. 18 is a schematic illustrating the effect of surface damage on twin boundary mobility. The
surface layers of spark eroded (Fig. 18a) and mechanically polished (Fig. 18b) samples contain a
large number of defects. Twin boundaries can move through the samples only in small steps until
they get pinned at defects in the surface layer or at groves that produce local stress concentrations.
The defects and local stress concentrations act as finely dispersed pinning sites at which twin
boundaries get stopped. When one twin boundary gets pinned, the stress raises upon further
deformation until another twin boundary, which is pinned at a defect with a smaller stress field,
breaks loose and moves. The twin boundary moves then from the weak obstacle to the next stronger
obstacle. This results in small localized movements of the twin boundaries throughout the sample.
Each pinning event leads to a small stress increase and each unpinning event leads to a small stress
relaxation. However, these subtle changes cannot be resolved individually and, thus, the stressstrain curve appears to be smooth. Electropolished samples contain only a small amount of defects
in the surface layer and some defects in the bulk. Thus, twin boundaries can move rapidly through a
sample when being mechanically loaded. The twin boundaries get pinned at coarsely dispersed
defects within the bulk of the sample (see Figure 18c). A rapid increase in strain and decrease in
stress is, therefore, visible in the stress-strain curves as serrations. In mechanically polished and also
in spark eroded samples, surface layer defects dominate the twin boundary pinning.

Figure 18: Schematic illustrating the effect of a deformed surface layer on the
twin-microstructure resulting from deformation experiments. The surface
conditions correspond to (a) the spark eroded, (b) the mechanically polished, and
(c) the electropolished surface. The darker top layer indicates a thermally or
mechanically influenced layer with defects, below the defect free region not
affected by surface treatments. Also shown is a twin with preferred orientation
relative to an applied stress during deformation experiment, and positions (dashed
lines) at which the twin boundary arrests. Twin boundaries can move until they
get stopped at defects in the surface layer. Crevices or other defects in the surface
layer are hindering twin boundary motion. (b) The mechanically polished surface
has a thinner layer of defects which nevertheless act as pinning sites for twin
boundaries. In (c), the twin boundary motion comes to a hold at coarsely
dispersed internal obstacle and defects, while in (a) and (b), twin boundary
motion stops due to residual stresses at surface irregularities [72,74].

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The pinning of twin boundaries is also reflected in Figs. 9 and 10, which are optical micrographs
corresponding to surface damage imposed on samples A1 and A3. The micrographs reveal that
twins become thinner after the surface was treated with increasingly larger and heavier particles (9
m diamond suspension and 1200 grit SiC particles). With larger size and mass of the particles, the
impact energy is larger and, thus, the damage is more severe, i.e. the stronger the surface
deformation. Stronger surface deformation implies a larger number of stronger defects. Most
probably, the distribution of defect strength increases with increasing degree of damage. For smaller
particles, the distribution of impact energy is narrower. Due to an increased average impact energy
and larger particle size distribution, the stress-strain curves of samples with more heavily damaged
surfaces are steeper than the curves for the crystal with less damaged surface layers (Fig. 8). The
twinning stress is, thus, controlled by the mobility of twin boundaries. This is different from the
situation of single-domain crystals with defect-free, electropolished surfaces, where the twinning
stress is nucleation-controlled at the onset of deformation and constant once the first twin boundary
is nucleated [77].
Plastic deformation of the surface layer which creates pinning sites for twin boundaries not only
results in increasing twinning stress as discussed above but also in a partial, non-linear elastic strain
recovery (Fig. 8, dotted lines). The elastic strain recovery increases with increasing amount of
deformation at the surface. In particular, with increasing the surface damage, the magnetoelastic
behavior [78] can be increased. Modification of the surface-near microstructure can be tailored to
achieve desired twinning stresses (implying optimal twin width) for magnetically driven
applications. The surface modification was achieved here with deformation through grinding. It
might be achieved through any other method including spark erosion, laser cutting/structuring, cold
forging, ion implantation, and abrasive wearing. Additionally, tailored surface modifications can be
used to conserve an established twin-microstructure (i.e. twins with a defined thickness, orientation,
and length) during dynamical loading.
Twin boundaries move via the propagation of twinning disconnections [79]. When twinning
disconnections are blocked at strong obstacles, they form dislocation pile-ups. For very thick twins,
the large number of twinning disconnections multiplies the stress on the leading disconnections.
The stress concentration at the pile-up head may easily exceed the by-pass stress. As a consequence,
the twinning disconnections can overcome the obstacle [80]. For thin twins, the stress at the head of
the pile-up is below the by-pass stress and the disconnections remain in the pile-up configuration.
Because of the repulsive interaction of identical disconnections, potential energy is stored in the pile
up. Upon unloading, this energy gets released by the dislocations moving away from the obstacle.
This results in a pseudo-elastic strain recovery as seen in Fig. 8. Pseudo-elasticity typically appears
when twins are thin [78]. Therefore, the amount of strain recovery increases with increasing degree
of surface deformation, which stabilizes a densely twinned microstructure (Figs. 9 and 10).
Locking of twin boundary motion is the blocking of twin boundaries caused by external
constraints. Constraints have significant influence on the MFIS of MSMAs and may even result in
the complete blockage of twin boundary motion. The influence of the constraints on the MFIS
depends on the mechanical properties of the MSMAs. Here, two samples with two different types of
mechanical properties were tested. Sample C with a serrated stress-strain behavior and a twinning
stress of above 1 MPa, which is defined here as hard MSMA, and sample D with a smooth stress
strain curve and a twinning stress of below 1 MPa, which is defined here as soft MSMA [75]. The
value 1 MPa as discriminator between hard and soft MSMA is somewhat arbitrary and should not
be taken as an absolute measure. Rather, we introduce the terms hard and soft to qualitatively
describe two different mechanical behaviors. Magnetically actuated, hard MSMAs deform rapidly
and in distinct steps with few twin boundaries moving through the sample while soft MSMAs
deform in a constant, smooth manner with several twin boundaries moving simultaneously through
the sample. Hard MSMAs only deform in regions which are not constrained (hatched regions in
Fig. 19). For samples with a single active twinning system, constraining the sample on both ends

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leaves only a small volume free for deformation. The unconstrained volume is hatched in Fig. 19a
(see also discussion in Ref. [71]). The nominal constrained volume fraction, vc, is given by
vc = fw/(2l)

(1)

where w and l are the width and length of the sample (see Fig. 12b) and f the number of constrained
ends (i.e. f = 1 and 2 for one and two-end-constrained case, respectively). The fractions of
constrained volume were 62% and 31% for sample C when it was constrained at two ends and at
one end, respectively. For sample D, these values were 72% and 36%. The nominal free or
unconstrained volume is 1-vc.

Figure 19: Schematics of free deformation in the one-end- and two-endconstrained conditions. In setup (a), where both ends are glued to sample holder
and decoupler, two volume wedges (bright) are locked at the constraint ends.
Only in the center volume fraction (hatched area) twin boundaries might be able
to move. In setup (b) the sample is only constrained on one end, therefore the free
volume (hatched area) is larger [76].
Assuming that the material can freely deform in the unconstrained volume, the expected strain
(MFIS) is (1-vc)(1-c/a) where c and a are the lattice parameters. For sample C, the expected MFIS
values were 3.5% (two-end-constrained) and 6.9% (one-end-constrained). The expected MFIS
values of sample D were 1.1% and 2.2%, respectively. These values are based on the c/a ratios
indicated above. With zero and 1.8% MFIS for the two-end-constrained and one-end-constrained
cases, sample C was clearly below the expected values. Sample D, on the other hand, showed with
0.6%, almost half of the expected MFIS of the two-end-constrained case, and exceeded with 2.7%
the expected MFIS when it was constrained on one end only.
These results unequivocally show that soft samples can adapt to constraints much easier than
hard samples. If only one twin boundary is moving through the sample, as in hard MSMAs, tilting
needs to be possible in order to deform with the unconstrained volume (as indicated in Fig. 19b).
When tilting of the sample is hindered, e.g., by guiding with the decoupler (Fig. 19a), hard MSMAs
do not deform at all. By gluing the sample at only one end, tilting can take place and the twin
boundary can move through the sample until it is stopped at the one constrained end of the sample
(Fig. 19b). The MFIS below the expected value of sample C, is likely caused by stress fields
(induced by the constrained ends) interfering with the shaded region in Fig. 19b. In contrast sample

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D, which is a soft MSMA, shows 2.7% MFIS when constrained at one end, which is higher than the
expected value of 2.2%. This large MFIS demonstrates a good adaption to the constraints. We
quantify the adaption to constraints with the adaption coefficient, , which is the ratio of the
measured MFIS to the theoretical MFIS (i.e. 1-c/a) that should be produced by the fraction, 1-vc
(see Eq. 1), of unconstrained (or free) volume in the center of the sample (i.e. the shaded region in
Fig. 19). The adaption coefficient thus is:
= MFIS/[(1-c/a)(1-vc)]

(2)

