# QUANTITATIVE MODEL OF LARGE MAGNETOSTRAIN EFFECT IN FERROMAGNETIC SHAPE MEMORY ALLOYS

## I Introduction

In addition to some giant magnetostriction materials, ferromagnetic shape memory alloys was recently suggested as a general way for the development of a new class of the magnetic-field-controlled actuator materials . It is now a goal of research projects in several groups directed on the development of ferromagnetic alloys exhibiting also a martensitic phase transition that would allow control of large strain effect by application of a magnetic field at constant temperature in a martensitic state. Numerous candidate shape memopy materials were explored including Ni<sub>2</sub>MnGa, Co<sub>2</sub>MnGa, FePt CoNi, and FeNiCoTi during past few years . Magnetically driven strain effect is expected to occur in these systems. According to results reported in  the large strains of 0.19% can be achieved in a magnetic field of order 8 kOe in the tetragonal martensitic phase at 265 K of single-crystal samples of Ni<sub>2</sub>MnGa. This strain is an order of magnitude grater than the magnetostriction effect of the parent, room temperature cubic phase.

Ni<sub>2</sub>MnGa is an ordered by L21 ferromagnetic Heusler alloy having at high temperature cubic (a = 5.822 A) crystal structure that undergoes martensitic transformation at 276 K into a tetragonally distorted structure with crystalline lattice parameters: a=b=5.90 A and c=5.44 A . The martensitic phase accommodates the lattice distortion connected with transformation by formation of three twin variants twinned usually on $`110`$ planes and having the orientation of the tetragonal symmetry axes nearly to three possible $`\left[100\right]`$ directions. The saturation value of magnetization was found to be about of 475 G. Magnetization curve of the low-temperature twinned phase usually displays two-stage structure at 265 K  with a sharp crossover at about of 1.7 kOe from easy low-field magnetization below to a hard stage above this value up to the 8 kOe saturation field value. Such a behavior is connected with a different response of different twin variants to the applied field. The measurements usually show a definite magnetostrain value along $`\left[100\right]`$ as a function of the magnetic field applied in the same direction . It is generally expected that a large macroscopic mechanical strain induced by the magnetic field in similar type systems is microscopically realized trough the twin boundaries motion and redistribution of different twin variants fractions in a magnetic field. The main thermodynamic driving forces have in this case magnetic nature and connected with high magnetization anisotropy and differences in magnetization free energies for different twin variants of martensite .

The main goal of this brief publication is to give the right thermodynamic consideration of the mechanical and magnetic properties of a similar type materials and represent the quantitative model describing large magnetostrain effect observed in several ferroelastic shape memory alloys such as Ni<sub>2</sub>MnGa. It is shown that the magnetic field induced deformation effect directly follows from the general thermodynamic rules such as Poisson equation and connected with the strain dependence of magnetization. A simple model of magnetization for the internally twinned martensitic state and its dependence on the strain is considered and applied to explain the results of experimental study of large magnetostrictive effects in Ni<sub>2</sub>MnGa.

## II General Thermodynamic Consideration

Consider the general thermodynamic properties of the materials which can show both the ferroelastic and the ferromagnetic properties. Most of the shape memory alloys usually display ferroelastic behavior in martensitic state connected with redistribution of different twin variant fractions of martensite under the external stress applied through the motion of twin boundaries. Ferromagnetic shape memory materials have an additional possibility to activate the deformation process in a twinned martensitic state by the application of magnetic field simultaneously with magnetization of the material. According to general thermodynamic principles both the mechanical and the magnetic properties of similar type materials can be represented by the corresponding state equations:

$$\sigma =\sigma (\epsilon ,h)$$
(1)   
$$m=m(\epsilon ,h)$$
(2)   
where, the Eq.(1) reflects the mechanical properties through stress-strain $`\sigma \epsilon `$ equation in presence of magnetic field $`h`$ and Eq.(2) gives the magnetization value $`m`$ as a function of magnetic field applied $`h`$ and strain $`\epsilon `$. Both these equation can be obtained from an appropriate thermodynamic potential as follows:

