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3rd International Symposium on Shape Memory Materials for Smart Systems

Deformation Studies of Ni55Fe19Ga26 Ferromagnetic Shape Memory Alloy

Aniruddha Biswas* and Madangopal Krishnan Materials Science Division, Bhabha Atomic Research Centre, Mumbai-400085, India

Abstract

Ni-Fe-Ga-based alloys form a new class of Ferromagnetic Shape Memory Alloys. The problem of brittleness of the Ni-Mn-Ga-based alloys can largely be overcome in case of Ni–Fe–Ga-based ones by introducing a disordered fcc �-phase. The current study explores thermo-mechanical processing of this alloy using an off-stoichiometric Ni55Fe19Ga26 alloy containing the ductile �-phase. Hot-rolling of Ni55Fe19Ga26 alloy was carried out at 9500C and 10000C, both with and without mild steel jacket. The microstructure of the hot-rolled products was analyzed in detail. Microtexture analyses were carried out both for the L21 and the �-phase independently using Electron Back-Scattered Diffraction technique. PACS: 75.50.Cc; 62.20.fg; 81.40.Ef

Keywords:Ferromagnetic shape memory alloy; NiFeGa; Martensite; Hot-rolling; EBSD

1. Introduction

Heusler Ni-Mn-Ga-based Ferromagnetic Shape Memory Alloys (FSMAs) are known to exhibit large magnetic-field-induced-strain (MFIS) reaching up to 10% [1] and thus, have genuine potential for application in sensors and actuators. This is especially the case for high frequency actuator applications. But, poor ductility is one of the major challenges limiting the technological development of Ni2MnGa alloys. Similar problem is also encountered in structurally analogous Ni-Al-based system, where considerable formability could reportedly be achieved by introducing a disordered fcc �-phase to the B2-matrix [2-3]. Oikawa et. al. [4] first identified the possibility of utilizing similar method in case of ferromagnetic Huesler alloys and introduced this new class of Ni–Fe–Ga-based two-phase ductile FSMAs. This alloy system has since attracted attention of a large number of researchers [5-7]. There have also been studies on a few other similar two-phase FSMAs such as CoNiAl [8] and NiMnGaFe [9]. Ternary Ni–Fe–Ga alloys with compositions close to the Ni2FeGa stoichiometry show thermoelastic martensitic transformation (MT) with characteristics quite similar to Ni2MnGa alloys [10]. The parent austenite phase is ordered cubic L21 that changes to B2 above the L21-B2 order transition temperature. Three different types of martensite

* Corresponding author. Tel.: +91-22-2559 3815; fax: +91-22-2550 5151 E-mail address: abiswas@barc.gov.in

c⃝ 2010 Published by Elsevier Ltd

Physics Procedia 10 (2010) 105–110

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1875-3892 c⃝ 2010 Published by Elsevier Ltddoi:10.1016/j.phpro.2010.11.083

Open access under CC BY-NC-ND license.

Open access under CC BY-NC-ND license.

Aniruddha Biswas/ Physics Procedia 00 (2010) 000–000

crystal structures, both modulated and non-modulated (NM) are known to occur in this system, depending upon the magnetic transition temperature. Two different types of modulated martensites namely, 14M and 10M are observed when the magnetic transition precedes the structural transformation. A third tetragonal non-modulated (NM) martensite L10 phase is observed when the Curie temperature (TC) is lower than the MT temperature. In fact, the phase and microstructure in this system are decided to a great extent by the chemical composition since it has strong influence on both TC and MT temperatures. In addition, aging treatment also plays key role in changing both MT temperatures and the microstructure of NiFeGa alloys. In particular, the volume fraction of the ductile �-phase, hence its mechanical behaviour can be tailored by tuning both the composition and aging treatments [7,10]. It is, thus important to select an appropriate Ni–Fe–Ga alloy composition in order to obtain the martensite transformation temperature close to room temperature [4,10], which is a crucial condition for most possible applications. In case of the current study, Ni55Fe19Ga26 is chosen as the alloy composition so that both TC and martensite start (Ms) temperatures are above room temperature. The main objective of this work is to study the thermo-mechanical processing and deformation behavior of Ni-Fe-Ga alloy. Even though these two-phase Ni-Fe-Ga-based alloys are known for their improved ductility, there has not been any systematic study on their formability and the resultant deformation microstructure and texture. This is particularly important since, the disordered �-phase can make the alloys amenable to thermo-mechanical processing and thus open up the possibility of achieving a favourable texture in polycrystalline materials. This article will present the evolution of the two-phase microstructure of Ni-Fe-Ga alloys upon hot deformation, explore the effect of aging treatments, role of the disordered �-phase and development of the deformation texture.