If equals 1, this means that the free volume is indeed free to deform. If is larger than 1, the
actual twin structure is adapting to the constraints well and deformation is taking place in a volume
larger than the unconstrained volume (i.e. deformation occurs also in the non-shaded part in Fig.
19). If is smaller than 1, the constraints confine the active portion of the sample to a volume
which is smaller than the shaded volume in Fig. 19. For sample D, for the one-end-constrained
case is 1.22, while for the two-end-constrained case is 0.55 indicating good adaption for the oneend-constrained case ( > 1) and inferior adaption in the two-end-constrained case ( < 1). The
inferior adaption in the two-end-constrained situation may result from the guidance imposed by the
decoupler, which touches the side walls of the sample holder. For sample C, is smaller than 1 for
both cases, indicating inferior adaption to constraints. The situation with larger number of moving
twin boundaries in the soft MSMAs is comparable to the one typical for the fine twinmicrostructure buffering large MFIS due to the constrained surface in inefficiently trained MSMAs
with a self-accommodated martensite [23,24].
The characteristics of the stress-strain curves (i.e. serrated curves for sample C and smooth
curves for sample D) show very distinct differences. These characteristics coincide with those of
electropolished samples and samples with deformed surfaces [72,74,75]. In fact, the surface of
sample C was electropolished while the surface of sample D was not, showing cutting or
mechanical grinding marks.
Twin adaption is the reorganization of the twin-microstructure under the combined stresses of
constraints and external load with the result to buffer the stresses of the constraints by establishing
macroscopic strain gradients. Twin adaption opposes twin locking as discussed above. Twin
adaption promotes magnetoplasticity and inhibits crack nucleation and fracture. On the macroscopic
scale, stresses occurring during rotating-field experiments are limited to the magnetostress which
amounts to only a few MegaPascals. This stress level is far below the fracture stress of Ni-Mn-Ga
single crystals. The magnetostress can, thus, not directly cause crack formation and fracture. Crack
nucleation requires stress concentrations. It was proposed in [21] that interacting twins provide sites
of stress concentration. These stress concentrations are sufficient to nucleate and propagate cracks if
the twins are thick enough. In the following, a sequence of events is outlined based on results
presented in Fig. 15 [21], describing the evolution of the twin-microstructure with emphasis on the
effects of this microstructure on MFIS, crack nucleation, and damage accumulation.
During 108 MMC, the sample (glued on both ends to the sample holder and sliding head) had
shown a maximum MFIS of 2.15% at 6 x 105 MMC. Above 1 million cycles, the MFIS decreased
to and stayed nearly constant at 1.2% for the last 3 x 107 MMC. The reduction of MFIS is likely to
be related to the cracks found with micro computer tomography (Fig. 16) and optical microscopy.
Fig. 20 is a scanning electron microscopy image of a crack surface which formed macroscopically
on a {110} plane. The crack formed during high-cycle magneto-mechanical testing and grew along
parallel crystallographic planes to a length of several millimeters with certain distinct micrometersized steps (arrows in Fig. 20). At the steps, the crack jumped from one {110} plane to another such
plane.
The cracks in the center of the sample are nearly perpendicular to each other (Fig. 16). The intact
regions between cracks span surface areas between 0.5 mm2 and 2 mm2. Magnetic-field-induced
twins carrying a large magnetoplastic strain are coarse with a thickness in the order of 100 m [65].
Orientation and size of the regions between the cracks suggest the presence of these large magnetic-

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field-induced twins. As described in Ref. [19], a larger number of dislocations pile up in walls
between large interacting twins (unlike between thin, needle-like twins). With increasing number of
dislocations in a wall, the stresses introduced at the dislocation walls eventually lead to the initiation
and growth of cracks along the interface of the blocking twin [81,82]. As shown in Ref. [23], the
initial twin thickness was below 10 m. Owing to magneto-mechanical cycling, these thin twins
merged by overcoming obstacles and formed larger twins. During the first 2 x 105 MMC, the twin
thickness did apparently not reach the critical thickness [19] above which dislocation walls are large
enough to induce critical stresses to initiate crack growth. Then, above 2 x 105 MMC, larger twins
were formed and twin boundaries were able to sweep through a larger portion of the specimen, thus
generating a larger MFIS (Fig. 15). These larger twins also form larger dislocation walls inducing
cracks that grow slowly until they are intercepted by other cracks growing perpendicular to them.
This can be seen in Fig. 16 where many cracks are terminating at intercepting perpendicular cracks.

Figure 20: Scanning electron micrograph of a part of the fracture surface that was
cracked before the sample was broken forcibly. The surface is micro-facetted.
Between the layers of the crystal, there are very distinct ripple like steps between
layers of the crystal of less than 1 m (indicated by the arrows) [24].
In a subsequent experiment, the sample was deformed mechanically in compression in an
orthogonal magnetic field of 2 T. The sample was not glued in this experiment. Thus, there were
only weak constraints due to friction. The compressive deformation aligned all twins even those
formerly restrained by the glue in the dynamic magneto-mechanical test over 108 MMC with the c
direction parallel to the direction of compression. The recovered strain was 5.9%, which is very
close to the theoretical 1-c/a and nearly 3 times larger than the largest MFIS measured during the
high-cycle test with a rotating field (Fig. 15). The lower magnetic field of 0.97 T in the dynamic
magneto-mechanical test does not account for this reduction because the recoverable strain reached
a plateau-like maximum above 0.7 T [24]. The lower value of maximum recovered strain during the
high-cycle test was caused by the constraints imposed by gluing the sample to the holder [23].
The microcracks parallel to the fracture surface of the forced crack confirm that the volume that
was not cracked during the high-cycle magneto-mechanical tests consists of small twins with
thicknesses in the micrometer range and below (as also evident from the ripples marked by arrows
in Fig. 20). The small twins created during inefficient training are restrained from merging during
the high-cycle magneto-mechanical test. A twin-microstructure with thin twins contains weaker
stress concentrations than a coarse twin-microstructure (Fig. 21), i.e. the stress distribution is more
homogeneous [23]. Thus, in agreement with the observations, no cracking is expected in the sample
corners.

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At first glance, one would expect that a sample with an extended network of cracks should
display a significant degradation of magneto-mechanical properties. It was shown in [24], however,
that the magneto-mechanical properties of this sample are comparable to those of similar samples
without cracks. After mechanical compression, the sample showed excellent magneto-mechanical
properties over at least 20 loading-unloading cycles without decay of the recoverable strain and
without change of crack size and crack number. Thus, the functionality of MSMAs is not
susceptible to degradation due to cracks, as long as mechanical integrity is maintained. This damage
tolerance of MSMAs originates in the low stress level needed for twin boundary motion and the
equally low stress level generated through a magnetic field (i.e. the magnetostress). Damage occurs
at sites of stress concentration. Consequently, development of high-performance devices with
MSMA transducers requires managing stress distributions through design and control of surface
properties, microstructure, and constraints.

Figure 21: Schematic of the twin structures for (a) the initial state after thermomechanical heat treatment and (b) after a high number of magneto-mechanical
cycles. (I) and (II) show the development of twin structures for an effectively (I)
and an ineffectively (II) trained sample. The gray boxes on the right and left side
of the specimen indicate the sample holder (2) and the sliding head (3) that
constrain the sample. The twins which are present at the ends (due to sample
constraints) are thick in (I) while they are thin in (II) [23].
Summary and Conclusions
The twin-microstructure, mechanical behavior, and magneto-mechanical behavior is influenced by
constraints. These constraints can be a result of surface damages, e.g. by abrasive surface treatment
or ion implantation, and are located within a thin surface layer of the sample. External constraints
are imposed onto a MSMA by holding and guiding mechanisms. The results of this study are
-

Initial training and twin-microstructure influence the magneto-mechanical behavior of


MSMA and need to be taken into account for different applications, desired twinning
stresses, MFIS, and operation lifetime.
Twin-microstructure, twinning stress, tw, twinning stress range, tw, and hardening rate
can be tailored via modifications of the surface layer.
External constraints result in a reduction of the MFIS. In the case of hard MSMAs and
constraints on two ends of the sample even cancel MFIS.
The adaption coefficient, , is a sample specific factor describing the measured vs expected
MFIS and indicates how well the twin-microstructure is adapting to external constraints.

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Three mechanisms were proposed to cause the observed effects:


1. Surface pinning of twins due to surface preparation increases the twinning stress and the
hardening rates, and also increases and stabilizes the twin density.
2. Locking of twins and twin boundary motion due to external constraints increases with
increasing number of external constraints and with increasing twinning stress and leads to a
decrease or even canceling of MFIS.
3. Adaption of the twin-microstructure to constraints over the course of magneto-mechanical
cycling results in an increase and stabilization of MFIS over the course of magnetically
induced actuation and is most effective for soft MSMAs with a high twin density.
In conclusion, this study emphasizes the importance of constraints and their influence on MFIS
of MSMAs. In particular, external constraints imposed by sample mounting hinder and may even
suppress twin boundary motion. The design of MSMA-based devices must reflect constraints
imposed on MSMA single crystals through holding and guiding settings.
Acknowledgment
We are thankful to a our colleagues for many helpful discussions: Cassie Witherspoon, Robert
Wimpory, Chad Watson, Kari Ullakko, Inara Thomas, Rainer Schneider, Adrian Rothenbhler,
Katharina Rolfs, Matt Reinhold, Walter Reimers, Robert Pond, Andreas Paulke, Gernot Kostorz,
William Knowlton, Linda Kenoyer, Jens-Uwe Hoffmann, Andr Hilger, Illya Glavatskyy,
Vlodymyr Chernenko, Dave Carpenter, Phil Boysen. We acknowledge financial support of DOE
Office of Basic Energy Sciences (BES) Contract No. DEFG-02-07ER46396 (M.C. and P.M.) and
the Deutsche Forschungsgemeinschaft (Grant No. SPP1239 Schn 1106/1, M.C.). P.M. is grateful to
ETH Zrich for donating magneto-mechanical testing devices.
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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.203

Long-term cyclic loading of 10M Ni-Mn-Ga alloys


Ilkka Aaltioa, Outi Sderbergb, Yanling Gec and Simo-Pekka Hannulad
Aalto University, School of Science and Technology,
Department of Materials Science and Engineering, P.O. Box 16200, FI-00076 Aalto, Finland
a

ilkka.aaltio@tkk.fi, bouti.soderberg@tkk.fi, cyanling.ge@tkk.fi, dsimo-pekka.hannula@tkk.fi

Key words: magnetic shape memory; Ni-Mn-Ga; fatigue; cracking

Abstract. Martensitic 10M Ni-Mn-Ga single crystals are usually applied in the magnetomechanical
actuators. Their behavior in the long-term cycling and the factors influencing upon are thus important to know. There are several publications concerning this. However, consistent statistical data
is still missing to large extent. In this report we review and analyze the data available in the literature. In conclusion it can be stated that 10M Ni-Mn-Ga single crystals survive well in long-term
actuation (millions of cycles) when the frequency of twin variant reorientation is not exceeding 250
Hz, and the strain used in actuation is below 3 %. There are several factors influencing the longterm behavior and these are discussed in more details in this work.
Introduction
Ni-Mn-Ga alloys with 10M martensitic (also called 5-layered or 5M) structure, have attracted interest as magnetic shape memory (i.e., MSM or FSM) alloys due to the high obtainable strain of 6
% [1]. The 10M martensite has a close-to-tetragonal crystallographic structure, where the short axis
is also the easy axis of magnetization (expressed in the parent phase coordinates). In the 10M NiMn-Ga the magnetic anisotropy provides high enough magnetic stress that can exceed the stress
needed to move the twins, i.e. the twinning stress, and thus, the actuation is possible even at a moderate applied magnetic field. It takes place as one martensite twin variant, short axis of which aligns
to the direction of the applied field, grows at the expense of another variant via twin boundary
movement [1-3]. When heated above the As temperature, the cubic parent phase starts to form and
above Af the structure is completely austenitic. If the material is deformed close above to the reverse transformation temperature (Af), but below the stress induced martensite forming temperature
(Md) also reversible stress induced martensite can form. Therefore, cyclic deformation in these alloys may be triggered by the change of temperature, applied mechanical stress, or applied magnetic
field (Fig. 1). High strain is obtained by the thermal shape memory effect (SME) based on the phase
transformation from austenite to martensite and vice versa, or by the reorientation of twin variants
in the martensitic phase. Of these, the SME allows higher stress generation by the material, while
the response time in cycling is shorter in twin reorientation when no temperature change is required.
It is noteworthy that the long-term actuation is not usually carried out with the maximum possible
shape changes, as this may lead to deterioration of the material quite quickly due to uncontrollable
change of variants into another.