$$\sigma (\epsilon ,h)=\frac{}{\epsilon }\stackrel{~}{G}(\epsilon ,h)m(\epsilon ,h)=\frac{}{h}\stackrel{~}{G}(\epsilon ,h)$$
(3)   
where, $`\stackrel{~}{G}(\epsilon ,h)=G(\epsilon ,h)hm(\epsilon ,h),`$ and $`G(\epsilon ,h)`$ is the specific Gibbs free energy at fixed temperature and pressure condition. Both state equation are not completely independent functions and must satisfy known Poisson’s rule:

$$\frac{}{h}\sigma (\epsilon ,h)=\frac{}{\epsilon }m(\epsilon ,h)$$
(4)   
Integration of this equation over the magnetic field starting from $`h=0`$ at a fixed strain gives an important representation of the mechanical state equation including magnetic field effects:

$$\sigma =\sigma _0\left(\epsilon \right)\frac{}{\epsilon }\underset{0}{\overset{h}{}}𝑑hm(\epsilon ,h)$$
(5)   
According to this equation the external stress on the left is balanced in equilibrium by both the pure mechanical stress $`\sigma _0\left(\epsilon \right)=\sigma (\epsilon ,0)`$ resulting from the mechanical deformation of the material at $`h=0`$ and the additional magnetic field induced stress that is represented by the second term on the right in this equation. It is also important to note that all the effect of the magnetic field on the mechanical properties is directly determined by the strain dependence of magnetization. In a particularly important case: $`\sigma =const=0`$ one can obtain a general equation determining magnetically induced strain (usually called as a magnetic shape memory or MSM-effect) as follows:

$$\sigma _0\left(\epsilon \right)=\frac{}{\epsilon }\underset{0}{\overset{h}{}}𝑑hm(\epsilon ,h)$$
(6)   
and its linearized solution:

$$\epsilon ^{msm}\left(h\right)=\left(\frac{d\sigma _0}{d\epsilon }\right)_{\epsilon =0}^1\left(\frac{}{\epsilon }\underset{0}{\overset{h}{}}𝑑hm(\epsilon ,h)\right)_{\epsilon =0}$$
(7)   
that can be used when $`\epsilon `$ is much less than a martensite lattice tetragonal distortion value $`\epsilon _0`$. According to Eqns.(6) and (7) the magnetization and its dependence on the strain is responsible for the MSM-effect and is the main subject for detailed discussion and modeling.

## III The model and its application to Ni<sub>2</sub>MnGa tetragonal martensite

Consider a typical situation corresponding to measurements of large strain induced by the magnetic field in the tetragonal internally twinned martensite of Ni<sub>2</sub>MnGa obtained from the austenitic single crystal studied in  when the magnetic field is applied along $`\left[100\right]`$ direction of parent austenitic phase and strain measurements were performed in the same axial direction. In this case the crystallographic $`\left[100\right]`$ $`\left[010\right]`$ $`\left[001\right]`$ axes for all three possible twin variants of the tetragonal martensitic phase will be nearly parallel to the external field applied. More exactly, the crystallographic orientation relationships between the austenitic and martensitic phases can be obtained by using the usual methods of the crystallographic theory. Additional small rotations of the tetragonal phase axes are expected but the corresponding rotation angles can not exceed few degrees in the case of Ni<sub>2</sub>MnGa and may be neglected for simplicity. Fig.1. schematically shows the expected alignment of the magnetic field applied, crystallographic orientations and magnetization curves for three possible tetragonal phase variants.