2. Experimental

Buttons of Ni55Fe19Ga26 were made by vacuum arc melting Ni (99.99%), Fe (99.99%), Ga (99.99%) in appropriate proportion. The buttons were solutionized at 1353 K for 24 h in sealed quartz ampoule. The solutionized buttons were further aged for 5 h each at below the B2-L21 transition temperature (i.e., 873 K) and above the same (i.e., 1023 K). Hot-rolling experiment of Ni55Fe19Ga26 alloy was carried out at 1223 K and 1273 K, both with and without mild steel jacket. Typically, the vacuum arc-melted button of 60 gm weight is hot-rolled with a total reduction of thickness from 10 mm to 1 mm. An interlayer of thin niobium / tantalum foil is used to avoid any interaction with the mild steel jacket. Prior to hot-rolling, microhardness of the matrix and the second phase � were evaluated both in as-solutionized condition and after aging treatment. The phase analysis was carried out by X-ray diffractometer using Cu K� radiation. The MT temperatures and B2-L21 transition temperature were determined by Differential Scanning Calorimetre (DSC). Magnetization experiments were carried out using superconducting quantum interface device (SQUID) magnetometer, both at zero field cooled (ZFC), field cooled (FC) modes and at an applied field of 100 Oe. Tc was determined from the point of overlap between the magnetization vs. temperature plots at ZFC and FC modes. The microstructure at different stages was analyzed in detail using a series of techniques including Optical Microscope, Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM). Nital solution was used as the etchant for metallography. The chemical compositions of the specimens were determined by Electron Probe Micro-Analyzer (EPMA) and Energy Dispersive X-ray Spectrometer attached to SEM. Specimens for TEM were prepared by Electro Discharge Machining followed by dimpling and ion milling. Microtexture analysis of the deformed microstructure was carried out by Electron Back-Scattered Diffraction technique.

3. Results

3.1. Structural and Magnetic Transition Both the structural and the magnetic transition are found to occur above room temperature in the solutionized

sample of Ni55Fe19Ga26 alloy. These are depicted in the DSC plot (Fig.1a) and the magnetization plot (Fig.1b) respectively. The MT temperatures are Ms : 305 K and Mf : 296 K, whereas Tc is found to be 295.4 K. Tc, in this case, is lower than Ms, thus, the microstructure should ideally contain NM martensite. However, because of the fact that Tc overlaps with the martensitic transformation, the modulated martensite may be present as well.

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Fig. 3. XRD pattern shows the presence of NM, 14M, � and L21 phases.

Fig. 1a. DSC plot shows the forward and reverse martensitic transformation; 1b. Magnetization plot shows the ferromagnetic tran

0 20 40 60 80 100

sition.

Heat

flow

(a.u

.)

Temperature (°C)

Solutionized

0 20 40 60 80 100

Heat

flow

(a.u

.)

Temperature (°C)

Solutionized

(a)

200 240 280 3200.00

0.02

0.04

0.06

0.08

H = 100 Oe

ZFC

FC

� (=

M/H

, em

u/g

)

T(K)

(b)

3.2. Microstructure and Phase Analysis Microstructure in as-solutionized condition shows (Fig. 2a) martensitic matrix and �-phase precipitates. As

suggested before, TEM analyses (Fig.s 2b-2d) confirm the martensite to be tetragonal NM type. In addition, it contains some amount of the modulated martensite (14M) as well, as is depicted in the corresponding XRD pattern (Fig. 3).