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Figure 1. The different shape change possibilities for cycling in the 10M Ni-Mn-Ga alloys.
Applications where the cyclic loading can be utilized
MSM materials are expected to suit for many actuation purposes [4], although so far no large-scale
industrial applications exits. Their advantages in the actuator use are the rapid response, proportional controllability, high intrinsic damping, wide frequency range and large obtainable strains together
with the small size and high reliability [5]. The main drawbacks are the limited force output, the
limited operating temperature range and different controllability when compared to e.g. electromagnetic transducers due to hysteresis [6-8]. The applications are expected to include also sensors,
vibration damping and microsystems [9]. Cyclic MSM actuation has been studied for use in e.g.
proportional valves [8], automotive microscanners [10], hybrid micro actuators [11] and propulsion
flapper application [12]. The control of the nonlinear and hysteretically behaving MSM actuator has
been studied in [13]. Cyclic loading of MSM materials can also be applied in vibration damping
[14] and energy harvesting [15].
There are some new material solutions that may be also applicable in the cyclic loading, although
they have not yet been extensively studied. The polymer composites produced by using 10M NiMn-Ga [16-19] alloy particles are of special interest in this respect. It has been shown that the polycrystalline 14M Ni-Mn-Ga foam materials can be used in the cyclic loading [20,21], and it would be
interesting to know, if this was applicable for the 10M martensite alloys also. In all these applications, twin boundaries between the twin variants are driven back and forth at each operating cycle,
such as one actuation stroke. Thus, adequate fatigue properties of the material are essential for high
functional reliability.
Cyclic loading induced reorientation of twin variants and influencing factors
The stress levels in cyclic loading induced reorientation of the twin variants of the 10M martensite
Ni-Mn-Ga the stress levels are low, since the twin boundaries are mobile. The maximum obtainable
strain depends on the magnitude of lattice parameters i.e., on the axial ratio of tetragonal lattice as
0=(1-(a/c)) [2]. In actuation the strains typically are kept below 3 % [3]. The active MSM element
is usually cut off from the favorably oriented single crystal that has been homogenized and ordered
in order to provide the most suitable modulated atomic structure. Motion of twin boundaries occurs,
when a sufficient shear stress is applied in the crystallographic shear direction <101>. This can be
accomplished either by the uniaxial external stress or by the magnetic field induced stress provided
they exceed the twinning stress. In a high quality material the twin boundaries move even at 0.05
MPa stress [22], while in materials with lower quality, higher stress or higher triggering magnetic
field is needed. In twin boundary mobility also the twin modulation is a factor: modulation is much
more even throughout the sample in high quality material than in the one with lower quality. If the
twinning stress exceeds the maximum magnetic stress that can be created in the alloy, the magnetic
field is not alone capable to move the twin boundaries [1]. It is noteworthy that reversed twin

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movement in MSM material does not occur if the applied magnetic field is removed. However, the
crystal can be returned to its original shape either by applying an opposite mechanical stress or by
applying a magnetic field at the 90 angle in relation to the original field, or by combining the mechanical and magnetic stress in proper direction. When a constant pre-stress is applied to the MSM
material, the obtainable magnetic field induced stress may be reduced from 0 [7]. Thus, MSM material utilizing twin reorientation can be cycled by three different ways: (i) magnetomechanically,
when the material is actuated by the magnetic field, and returned to its original shape by external
stress, such as by a pre-stress spring; (ii) mechanically, when material is strained by external tensile
and compressive stress back and forth; and (iii) magnetically, when the motion of MSM specimen is
generated by changing the direction of the applied field direction.
Defects and other constraints in the material. The twinning stress of the material seemingly
depends on its purity, crystallographic faults, and martensite variant structure. In crystals exhibiting
a single variant state more energy is needed to nucleate and move the secondary variant than in
crystal where there already exists a secondary variant [23,24] and energy is only needed for the
movement of the second variant. Constrains and defects in the material may block the motion of
twin boundaries partially or even completely. Such constraints may be grain boundaries [25], incompatible twin variants [26], crystal defects and impurities [22], and mechanical damage of the
surface [27]. Thus, the highly constrained polycrystals of 10M Ni-Mn-Ga have a tendency to deteriorate soon when deformed, though in the well trained textured polycrystalline material 1 % MFIS
is obtainable [28], and there are not publications of their use in the long-term cycling. In Fig. 2c it is
shown, how an inclusion can be origin of the microcracks in magnetomechanical cycling as comparison, also microcracks developed at the surface scratch are shown (Fig. 2d). Etch pits (Figs. 2a
and b) in the not-cycled surface may be addressed to existing dislocations in the single crystal.

Figure 2. (a) and (b) Etch pits on the surface of the polished 10M Ni-Mn-Ga alloy. (c) Microcracks
at inclusions of the surface and (d) a surface scratch with microcracks indicated by arrows, after
magneto-mechanical cycling. (Images on courtesy of X.W. Liu) [29]
The influence of the incompatible twin boundaries is shown in Fig. 3. The traces of the macroscopic
intervariant boundaries with different widths reveal that the easily and hard moving twin boundaries
are located in the sample at distinct regions. The variant boundary at the left side can be moved with
a very low axial stress below = 0.1 MPa. When considering the region with the hard moving twin
boundaries, deformation requires higher stresses, for example = 1 MPa for the boundary of Fig. 3.
During the cycling, the locations and amounts of the actively moving boundaries change. This development is resulted by the increasing or decreasing local constraints for the twin boundary motion.

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Region of the
easily moving
twin boundaries

Hard to move

Hard to move

87.46o
92.35o

92.55o

86.93o

Tilt
4.43o

Figure 3. Schematic presentation of the region with easily moving twin boundaries and that where
the twin boundaries are hard to move [29]. Optical image of the long-term cycled sample surface
with region of the hard moving twins on the upper end, and easily moving twins in the lower part of
the sample (image on courtesy of H. Pulkkinen).
The surface stresses may prevent the motion of the twin boundaries, and thus, the 10M Ni-Mn-Ga
MSM materials are usually electropolished in order to reduce stresses arising form the mechanical
grinding. However, it is noteworthy that the surface of the material may be damaged also during the
cycling test. This was observed in magnetomechanical cycling [27], when the twins in the damaged
regions were constrained resulting in decreased maximum obtainable magnetic field induced strain
(MFIS). In fact, the fraction of the damaged surface correlated directly with the decrease of the
MFIS. In the magnetic and magnetomechanical actuation, there occurs easily contact and thus friction between the MSM element and the static magnetic circuit since the air-gap in between them
should be as small as possible in order to apply a sufficiently high field for inducing the MFIS. Actually, if the MSM element is readjusted during the long-term cycling to reduce the friction (in case
where this occurs), this may even increase the MFIS.
Deformation mode. Cyclic reorientation of the twin variants can occur either by uniaxial straining,
shear straining or bending [30]. However, the contraction and extension takes place in the plane
defined by a and c axis, because of the tetragonal crystal structure of the 10M material. If deformation occurs to other directions, incompatible twins with crossing planes appear. They result in
stress concentrations and constraints leading to premature cracking. Thus, some commonly used
deformation methods such as rotational torsion is not appropriate for these alloys. In addition, especially in uniaxial cycling at a high frequency, the axial alignment and the mechanical balance of the
cycling equipment are important as in unbalanced system the transverse strains can appear [6,9].
Applying the magnetic field. It has been shown that theoretically the field penetration depth decreases from 100 mm at 1 Hz to 1 mm at 10 kHz, and the eddy current losses increase with frequency limiting thus the maximum operating frequency of the MSM material [5]. The speed of the MSM
actuator is high. Velocities of 1.3 m/s have been measured [31], though the velocity may be higher
if no eddy currents exist. Eddy currents reduce the magnitude and delay the phase of the magnetic
field [32,33]. The frequency spectrum shows a monotonous decay of strain magnitudes with increasing even harmonics up to an actuation frequency of 100 Hz. From 150 Hz onwards the decay
is not monotonous, which is seen in the strain-field plots as the rounding-off of the hysteresis loop
[32]. When higher frequencies are needed the moving mass of the actuator must be small and the
MSM element can be laminated to reduce eddy currents. Actuation can be triggered for example by
applying a 360 rotated magnetic field of a constant magnitude [34] or by the transversely applied
magnetic field of alternating magnitude and with the pre-stressed spring in a fixed direction [4,27].
When a 360 rotating field is applied to a specimen in the crystallographic a-c plane, there are two
maxima of MFIS per each rotation [34], as can be seen of the -H behavior in Fig. 4. This was applied in [34] by using the 6 % MFIS, but resulted in severe cracking, so in the long-term cycling

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with pure magnetic field, the smaller strain is favorable. Application of the alternating field magnitude and pre-stress spring has been used in MSM actuators, where the field is generated by an electromagnetic circuit, which can be biased by permanent magnets. Such actuators are preferably driven with current control [6].

Figure 4. (a) Magnetic field induced strain (%) of 10M Ni-Mn-Ga as a function of the angle of the
applied field. is the angle between the [100]A direction and the applied magnetic field and the
field is rotated in the a-c plane [35]. In (b) the pre-stress is applied in the [100]A direction.
Control mode of the cycling. In mechanical cycling the intrinsic magnetic properties do not limit
the stress. In long-term actuation the strain control is more stable and reliable than the stress control.
E.g., 10M crystal can contract and extend by the reorientation of twin variants in the strain region B
from 0 < < 0 between the single variant states A and C in Fig. 5. Cycling in this region (case r1)
requires only a low stress as there are always two martensite variants present. If straining extends to
single variant state as in cases r2 or r3, the stress increases rapidly as twin reorientation is not anymore possible, and the further strain change cannot be accommodated by it. Such a strain may be
caused by e.g. thermal expansion or contraction of either the specimen or of the parts of the test
equipment. This can significantly increase the cycling stress and, e.g., speed up the cracking of the
cycled material.

variant reorientation
regime (B)

A
0

C
0

Strain

Figure 5. Strain regime of variant reorientation.