Therefore, the magnetic field is applied along the tetragonal symmetry axis only for one type twin variant (which is called here the axial, or $`a`$-type) and simultaneously in the transversal direction in respect to the tetragonal symmetry axes of another two (transversal, or $`t`$-type) variants. The investigation of magnetization properties of Ni<sub>2</sub>MnGa performed for a single tetragonal variant of martensite obtained by the mechanical compression method  has shown a considerable difference between the magnetization curves along the tetragonal $`\left[100\right]`$ direction in comparison to another transversal $`\left[010\right]`$ and $`\left[001\right]`$ directions. It was found that a tetragonal axis is the easiest magnetization direction and requires considerably less value of saturation field $`h_a`$ than a saturation field $`h_t`$ characterizing magnetization in two hard transversal directions as it is schematically shown in Fig.1. In a general case the calculation of magnetization for the material with a complicated twin microstructure geometry requires some special approach. In this paper we will ignore, for simplicity, a similar type problem and will consider these effects in other publications. Taking into account the presence of magnetic anisotropy and difference in magnetization behavior between the axial $`m_a(h)`$ and transversal $`m_t(h)`$ twin variants we consider a simple model of magnetization for the multi-variant martensitic state that gives the main contribution into magnetisation insensitive to the fine details of twin microstructure. This model treats the multi-twin martensitic state as a composite material consisting of an easy magnetization area occupied by axial type twins and hard magnetization region of two transversal twin variants. Denoting as $`x`$ the total volume fraction of the axial twin domain and $`(1x)`$ \- transversal type twin domain fractions, respectively, one can write the magnetization of the material as follows:

$$m(x,h)=xm_a(h)+(1x)m_t(h)$$
(8)   
where, $`m_a(h)`$ and $`m_t(h)`$ are specific magnetization functions for the axial and transversal variants, respectively. On the other hand, the macroscopic strain along the axial direction can be found from a similar type equation:

$$\epsilon =x\epsilon _a^0+(1x)\epsilon _t^0=\frac{3}{2}\epsilon _0(x\frac{1}{3})$$
(9)   
where, the diagonal matrix elements $`\epsilon _a^0=\epsilon _0`$ and $`\epsilon _t^0=\frac{1}{2}\epsilon _0`$ represent the relative tetragonal distortion of the martensite crystal lattice along its tetragonal axis and two transversal directions, respectively. The compression distortion $`\epsilon _0=5.4\%`$ along the tetragonal symmetry axis was found in case of Ni<sub>2</sub>MnGa. One can easily exclude the fraction dependence from these two equations and obtain the magnetization as function of the macroscopic strain for the internally twinned martensitic state:

$$m(\epsilon ,h)=\left\{\frac{1}{3}m_a(h)+\frac{2}{3}m_t(h)\right\}+\frac{2}{3}\left(\epsilon /\epsilon _0\right)\left\{m_a(h)m_t(h)\right\}$$
(10)   
This equation immediately reproduces all the main peculiarities of the experimental magnetization curve including the sharp change of its slope at $`h=1.75kOe`$ as indicated in Fig.2. This singularity exactly appears at $`h=h_a`$ where the easy stage of magnetization process inside of the axial twin variants domain is finished. According to Eq.(10) $`m(\epsilon _0,h)=m_a\left(h\right)`$ and $`m(\epsilon _0/2,h)=m_t\left(h\right)`$ so, one can use this fact to obtain both the $`h_a=1.75kOe`$ and $`h=8kOe`$ from the experimental magnetization curves measured in the multi-variant state. The model magnetization curve $`m(0,h)`$ corresponding to zero strain value shows the same type behavior and singularity in slope as the experimental one. The difference between them is caused by the second term in Eq.(10) that gives an additional strain dependent contribution into the magnetisation. This contribution is directly connected with the MSM-effect and can be easily taken into account just after its calculation.

One can also obtain the final equations representing the effect of magnetic field on the strain by using basic expressions (7) derived before from the general thermodynamic consideration:

$$\epsilon ^{msm}\left(h\right)=\frac{2}{3}\left(\epsilon _0\frac{d\sigma _0}{d\epsilon }\right)_{\epsilon =0}^1\underset{0}{\overset{h}{}}𝑑h\left\{m_a(h)m_t(h)\right\}$$
(11)   
## IV Discussion and conclusions