In the load controlled cycling, the strain should vary between two constant values. However, during
the twin variant reorientation, there are serrations in the stress-strain curve which are characteristic
for twinning. Also, the stress-strain curve of the material is not always reproducible, but it can show
different stress levels at different variant states [29]. The variation of the stress-strain behavior will
usually abruptly reduce the strain region r as was observed in [36].
Influence of the long-term cycling on the 10M alloys
When applying material in dynamic actuation applications information of their long-term cycling
properties is required. Several works provide detailed data of this matter [26,27,29,30,34,35,37],
although many of the published works describe the structure and actuation principles of the actuators [4,6,8,9]. In general, these studies have shown that cycling decreases the obtainable magneticfield-induced strain (MFIS) and promotes crack growth.
Long-term magnetic cycling. In magnetic actuation 10M single crystal based actuators have
demonstrated more than 2 x 108 cycles without major deterioration of stroke [30]. More detailed
structural study during the long-term actuation at room temperature was made by Heczko et al.
[34]. Sample was in rotating 0.7 T magnetic field and its structure switched between two differently

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oriented martensitic twin variants providing the maximum MSM effect of 6 %. Sample elongated
perpendicular to the magnetic field and contracted in the direction of the field with actuating frequency of 11.4 Hz (i.e., rotation at 5.7 Hz). The maximum frequency was in this case limited by
sample heating that was caused by the eddy currents in the bulk sample and by internal friction (energy dissipation) during the MSM effect. This kind of a test is very demanding for the sample, as it
in addition to the 6 % pulsating strain there is a torque created by the rotating magnetic field. Thus,
it is likely that the damage evolves faster in the test than in actual actuators. Studied samples had
small cracks before test, which may lock the secondary twin variants during cycling (Fig. 6a), and
on the other hand these residual twin variants may induce new cracks during cycling. Both of these
mechanisms are expected to enhance crack propagation. The evolution of the cracks with the number of cycles is presented in Fig. 6b. The MSM strain decreased from its original value (6 %) to
about half (3 %) during the first few million cycles, which value remained till the end of the test at
74 x 106 actuation cycles (37 x 106 rotation cycles).

(a)
(b)
Figure 6. Crack evolution in magnetic cycling. (a) Cracks (black horizontal regions) and residual
twin variants (dark gray vertical bands) interacting before cycling. Round etch pits and the cell
structure are also shown. Magn. ~ 230x. (b) Evolution of the crack pattern with the number of actuation cycles. Cracks are shown with black lines; the gray line is some kind of a surface formation.
Magn. ~ 30x. (Pictures made from images by O. Heczko and L. Straka, used on their courtesy.)
In [36] magnetic cycling was used to evaluate the influence of dislocations on the cyclic behavior of
Ni-Mn-Ga alloys. MSM fatigue of 10M and 14M samples with different magneto-mechanical histories was studied in a rotating magnetic field at 1 T and 2 T and angular frequencies up to 420 rad/s
(corresponding roughly to the actuation frequency of 134 Hz). It was suggested based on the tests
that if the twinning dislocations are allowed to move freely, the full spontaneous strain is obtainable
by the application of a rotating magnetic field. The local constraints (i.e., stress concentrations) restrict the dislocation movement, and thus their interaction with the twins lead to the formation of the
voids and microcracks.
Long-term mechanical cycling. In order to avoid the influence of the certain external factors,
the structure evolution of the 10M Ni-Mn-Ga has also been studied by using mechanical cycling.
Several 10 M single crystal samples were cycled in uniaxial tension/compression to avoid any surface friction or magnetically induced effects on the structure [37]. The longest test at 250 Hz included 2 109 cycles, and was stopped without breakage of the sample. However, there also were
samples that could not survive as long in cycling. Anyhow, the obtained results indicated that the
10M Ni-Mn-Ga alloys were very stable in cycling loading when mechanical damage or wear of the
sample surfaces were minimized or avoided. No notable change in the transformation temperatures
or the Curie point was observed. Although the cycling was carried out mechanically, the magneticfield-induced strain of the strain was measured after the long-term cycling. MFIS had not decreased
from the theoretical maximum, which confirmed that the full sample length acted as an MSM element. The twinning stress, when observed from the stress-strain-loops (Fig. 7a), showed an increase
as the number of cycles accumulated to level of several hundred millions. In Fig. 7a the height of
the loops at zero strain increases with increasing number of cycles, and the differences of the max-

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imum and minimum stress of the loops increase even more clearly. In [26], where twin structure
was regarded to be interlocked in the beginning of cycling, the twinning stress did not change
markedly during the cycling, and remained quite high (1.5 MPa) in comparison to the value when
the interlocking was not present (0.11 MPa). As twinning stress depends on temperature the heating
as a result of the hysteretic stress-strain behavior during the high-cycle actuation should be taken
into account. In [26] temperature rise of 2 K was observed at 300 Hz mechanical actuation of 10M
Ni-Mn-Ga alloy. This should decrease the twinning stress by about 5 %. In [37] the steepness of the
dynamic stress-strain loop of the material started to increase already after about 106 cycles simultaneously with the twin width decrease and appearance of the new mobile regions in the sample (Fig.
7b). This can be observed as steepening of the stress-strain curve (Fig. 7a).

(a)
(b)
Figure 7. (a) An example of steepening of the stress-strain curve in high-frequency long-term mechanical cycling at room temperature. (b) Schematic presentation for the twin structure refinement
in mechanical cycling from the situation after 0.7 x 106 cycles to 70 x 106 cycles. (Pictures made
from images by A. Soroka, used on his courtesy.)
There may be different types of pre-existing faults in the material before cycling as presented in,
e.g., Fig. 2. When the evolution of the pre-existing cracks was studied, it was noted that depending
on their orientation in respect to the applied stress, they could act as a starting point for the fatigue
crack. In general, the cycling caused quite regular crack patters on the surface consisting of the microcracks along the traces of the twin boundaries (Fig. 8a) and voids that seem to have formed as
chipping off material between the microcracks. As cycling continues, microcracks grow and join
forming larger cracks, and gradually on the surface large chipped crack regions will appear (Fig.
8b). In microscopic scale the fracture propagates in a step-like manner seemingly along the crystallographic planes (Fig. 8c), while macroscopic cracking occurs roughly in 45 angle (i.e. along the
{111} plane) in respect to the direction of the applied load. The sample fractures producing a steplike fracture surface (Figs. 8c and d).
The crack propagation and fracture mechanics of the 10M shape memory alloys have also been
studied in thermal cycling [39-41]. According to these studies martensite morphology did not
change in more than 200 thermal cycles over the phase transformation region with the cycling rate
of 2 oC/min. However, in less than 50 cycles at faster thermal change rate of 5 oC/min remarkable
morphology change did take place. Differently oriented martensite twin bands were well accommodated with each other and 100-150 m cracks were formed. It was suggested that these cracks were
initiated from the specimen surface and there also were other cracks (1-2 m wide, millimeters
long) in the vicinity of the main crack. Jumps of the fracture plane into the adjacent parallel plane
existed and were regarded as a feature of pre-cleavage microcrack. It is noteworthy that the thermal
cycling rate seems to be a relevant factor for the cracking of Ni-Mn-Ga.

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Figure 8. Evolution of the sample in mechanical cycling. (a) Cracks and voids at the traces of the
twin boundaries in a cycled sample (SEM BE image). (b) After 2 x 109 cycles voids and microcracks along the trace of the twin boundaries have been formed at the surface of the sample
(SEM BE image). (c) The fracture surface of the cracked sample after cycling (SEM SE image). (d)
The macroscopic crack of the cycled sample still clamped to the test jig.
Long-term magneto-mechanical cycling. Magneto-mechanical cycling on the 10M alloys
seems to be more complicated case than that of the mechanical cycling. The generated local magnetic flux may vary in the different parts of the material, and its strength depends on e.g. field homogeneity, shape anisotropy, and such material properties as magnetic domain configuration and
local differences of magnetic properties. In addition to these also eddy currents influence on the
long term cycling behavior. Also wear or friction from the components surrounding the MSM element cause additional complications. Eddy currents heat up the MSM element, and thus, it is important to control the temperature of the sample in order to avoid overheating to the two-phase or
austenite region. On the other hand one must also take into account the softening of the material due
to the decrease of twinning stress [42]. Long-term magneto-mechanical cycling tests have also been
carried out under a constant pre-stress to over 200 x 106 cycles without failure [27]. There was a
decrease of 0.5 % relative to the sample length in the dynamic stroke and also the magnetic-fieldinduced strain decreased as the cycling proceeded. The twinning stress simultaneously increased by
10 %. Microstructural changes were studied at certain cycling intervals and crack formations were
observed. The influence of surface wear resulted in formation of the areas with twins blocked. Usually, this blocking leads to increase of the twinning stress and thus applied load in order to keep the
working strain constant. As a result there may appear new active regions that originally had higher
twinning stress for the twin reorientation.
A Ni-Mn-Ga single crystal stick with dimensions of 3 x 5 x 20 mm3 was magnetomechanically cycled in an MSM actuator at 20 Hz frequency by ETO Magnetic GmbH [43]. Strain, when measured
from the removed actuator element at intervals of 100 x 106 cycles, seemed to decrease continuously over more than 4.25 x 108 cycles after which the cycling test was stopped (Fig. 9). Both the test
material and the actuator were produced by ETO Magnetic.

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Figure 9. Strain output as a function of number of cycles of a Ni-Mn-Ga stick with dimensions
3x5x20 mm3 cycled at 20 Hz in a MSM actuator. ETO MAGNETIC GmbH, published with permission.
In [44] magneto-mechanical cycling with 400 Hz (12 x 103 rpm rotation) was carried out with the
10M single crystal quaternary Ni-Mn-Ga-Fe alloy. In this study, the maximum MFIS was obtained
in multiple steps with increasing magnetic field. This was explained with the different twin boundary variants in the structure, and other obstacles (pores, impurities, dislocations) that could hinder the
twin boundary motion through the entire sample volume. The fatigue results were comparable with
the Ni-Mn-Ga single crystals. The MFIS was at the beginning of the test low (0.5 %), but it increased to a maximum value of 4.5 % after 62.4 x 103 actuation cycles. It reduced again and stayed
at 0.4 % until the 2 x 106 actuation cycles, when the test ended and sample broke while it was taken
out from the test jig.
Summary
It is clear based on the existing information presented in the literature that the 10M Ni-Mn-Ga alloy
single crystals perform quite reliably in long-term actuation. Twin variant reorientation occurs in a
predictable way for millions of cycles at least when frequency is not exceeding 250 Hz, and provided that the strain used in actuation is such that the crystal does not enter the single variant state during the cycling. However, it seems that conventional thermal actuation is not feasible in case that
long-term cycling is needed.
When the long-term use of these materials is optimized one should be aware of several factors: (i)
the actuator system works best in strain controlled (when using feedback control) and current controlled mode; (ii) the construction of the actuator should be optimized to minimize the dynamic
mass, to avoid the disturbance of harmonic frequencies, and to avoid the material from entering into
single variant state; (iii) actuator system should not cause any surface damage to the material; (iv)
service temperature and the heating of the sample (due to the heating of the coils and the effect of
eddy currents) must be controlled so that there is no possibility for the material to overheat to the
phase transformation region; (v) the material failure will occur to some crystallographically preferably directions as the actuation is carried out to the best working direction; (vi) the final stages of
the failure may be very sudden.
The 10M Ni-Mn-Ga crystals usually contain various intrinsic material defects and constraints. These influence the behavior of the material also in the long-term cycling. However, as the early results
from the beginning of 2000s show, even materials with quite poor quality having about 1 MPa
twinning stress show reasonable long-term cycling resistance. In the beginning of the highfrequency cycling (at 250 Hz) the twin structure of the material refines, and the originally low twinning stress increases to some extent. It may be that during the cycling some of the active regions in

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material will become blocked, but usually they are replaced with new active regions that originally
had to some extent higher twinning stress. As the cycling continues voids and small cracks start to
evolve at the active twin reorientation regions. In further cycling cracking intensifies and the cracks
together with some pre-existing structural cracks may start to grow, usually in certain crystallographic direction. The macroscopic crack propagation occurs roughly in 45o direction in respect of
the applied loading. This crack growth involves shifting from one crystallographic plane to another
one with same direction, seen in the fracture surface as a step-like advance. When the remaining
cross-section area bearing the applied load becomes too small in respect to the strength of material,
the final fracture takes place in the brittle manner.
Even though the long-term cycling of the 10M materials is a prerequisite for their service life evaluation, systematic, statistic data of it is so far missing, as the emphasis of the research has been mainly in the material development. The results reported so far in the literature have been summarized in
Fig. 10. The scatter of the data presented strongly suggests there should be a systematic study, preferably with standard material involving not only the statistic long-term data, but study on the influence of frequency, service temperature, different actuation modes, and different deformation modes.
Also, the influences of the different material properties twinning stresses, purity, alloying, variant
structure, etc. are matters of further studies.

Figure 10. Collection in cycle-strain plot of the 10M long-term cyclings published in different
sources. The tests which have been terminated due to fatigue cracking have dark filled markings.
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(2011) Trans Tech Publications, Switzerland


doi:10.4028/www.scientific.net/MSF.684.215

Surface study of Ni2MnGa(100)


S. W. DSouza1, a, R. S. Dhaka1,b, Abhishek Rai1,c, M. Maniraj1,d, J. Nayak1,e,
Sanjay Singh1,f, D. L. Schlagel2,g, T.A. Lograsso2,h, Aparna Chakrabarti3,i,
and S. R. Barman1,j
1

Surface Physics Laboratory, UGC-DAE Consortium for Scientific Research, Khandwa Road,
Indore 452001, Madhya Pradesh, India

Materials Sciences, Ames Laboratory U.S. DOE, Iowa State University, Ames, Iowa 50011-3020,
USA
3

Raja Ramanna Centre for Advanced Technology, Indore 452013, Madhya Pradesh, India
a

sunilwilfred@gmail.com, brsdhaka@ameslab.gov, cabhishek_ri@rediffmail.com,


maniraj@csr.ernet.in, ejayitanayak@gmail.com, fsanju8419@gmail.com, gschlagel@iastate.edu,
h
lograsso@ameslab.gov, iaparna@rrcat.gov.in, jbarmansr@gmail.com

Key words: Ferromagnetic shape memory alloy, martensite transition, surface, low energy
electron diffraction, photoelectron spectroscopy.

Abstract. The (100) surface of Ni2MnGa ferromagnetic shape memory alloy exhibits intrinsic
surface property dissimilar to the bulk as well as influence of compositional variation at the surface.
It is shown that by sputtering at room temperature and annealing at high temperature, it is possible
to obtain a clean, ordered and stoichiometric surface. However, for even higher annealing
temperatures, the surface becomes Mn rich. The (100) surface of Ni2MnGa is found to have MnGa
termination. A surface reconstruction to p4gm symmetry is observed in the austenite phase, while
the expected bulk truncated symmetry at surface is p4mm. For the stoichiometric surface, the XPS
valence band is compared with our calculations based on first principles density functional theory
and good agreement is obtained. The ultraviolet photoelectron spectroscopy (UPS) valence band
spectra depend sensitively on composition varying from Ni rich to Mn rich surfaces. A satellite
feature observed in both Ni 2p core-level and valence band spectra is related to the narrow 3d
valence band in Ni2MnGa.

Introduction
Recent advent of ferromagnetic shape memory Heusler alloys like Ni-Co-Mn-In, Ni-Mn-Ga
has ushered a flurry of activity in this field [1,2,3,4,5,6,7,8,9,10]. In these functional materials, the
shape memory effect can be driven by magnetic field, which makes the actuation faster than
conventional shape memory alloys that are driven by temperature or stress. Among the different
ferromagnetic SMA's, Ni2MnGa has the highest reported magnetic field induced strain (MFIS) of
10%[3,4]. Besides, Ni2MnGa exhibits giant magnetocaloric effect [11] as well as large negative
magnetoresistance [8]. The combination of these properties with MFIS makes Ni2MnGa a
technologically promising material.
Ni2MnGa is ferromagnetic at room temperature with Curie temperature of 376 K. It has a
cubic L21 structure in the austenite phase [12]. For the nonstoichiometric Ni2+xMn1-xGa, the
martensitic and magnetic transition temperatures, magnetocrystalline anisotropy, enthalpy and
saturation magnetization vary sensitively with composition [10,13,14]. The substitution of Mn with
Ni results in the increase of martensitic start temperature and decrease of Curie temperature with
increasing x. For the compositions with x greater than 0.2, martensitic start temperature is larger
than Curie temperature [15,16]. Depending on composition, the Ni-Mn-Ga martensite phases have
been reported to assume complicated monoclinic or tetragonal structure with 5M modulation or

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orthorhombic structure with 7M modulation[3,12,17,18,19,20,21]. The 7M (5M) phase corresponds


to 7-layer (5-layer) modulation of the (110) planes in [11 0] direction in the austenite phase.
However, a tetragonal phase that does not exhibit any modulation has been reported for nonstoichiometric Ni excess Ni-Mn-Ga [10,17,18,22].
The surface study of Ni2MnGa is important because, being a shape memory alloy, it can
undergo macroscopic change in surface relief that might have interesting influence on the adlayer or
nano structures grown on it. Besides, being ferromagnetic with large moment, it might induce
ferromagnetism in the adlayer. Spintronics applications, where Ni2MnGa might act as a spin injector
source, could be envisaged since recent band structure calculations have shown that Ni2MnGa
exhibits a half-metallic character along certain directions of the Brillouin zone with a gap of about
0.7 eV in the majority-spin bands, while the minority-spin bands that cross EF have no gap [23]. For
such device applications heat treatment might be required and this can change the surface and
interface properties because of change in composition. Since the properties of Ni2MnGa are
sensitive to composition, changes of surface composition might lead to the modification of the
surface electronic structure compared to the bulk.
Although in recent years, extensive studies have been performed on polycrystalline, thin
films and the bulk properties of Ni-Mn-Ga single crystals, to the best of our knowledge, there are
hardly any studies on the surface properties. This may be related to the difficulty in obtaining an
atomically clean single crystal surface with composition similar to the bulk. In this work, we review
the work that has been performed by us to study the atomically clean surface of Ni2MnGa(100) with
different surface compositions. The surface composition has been determined by x-ray
photoelectron spectroscopy (XPS). From angle dependent XPS, we determine that the surface
terminates in the Mn-Ga plane. We observe the intrinsic influence of the free surface as well as
effect of compositional variation on the spectral shape in ultraviolet photoemission spectroscopy
(UPS). A surface reconstruction to p4gm symmetry is observed in the austenite phase from low
energy electron diffraction (LEED).

Experimental methods
Ni2MnGa single crystal was grown at the Materials Preparation Center of the Ames
Laboratory by the Bridgman method [24]. The ingot was oriented in the austenite phase by Laue
back reflection and the sample was spark cut. The polishing was done mechanically using quarter
micron diamond paste followed by electropolishing in nitric acid and methanol. The bulk
composition was confirmed by wavelength dispersive x-ray spectroscopy to be Ni2.03Mn1.01Ga0.96.
LEED was performed at a base pressure of about 410-11 mbar using ErLEED optics from Specs
GmbH, Germany. The stoichiometric Ni2MnGa(100) surface was prepared by sputtering with 1.5
keV Ar+ ions and annealing at 770 K for 1 hr. The cleanliness and the surface composition were
ensured using x-ray photoelectron spectroscopy (XPS). The photoemission studies were performed
by using a commercial electron energy analyzer (Phoibos 100 from Specs GmbH, Germany). To
obtain a single variant state in the martensite phase, the crystal was clamped along the vertical in the
[01] direction of the crystal in a sample holder designed for studying complex metal surfaces [25].
To check this, we recorded LEED patterns as a function of position over a grid on the crystal at 12
different positions. In each case, the patterns in both martensite and austenite phases remained
unaltered. The martensite transition temperatures for the bulk crystal have been determined using
differential scanning calorimetry using Model 2910 from TA Instruments at a heating and cooling
rate of 10 C/min. The latent heat was found to be 0.2 KJ/mole, in agreement with literature [10].