As follows from this equation, two factors determine the strain value and its field dependence. The first one is proportional to the slope of stress-strain curve and can be found from the usual mechanical compression test without magnetic field applied. The integral term reflects the effects of magnetic anisotropy and determines the functional magnetic field dependence of the strain. In particular, in absence of the magnetization anisotropy when $`m_a(h)=m_t(h)`$ deformation effect is also vanishes. The saturation level of the strain is achieved at $`h=h_t`$ and above where $`m_a(h)=m_t(h)=m^{sat}`$ and where the material has its maximal magnetization value $`m^{sat}`$. One can easily obtain the corresponding saturation value of the strain performing the necessary integrations in Eq.(11) as follows:

$$\epsilon _{sat}^{msm}=\frac{1}{3}\left(\epsilon _0\frac{d\sigma _0}{d\epsilon }\right)_{\epsilon =0}^1\left(h_th_a\right)m^{sat}$$
(12)   
Precise quantitative estimation of the saturation strain requires, in general, the corresponding mechanical testing. Here, we will use a simple estimation of $`d\sigma _0/d\epsilon \sigma _0/\epsilon _0`$. So, $`\epsilon _{sat}^{msm}\frac{1}{3}\left(\sigma _0\right)^1\left(h_th_a\right)m^{sat}`$ where the characteristic stress $`\sigma _0`$ representing ferroelastic mechanical behavior of the material is expected to be about of 20MPa in Ni<sub>2</sub>MnGa martensite. Using also the values of $`h_t8kOe`$ , $`h_a1.75kOe`$ and $`m^{sat}475G`$ found from the magnetization curve analysis one can obtain a simple estimation: $`\epsilon _{sat}^{msm}0.49\%.`$ More precise estimation that follows from the mechanical testing results gives $`d\sigma _0/d\epsilon \left(2÷3\right)\sigma _0/\epsilon _0.`$ Consequently, $`\epsilon _{sat}^{msm}(0.24÷0.16)\%`$ which is in a better quantitative agreement with $`\epsilon _{sat}^{msm}0.14\%`$ experimental value. In order to achieve the larger magnetostrain effect comparable with the lattice tetragonal distortion value $`\epsilon _05\%`$ one will need materials with very low $`\sigma _02MPa`$ detwinning stress value. This task seems can be considered as the realistic one because the observation of $`\sigma _02MPa`$  and $`\sigma _08MPa`$  were reported in some publications.

Fig.3. shows the field behavior of the strain that follows from the model and its change for the different values of the magnetic anisotropy factor $`k=h_a/h_t`$ defined as a ratio between the axial and transversal saturation fields.

The dimensionless strain response $`\epsilon ^{msm}\left(h\right)/\epsilon _{\mathrm{max}}`$ normalized by,

$$\epsilon _{\mathrm{max}}=\frac{1}{3}\left(\epsilon _0\frac{d\sigma _0}{d\epsilon }\right)_{\epsilon =0}^1h_tm^{sat}$$
(13)   
increases from zero value at $`k=1`$ simultaneously with a corresponding shape change and shows the maximal possible deformation effect and linear type singularity for the low field strain behavior at $`k=0`$. This case corresponds to the maximally strong anisotropy when the axial saturation field becomes infinitely small $`h_a0`$ and $`m_a(h)`$ immediately achieves its saturation level $`m^{sat}`$ starting from an arbitrary low magnetic field and then still remains equal to a constant $`m^{sat}`$ value during the magnetization process. Therefore, one can conclude that a linear low field behavior usually predicted in some previously developed models  is directly connected with their assumption on the complete saturation of magnetization for the axial type twin variants. According to the present model such a type of assumption can be physically reasonable in the limit $`h_a0`$ only. In other case the strain shows the normal parabolic type behavior in the low field $`h<h_a`$ region in agreement with the experimental observations. A good correspondence between the model and experimental results is indicated in Fig.4. We neglected here the small hysteresis effects which are usually observed assuming to give the more detailed discussion of this problem by using some new developments and quantitative descriptions of hysteresis in shape memory materials.

Acknowledgments

Authors acknowledge the Physical and Mat. Science Departments of the Helsinki Technological University supported this work.