V.A. Chernenko

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Results and Discussion


Determination of surface composition using x-ray photoelectron spectroscopy. XPS is a surface
sensitive technique and hence the relative intensities of the core-level peaks from the constituent
elements represent the composition within about 20 of the surface. The variation in the surface
composition of Ni2MnGa(100) single crystals with different sputtering and annealing conditions are
evident from the relative intensities of the Ni 3p, Mn 3p and Ga 3d core-level peaks in Fig. 1(a).
These spectra have been recorded as a function of annealing temperature (TA), and in each case after
15min sputtering by 1.5keV Ar+ ions. The Ni 3p, Mn 3p and Ga 3d core-level peaks appear at 66.6,
47.2, 18.4 eV binding energies (BE's), respectively. The core-level intensities, defined by the area
under the least-square fitted peaks, are used to estimate the surface composition. Because their BE's
are not very far apart, the analyzer transmission function and mean free path of the photoelectrons
turn out to be similar. For example, the mean free path for Ni 3p, Mn 3p, and Ga 3d are 19.8, 21.1,
and 19.1, respectively [26]. Moreover, the background for these core-levels are less since they
have relatively small BE and there is no interference from any other core-levels and Auger peaks
over the whole range unlike for the higher BE 2p levels. For example, the L3M23V Auger peak
interferes with the Mn 2p peak. Moreover, Ga 2p is too close to the secondary tail and this makes
the determination of the background quite unreliable in this case. Thus, the compositional analysis
is more reliable with the shallow core levels (Ni 3p, Mn 3p and Ga 3d), in contrast to the 2p levels,
which have larger inelastic background that introduces more uncertainty in the determination of
peak intensity. For finding the composition, the atomic photoemission cross-sections were taken
from [27]. The change in the relative intensities of the Ni 3p and the Mn 3p peaks is clear from the
spectra in Fig. 1(a) for Ni2MnGa. We find that sputtering has an opposite effect compared to
annealing; the former makes the surface enriched in Ni and deficient in Mn. For example, after
sputtering with Ei= 1.5 keV and 0.5 keV Ar+ ions (Fig. 1(b)), the compositions are Ni2.7Mn0.5Ga0.8
and Ni2.5Mn0.6Ga0.9, respectively, in contrast to the bulk composition: Ni2MnGa.

Fig.1.(a) Ni 3p, Mn 3p and Ga 3d XPS core-level spectra of Ni2MnGa(100) (a) as a function of


annealing temperature (TA), (b) recorded at 300K after sputtering at 0.5 and 1.5 keV incident ion
energies with no annealing, and (c) recorded after annealing at 770 K for different time period. The
spectra are staggered along the vertical axis for the clarity of presentation.

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In order to explain Ni enrichment due to Ar+ ion sputtering, we have performed Monte Carlo
calculations using the TRIM-2000 (Transport of Ions through Matter) code to calculate the
sputtering yields. The calculations have been done using full quantum mechanical treatment of ionatom collisions for 50,000 ions incident with energy Ei at normal incidence geometry [28]. We find
that if we take the composition to be NiMnGa, the sputtering yields of Ni, Mn, and Ga are 0.9, 1.4,
and 1.5 atoms/ion, respectively for 1.5 keV and 0.5, 0.8, and 0.8 atoms/ion, respectively for 0.5 keV
incident ion energy. Higher sputtering yield of Mn explains its preferential sputtering, and
consequent Ni enrichment at the surface. However, if the alloy composition is taken to be Ni2MnGa,
the sputtering yields are 1.5, 1.1 and 1.2 atoms/ion for Ni, Mn and Ga, respectively at 1.5 keV. This
would imply just the opposite of what is observed here experimentally. The reason for this
disagreement is possibly related to the structure of the alloy and the surface termination for single
crystalline surfaces, which are not considered in the calculation. If the surface is Mn-Ga terminated
(Fig. 3(b), discussed later), sputtering yield for Mn and Ga would be higher compared to Ni, since
sputtering involves mostly the upper monolayer of the target.
In some cases, the change in surface composition due to sputtering can be reverted by
annealing so that the near bulk composition is restored at the surface. For example, Mn enrichment
at the surface by annealing has been observed in other Mn containing alloys like half Heusler alloy
NiMnSb, [29] where annealing to 720 K restores the approximate bulk composition at the surface.
For Al-Pd-Mn quasicrystal surface, although sputtering causes Pd enrichment, subsequent annealing
to 800-900K restores the approximate bulk composition at the surface by segregation of Mn [30]. In
order to examine the effect of annealing, the amount of Ni, Mn, and Ga in a formula unit is plotted
as a function of TA for Ni2MnGa(100) in Fig. 2. Clearly, the Ni content decreases and Mn increases
with increase in TA. For TA= 770 and 950K, the surface compositions were Ni2.05MnGa and
Ni1.5Mn1.5Ga, respectively. Hence, TA= 770K restores the bulk composition at the surface. It may be
noted that this temperature is higher than what has been reported in Ref. 31 because of two possible
reasons: (i) the present composition, Ni2.05MnGa (Mn:Ni= 0.48) is closer to stoichiometric
composition compared to what was reported earlier (Ni2.1Mn0.8Ga1.1, Mn:Ni= 0.38) [31] and (ii) we
have observed that many cycles of sputtering and annealing lead to decrease in the amount of Mn
segregation to the surface, requiring higher TA to attain a particular composition. In order to
determine the time required to attain the stoichiometry at the surface, the sample was annealed at
770K for different periods (Fig.1(c)). The surface composition determined for 1 and 2 hr annealing
are very similar (Ni2.06Mn0.98Ga and Ni2.05Mn0.96Ga, respectively), which indicates that 1 hr is
sufficient to obtain the stoichiometric surface.

Fig. 2. Variation in the surface composition, as determined from x-ray photoelectron spectroscopy
(XPS), as a function of annealing temperature (TA) for Ni2MnGa(100). The temperature
corresponding to the stoichiometric surface composition is shown by a red bold arrow.

V.A. Chernenko

219

We show in Fig. 3(a) that the (100) surface of Ni2MnGa could have either Mn-Ga or Ni
termination. However, as discussed earlier, the TRIM calculation indirectly indicates that the
surface is Mn-Ga terminated. So, in order to experimentally study the termination, we have
performed the angle dependent XPS measurements (Fig. 3(b)). It is well known that at near grazing
photoelectron emission angles, XPS is more surface sensitive compared to normal emission [32,33].
An evidence of this effect is shown by the enhancement of surface plasmon loss peaks in the XPS
spectra of Al (111) at grazing emission angles [33,34]. The experimental geometry is shown in the
inset of (Fig. 3(c)), where is the emission angle. As decreases, the Ni intensity decreases and Mn
and Ga line intensities increase toward grazing emission (Fig. 3(b)). Note that from = 500 to 100,
the mean depth for no loss photoelectron emission would decrease from 15.15 to 3.45 .

(a)

(d)

Fig. 3. (a) The L21 unit cell of Ni2MnGa in the austenite phase. The separation between the MnGa
layer (solid arrow) and the Ni layer (dashed arrow) is d. (b) Variation in the surface composition as
a function of electron emission angle () for Ni2MnGa(100). (c) Ratio of Ni 3p and Mn 3p
intensities fitted with Eq. (1) (solid line). Inset shows the experimental geometry. (d) The
differential scanning calorimetry data of Ni2MnGa(100) single crystal, showing the first order
martensitic transition, the transition temperatures are indicated by ticks.

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Considering that the topmost layer is made up of Mn and Ga, while the next layer below is
Ni separated by a distance d (Fig. 3(a)) would give the ratio of Ni 3p to Mn 3p intensity INi:Mn to be:

INi:Mn = I0 exp(-d/sin)

(1)

where, is the mean free path, is the electron emission angle. The variation of experimental INi:Mn
obtained here (Fig. 3(c)) is more pronounced than reported in Ref. 31 because of lower angular
acceptance of the electron energy analyzer used in the present work. The fitting has been performed
by varying I0 and was kept fixed at 19.8. An attempt to vary d to determine possible surface
relaxation effect led to large deviation of d from the experimental bulk value obtained from x-ray
diffraction[10], possibly because of the scatter in the data. So, d was kept fixed at the experimental
value corresponding to the bulk structure (1.46). Thus, using expected values of d or , a
reasonably good fit is obtained showing that this simple model explains the Ni and Mn intensity
variation with emission angle showing that the surface is Mn-Ga terminated.
Low energy electron diffraction study of stoichiometric Ni2MnGa (100) at room temperature.
Having established that it is possible to obtain the stoichiometric surface of Ni2MnGa by sputtering
and annealing, we show that the surface exhibits atomic order corresponding to the austenite phase
at room temperature. At room temperature, the bulk crystal is in austenite phase. This is shown by
the bulk transition temperatures determined by differential scanning calorimetry (Fig. 3(d)), where
the martensitic start temperature (Ms) is 206.5 K and the austenitic start temperature As is 215.7 K.
The bulk structure of the austenite phase is L21 (Fig. 3(a)), which can be described as four inter
penetrating f.c.c. sublattices, where Ga, Ni, Mn and Ni atoms occupy each sublattice at (0, 0, 0),
(0.25, 0.25, 0.25), (0.5, 0.5, 0.5) and (0.75, 0.75 ,0.75), respectively [12]. The L21 structure is
generally described by a cubic unit cell of Fm3 m space group. So, the bulk truncated (100)
surface is expected to have p4mm space group. Although we observe sharp LEED spots with four
fold symmetry (Fig. 4(a-c)) in the austenite phase, a close inspection of the pattern shows that some
spots like (1 0) , (1 0), (0 1) and (01) are absent. The expected positions of these spots are
indicated by white cross marks in Fig. 4(a). In literature[35], the absence of these spots has been
related to the existence of glide lines resulting in p4gm surface symmetry. Thus, the Ni2MnGa (100)
surface reconstructs to lower symmetry p4gm space group. Such reconstruction has been observed
in Pd/Cu surface alloy [36], on Ni(100) by deposition of carbon [37,38] and recently in Ca2xSrxRuO4 (001) [39]. In Fig. 4(a), the primitive surface unit cell of Ni2MnGa(100) in the reciprocal
space is shown by a white dashed square. We find that with increasing electron beam energy from
85 to 110 eV, all the LEED spots move toward the (0,0) spot indicating absence of any faceting.

Fig. 4: Low energy electron diffraction (LEED) patterns of Ni2MnGa(100) in (a-c) the austenite
phase at room temperature. The electron beam energies (Ep) in eV are shown in the bottom right
corners. The [10] direction is shown by white arrow in (a).

V.A. Chernenko

221

In order to interpret the symmetry of experimentally observed LEED patterns, we have


generated a schematic of LEED pattern by using the LEEDpat program [40]. A square 2D lattice
was considered with different symmetry considerations as shown in Fig.5. For p4mm symmetry, (1
0), (1 0), (0 1) and (01) spots are shown in Fig.5(a) as filled blue circles. Fig.5(b) shows the

(a)

(b)

Fig.5. (a) Schematic LEED pattern for p4mm symmetry, the spots shown in blue are missing in the
lower symmetry p4gm space group (b) Schematic LEED pattern for p4gm symmetry.

LEED pattern for p4gm surface symmetry in which the (1 0), (1 0), (0 1) and (01) spots are
absent. The absence of these spots is interpreted as arising from structures containing glide planes
[35]. Generally, the reduction of symmetry from p4mm to p4gm is associated with rotation of
surface atoms. For example, deposition of carbon on Ni(100) results in rotation of the Ni atoms
surrounding the fourfold hollow adsorption sites of carbon resulting in p4gm reconstruction [37,38].
In Ca2-xSrxRuO4 (001), rotation of the RuO6 octahedra has been shown to be the reason for p4gm
symmetry [39]. In the present case, further studies are in progress to determine the surface atomic
positions of the p4gm reconstruction in Ni2MnGa(100).
Low energy electron diffraction at room temperature as a function of surface composition.
LEED patterns recorded at room temperature for different surface compositions from Ni-excess to
Mn-excess surfaces are shown in Fig. 6(a-h). After sputtering, if TA is not high enough (for example
for TA= 630K, only a uniform background is observed with no LEED spots (Fig.6(a)). This shows
that the surface, which is disordered by sputtering, expectedly, does not exhibit LEED. It is
surprising that by annealing to somewhat higher temperature (TA= 680K), four fold LEED spots
appear (Fig.6(b)), although the surface is clearly non-stoichiometric with Mn:Ni ratio of 0.3. In
Ni2MnGa, Mn:Ni is 0.5 for the stoichiometric composition, and for lower values the surface is Ni
excess and for Mn:Ni= 0.3, the corresponding formula unit is Ni2.3Mn0.7Ga. For this composition,
the bulk martensitic transition temperature is about 450 K, as determined by DSC and magnetic
measurements[41]. Thus, at room temperature the bulk should be in martensite phase. For Ni
excess compositions, the bulk structure exhibits tetragonal distortion in the martensite phase[10].
But, tetragonal distortion is not observed at the surface and as discussed below (Fig. 6(i)), austenite
LEED is observed. As TA is increased, the LEED spots grow in intensity. Annealing the surface at
740K (Fig.6(d)) exhibits the intermediate spots with weak intensity. The stiochiometric surface
(Mn:Ni= 0.48) is attained by annealing at 770K (Fig. 6(e)), which produces the best LEED pattern
with sharp spots and low background. Since the bulk martensitic transition temperature for this
stoichiometric Ni2MnGa crystal is 206 K, the specimen is in the austenite phase and this is evident
from the four fold LEED pattern.
A line profile along spots 1 and 2 is shown in Fig. 6(i). Clearly, the separation of the two
peaks in the profile that correspond to spots 1 and 2 remain unchanged. Similarly, the separation

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between the spots (3 and 4) in the vertical directions remain unchanged with composition. Thus
change in lattice constant and the tetragonal distortion or modulation are not observed at the
surface, indicating that the surface is austenitic with LEED pattern of four-fold symmetry. This
difference in behavior of the surface compared to the bulk for the Ni excess compositions (Fig. 6(bd)) may be related to larger disorder at the surface due to lower TA compared to that required to
reach stoichiometric composition (TA= 770K). Further annealing at TA= 830K and 950K (Fig.6(g,
h) respectively results in a Mn-excess surface, but the LEED remains unchanged. Thus, Fig.6
shows that the p4gm surface reconstruction in the austenite phase is independent of surface
composition.

Fig. 6: Low energy electron diffraction (LEED) patterns of Ni2MnGa (100) at room temperature
with Ep= 100 eV. The Mn:Ni ratio is shown in the bottom right corners. The surface composition in
terms of the formula unit for (ah) surfaces are Ni2.5Mn0.7Ga0.8, Ni2.35Mn0.7Ga, Ni2.2Mn0.8Ga,
Ni2.1Mn0.9Ga, Ni1.9Mn0.9Ga1.2, Ni1.85MnGa1.2, Ni1.8Mn1.1Ga1.2, Ni1.55Mn1.3Ga1.1.

V.A. Chernenko

223

Fig. 7: XPS valence band spectra of Ni2MnGa(100) in the austenite phase at room temperature
compared with the calculated valence band based on density functional theory in upper and middle
panel, respectively. The valence band of Ni metal is also shown for comparison in the bottom
panel.

XPS Valence band of stoichiometric Ni2MnGa(100) surface. The XPS valence band of
stoichiometric Ni-Mn-Ga(100) surface at room temperature in the austenite phase peaks at 1.5 eV
binding energy (Fig. 7). The valence band width (W) is determined by extrapolating the falling edge
of the valence band in the higher binding energy side[42] (Fig. 7). The width of the valence band is
relatively small (4.5 eV) and is similar to that of Ni metal (4.7 eV). Expectedly however, the shape
of the valence band is different from Ni metal (Fig. 7, bottom spectrum). A satellite feature is
observed in the valence band at 8 eV, and a similar satellite is observed in Ni metal valence band at
6.6 eV, as shown by ticks in Fig. 7. This satellite feature in the valence band and Ni 2p core-level
spectrum of Ni metal has been studied extensively in literature and has been ascribed to the narrow
3d band and correlation effect[43,44,45]. It is interesting that similar feature is observed for
Ni2MnGa, albeit at a higher binding energy. The origin of this satellite is discussed below in details
in the context of the Ni 2p core-level spectrum (Fig. 9).
In order to understand the spectral shape, we have calculated the valence band of Ni2MnGa
from the Ni 3d and Mn 3d partial density of states (PDOS). The density of states have been
calculated for the equilibrium L21 structure with lattice constant a= 5.82 by ab initio, relativistic,

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and spin-polarized full potential linearized augmented plane wave method with generalized gradient
approximation for the exchange correlation using the WIEN97 code. The details of the calculation
are given in Refs. [9,46]. In the valence band calculations, only the PDOS of Ni 3d and Mn 3d are
considered since the other PDOS contributions are much lower. Moreover, the photoemission crosssection of Mn and Ni 3d states are an order of magnitude higher than that of the other PDOS like Ni
4s, Mn 4s, and Ga 4s, p states. For example, the photoionization cross-sections of Ni 3d (Mn 3d) is
0.01 (0.0026) mega barn at 1253.6 eV photon energy, while that of Ni 4s, Mn 4s, and Ga 4s are
0.001, 0.00092, 0.0017, respectively[27]. The Ni and Mn 3d PDOS are multiplied by the respective
photoemission cross-section, added and multiplied by the Fermi function. This spectrum is then
broadened by the instrumental resolution and an energy dependent Lorentzian lifetime broadening
to obtain the calculated valence band[47]. The calculated valence band spectrum is in good
agreement with experiment, with the calculated peak of the valence band appearing at 1.5 eV (Fig.
7). Ni 3d states exhibit a single peak at 1.75 eV, while Mn 3d states show a double peak structure at
1.3 and 3.1 eV. Thus, the Ni2MnGa valence band is dominated by the hybridization between the Ni
3d and Mn 3d states. The main peak has maximum contribution from Ni 3d states, while the states
close to the Fermi level have a large contribution from the Mn 3d states. The influence of Mn 3d
states in the near Fermi edge region makes the Ni2MnGa valence band spectra sensitive to surface
composition, as shown below for the UPS valence band spectra.
UPS valence band spectra at room temperature as a function of surface composition. The UPS
valence band spectra show a dramatic change in shape as a function of surface composition i.e.
Mn:Ni ratio (Fig. 8). A broad rounded peak appears around 0.9 eV in the spectrum corresponding
to a Ni-rich surface with Mn:Ni= 0.27. For Mn:Ni= 0.3, this peak shifts to higher binding energy:
1.15 eV, and a shoulder is observed at a lower binding energy (0.6 eV). For Mn:Ni= 0.35, the main
peak shifts to 1.27 eV, and the shoulder seems to decrease in intensity. As the Mn:Ni ratio
approaches the stoichiometric value of 0.48-0.52, the main peak appears at 1.32 eV, and the
shoulder is observed as a small peak at 0.6 eV. If compared to the Ni excess spectrum (Mn:Ni=
0.27), the width of the main peak for the stoichiometric surface is substantially reduced. As the Mn
content increases at the surface above the stoichiometric value (Mn:Ni= 0.84), a sharp peak at 0.3
eV is observed. It was shown in the previous section that the states close to the Fermi level have
substantial Mn 3d contribution. So, for the Mn excess surface, this is manifested as an intense peak
at 0.3 eV. Density functional theory calculations performed by us for Mn2NiGa[48,49] indicate that
this peak is related to hybridized 3d states between Ni and the excess Mn that occupies the Ni site.
Recently, Opeil et al.[50] have published UPS measurements on single crystal Ni2MnGa. The
spectrum corresponding to the austenite phase has a sharp peak at 0.3 eV and is very similar to the
shape obtained here for the Mn excess surface. Moreover, such an intense peak close to the Fermi
level has not been reported earlier in photoemission studies on either polycrystalline or singlecrystal Ni2MnGa[31,51] or in any other related Heusler alloys like Ni2MnIn or Ni2MnSn[52]. Thus,
the conclusions of Ref.50 pertain to a Mn excess Ni2MnGa surface, rather than stoichiometric
Ni2MnGa.

V.A. Chernenko

225

Fig. 8: UPS valence band spectra for Ni2MnGa(100) recorded with He I (21.2 eV) radiation at room
temperature for different surface compositions given by the Mn:Ni ratio. The spectra are staggered
along the vertical axis for the clarity of presentation.

The spectrum for stoichiometric Ni2MnGa (Mn:Ni ratio= 0.48-0.52) surface exhibits the
main peak at 1.3 eV (Fig. 8). Firstly, this is slightly different from XPS valence band (1.5 eV)
because of the large relative difference of photoionization cross-sections of Ni 3d and Mn 3d
states at 21.2 eV and 1253.6 eV photon energies. For example, the photoionization cross-sections of
Ni 3d (Mn 3d) is 4.0 (5.3) and 0.01 (0.0026) mega barn at 21.2 eV (UPS) and 1253.6 eV (XPS),
respectively[27]. Thus, the Ni 3d to Mn 3d cross-section ratio is about 0.75 and 3.85 for UPS and
XPS, respectively. Thus for UPS, the relative contribution from Mn 3d states to the valence band is
higher, and since the Mn 3d states are closer to the Fermi level, the overall position of the valence
band peak shifts to lower binding energy.
Ni 2p XPS core-levels of stoichiometric Ni2MnGa(100) surface. Fig. 9 shows the Ni 2p corelevel spectra for clean ordered surfaces. The Ni 2p3/2 and 2p1/2 appear at 852.8 eV and 870 eV
binding energy, respectively, with a spin-orbit splitting of 17.2 eV (Fig. 9). The Ni 2p spectra show
features at 6.6 eV and 5.8 eV on the higher binding energy side of 2p3/2 and 2p1/2 peak, respectively

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Fig. 9: Ni 2p core-level spectra (open circles), the fitted spectra (thin solid line), and the satellite at
6.6 eV (shaded) obtained from least-squares fitting are shown. The 2p3/2 peak of Ni metal is aligned
to that of Ni2MnGa.

(ticks in Fig. 9). We have compared the Ni 2p core-level with that of Ni metal from [43]. For Ni
metal, satellite features are observed at about E= 5.8 eV and 4.3 eV (E is the BE separation
between the core-level and satellite) higher BE from 2p3/2 and 2p1/2 peaks, respectively. The authors
concluded that the satellite originated from the interaction of 3d states with s conduction electron
states through s-d hybridization and with 3d states of other atoms through d-d interaction. The initial
ground state of Ni metal is 3d94s, which can gives rise two possible final states due to creation of
the photo-hole. Upon creation of the core-hole, the 3d band is pulled down because of strong
Coulomb interaction between core-hole and 3d electrons. If the screening of the core-hole is better,
as the 3d hole is filled by the transfer of an electron from 4s conduction band, the final state with
3d10 configuration contribute in the main peak. On the other hand, if the screening is poor, i.e. the
3d hole remains since 4s conduction electron transfer does not occur, a satellite peak arises toward
higher binding energy side of the main peak corresponding to 3d9 configuration, which is the
excited state with one hole in the core-level and other in localized 3d states. The calculated XPS
spectra for Ni 2p assigns the 2p53d10 final state, which contribute in the main peak, while 2p53d9
state contributes to the satellite feature[53].
The separation between the core-level and satellite BE (E) for Ni 2p3/2 in Ni2MnGa is more
(6.6 eV) than that of Ni metal (5.8 eV). Similarly, E for Ni 2p1/2 is more (5.8 eV) in Ni2MnGa
than that of Ni metal (4.3 eV) [43,45]. The difference in E between Ni 2p3/2 and 2p1/2 satellites
can be understood on the basis of the difference in their multiplet splitting. For Ni metal the
multiplet splitting of 2p3/2 satellite is different from the satellite corresponding to the 2p1/2
component. The lower energy multiplets of 2p3/2 satellite are strongly decreased in intensity because
Udc is small and they do not form the bound states. Only high energy multiplets are visible for 2p3/2
satellite, whereas for 2p1/2 satellite, all of the multiplets form bound states. The multiplets are
intense and are wide spread. Thus, the position of the 2p1/2 satellite structure is a configuration
average giving rise to different satellite position as compared to the 2p3/2 satellite. This is also the

V.A. Chernenko

227

reason why the energy separation of the 2p1/2 satellite and main peak (4.3 eV for Ni) corresponds to
calculated Udc (4.6 eV). So, for Ni2MnGa, Udc can be taken to be equal to E for Ni 2p1/2 i.e., 5.8
eV. The relative intensity of the satellite is dependent on the 3d band width, Coulomb interaction
and the band filling. For Ni2MnGa, the 3d band width (W= 4.5 eV) is smaller than the Coulomb
interaction (Udc= 5.8 eV). This is also true for Ni metal. Thus, in both cases the satellite originates
due to the narrow 3d band width, which is related to correlation effect. Bosch et al. reported that if
the band width is much smaller, the number of holes (nh) in the 3d band can be calculated by the
following equation from [43]
I(2p53d9)/I(2p53d10)= n(h)/(1-n(h))

(2)

where I(2p53d9) is the area under the satellite peak and I(2p53d10) is the area under the main corelevel peak. The area has been calculated from the de-convoluted (excluding instrumental
broadening) fitted curve (Fig. 9) and I(2p53d9)/I(2p53d10) turns out to be about 0.18. So the number
of holes (0.15) in the 3d band of Ni2MnGa found to be less than Ni metal (0.6 holes).[45] The
decrease in number of holes in the 3d band of Ni2MnGa ensures better screening of the core-hole.
Due to the less number of holes in 3d band of Ni2MnGa, the intensity of the satellite is lower
compared to Ni metal. As mentioned earlier, this satellite feature is also observed in the XPS VB at
about 8 eV (tick in Fig. 7)[54].

Conclusions
We report surface study of Ni2MnGa(100) single crystal using low energy electron diffraction
(LEED) and photoelectron spectroscopy. Stoichiometric and atomically clean surface is prepared by
sputtering and annealing. This procedure is successful since Ni enrichment caused by sputtering at
room temperature is compensated by Mn segregation to the surface with annealing at high
temperatures. The properties of the surface are influenced by both intrinsic effect related to the free
surface as well as surface composition. An interesting intrinsic surface effect is that in the austenite
phase, a surface reconstruction to p4gm symmetry is observed. This surface reconstruction occurs
across a wide of surface composition. The XPS valence band for the stoichiometric surface of
Ni2MnGa is in agreement with our calculated spectra. The UPS valence band spectrum exhibit
dramatic change in line shape with surface composition. A satellite feature observed in both Ni 2p
core-level and valence band spectra is related to the narrow 3d valence band in Ni2MnGa.
Acknowledgment
Funding from Max-Planck Partner Group project is gratefully acknowledged. A. M. Awasthi and S.
Bhardwaj are thanked for support. DLS and TAL acknowledge the support of the US Department of
Energy. S.S., J. N. and S.W.D. thank C.S.I.R. for research fellowship.
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Keywords Index
A
Antiphase Boundary
Atomic Order

117
85

C
Constraints
Cracking
Crystal Structure
Curie Temperature

177
203
73
85

D
Domain Wall

117

E
Electron Holography
Entropy Change

117
49

F
Fatigue
Ferromagnetic Shape Memory
Ferromagnetic Shape Memory
Alloys (FSMA)
First-Principles Calculations
FSMA

203
85
49, 61, 215
1
177

H
Heusler Alloy

151, 165, 177

105
61
1

L
Layered Structure
Lorentz Microscopy
Low-Energy Electron Diffraction

139
117
215

49
73
139
151, 203
177
177
31
31
117
105
49, 85, 139,
151
215
49
139
139
31

N
Neutron Diffraction
Ni-Mn-Ga
Ni-Mn-Ga Ferromagnetic
Martensite
Ni-Mn-In
Ni-Mn-Sn

73
85, 129, 151,
177, 203
31
139
139

Phase Diagram
Phase Transition
Photoelectron Spectroscopy
Polycrystal
Powder Diffraction

165
165
215
129
105

R
Reverse Transformation

151

M
Magnetic Anisotropy
Magnetic Domain

Martensitic Transition
Metamagnetic Alloys
Metamagnetic Phase Transitions
Metamagnetic Shape Memory
Multiscale Twinning

31, 129, 139

I
Incommensurate Modulations
Incommensurate Structure
Intermetallic Heusler Alloys

Magnetic Field Induced Strain


(MFIS)
Magnetic Field Induced
Transformation
Magnetic Moment
Magnetic Property
Magnetic Shape Memory
Magnetic Shape Memory Alloy
(MSMA)
Magneto-Mechanical Properties
Magnetoelastic Model
Magnetostress
Martensite
Martensitic Structure
Martensitic Transformation (MT)

31
117

Single Crystal
Smart Materials
Stress-Induced Transformation
Superelastic Alloy

61, 177
1
61
151

232
Surface
Surface Treatment

Advances in Magnetic Shape Memory Materials


215
177

T
TEM
Texture
Thermal Treatments
Training

117
129
85
129

Authors Index
A
Aaltio, I.
Albertini, F.
Algarabel, P.
Arnold, Z.

203
105, 151
151
151

B
Barandiarn, J.M.
Barman, S.R.
Bhm, A.
Buchelnikov, V.D.

73
215
129
1

C
Cesari, E.
Chakrabarti, A.
Chernenko, V.A.
Chmielus, M.

49
215
1, 31
177

I
Ito, W.

139

K
Kainuma, R.
Kakeshita, T.
Kamarad, J.
Kanomata, T.
Kataoka, M.
Khovaylo, V.V.
Kimura, A.
Kustov, S.

117, 139, 165


61
151
139, 165
165
139
165
49

L
Lzpita, P.
Lograsso, T.A.
L'vov, V.A.

73
215
31

D
Dannenberg, A.
Dhaka, R.S.
D'Souza, S.W.

1
215
215

E
Endo, K.
Entel, P.

165
1

F
Fabbrici, S.
Feuchtwanger, J.
Fukuda, T.

105, 151
73
61

M
Maeda, H.
Maniraj, M.
Mllner, P.
Murakami, Y.

61
215
177
117

N
Nagasako, M.
Nayak, J.
Nishihara, H.

165
215
165

O
Obara, K.

165

G
Gaitzsch, U.
Ge, Y.L.
Gruner, M.E.
Gutirrez, J.

129
203
1
73

H
Hannula, S.P.
Herper, H.C.
Hrrich, C.

203
1
129

P
Paoluzi, A.
Prez-Landazbal, J.I.
Pernechele, C.
Porcari, G.
Ptschke, M.

105, 151
85
151
151
129

R
Rai, A.

215

234
Recarte, V.
Righi, L.
Roth, S.

Advances in Magnetic Shape Memory Materials


85
105, 151
129

S
Salas, D.
Snchez-Alarcos, V.
Schlagel, D.L.
Schultz, L.
Serrate, D.
Shindo, D.
Shishido, T.
Siewert, M.
Singh, S.
Sderberg, O.
Solzi, M.

49
85
215
129
151
117
165
1
215
203
151

T
Terai, T.
Tonomura, A.

61
117

U
Umetsu, R.Y.

139, 165

Z
Ziebeck, K.R.A.

165