Fig. 2a. SEM micrograph shows the martensitic matrix and

�-phase precipitates ; b-d. Internally twinned tetragonal NM martensite. b & c show the bright field and the dark field respectively; d. shows the corresponding SAD pattern of [01-2]NM zone. (b)

30 40 50 60 70 80 90

14M

(1121)

NM

(024)

�(022)

L21

(224)

NM

(220)

NM

(114)

14M

(20-1

4)

+

NM

(112)

14M

(1-1

-7)

14M

(117)

14M

(200) 14M

(0014)

NM

(211)

L21(2

22)

L21

(004)�(002)

L2 1

(022)

Inte

nsity (

a.u

.)

2�

�(111)

+

30 40 50 60 70 80 90

14M

(1121)

NM

(024)

�(022)

L21

(224)

NM

(220)

NM

(114)

14M

(20-1

4)

+

NM

(112)

14M

(1-1

-7)

14M

(117)

14M

(200) 14M

(0014)

NM

(211)

L21(2

22)

L21

(004)�(002)

L2 1

(022)

Inte

nsity (

a.u

.)

2�

�(111)

+

10 µm

Fig. 4. Microstructure after aging at 873 K for 5 h. The matrix is L21. L21 and �-grains are surrounded by �’-phase. �’-phase precipitates are visible within the L21 grain as well.

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3.3. Effect of aging

o suppress the martensitic transformation

.4. Hot-rolling: Process, Microstructure after Deformation and Aging

ffect of aging: �’-phase, as confirmed by EDS analysis (Table 1), is clearly seen to envelope the other two phases.

.5. EBSD Analysis: Aged Hot-rolled Product

)

DSC experiment has shown (Fig. 5) 923 K as the B2-L21 transition temperature and accordingly the aging experiments were performed above and below this temperature. Aging in general, leads to solute redistribution and suppresses the martensitic transformation and thus the microstructure shows L21 matrix along with �-phase precipitates. Additionally, grains of both the L21 and �-phase are surrounded by ordered �’-phase. �’-phase are also detected within the L21 grains. �’-phase is more prominent in 873 K aged specimens. Figure 4 shows a typical aged microstructure obtained after aging at 873 K for 5 h. Increasing aging temperature leads to the increase in Fe and Ga contents of L21 phase. Notably, aging at 1023 K is found tm han the 873 K aging. ore t

3

Buttons of Ni55Fe19Ga26 were successfully hot-rolled at 1223 K and 1273 K both with and without mild steel jacket. Mild steel jacket results in superior quality of rolled products and interlayer is found to be useful in avoiding interaction with the jacket. Fig.6 highlights the significant features of the hot-rolled microstructures and its aged counterparts. The hot deformation leads to the growth of L21 grains, whereas the �-phase precipitates get elongated along the rolling direction (Fig. 6a). Significant fragmentation of �-phase precipitates is observed in the hot-rolled microstructure (Fig. 6b). �’-phase is also detected in some areas of the deformed microstructure (Fig. 6c). Another important finding is the presence of twins in �-phase. Fig.s 6e and 6f display the e

3

The hot-rolled product was aged at 873 K to obtain L21 phase at RT and analyzed by EBSD technique for the

(at% Ni Fe Ga � 54.53 25.58 19.90 �’ 57.36 17.19 25.46

Fig. 6. a-d. Different features of the hot-rolled microstructure: elongation, fragmentation & twining in �-phase, and presence of �’-phase (marked by arrow); e & f. Microstructure after hot-rolling: envelope of �’-phase.

(b) (c)

(d) (f)

(a)

Tabl nalyse 1. EDS a is of � and �’-phases

(e)

600 800 1000

Heat

flo

w (

a.u

.)

Temperature K

923 K

B2-L21

Fig. 5. DSC plot shows the B2-L21 transition.

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transformed into disordered � phase at rolling temperature.

deformation microtexture. Since both the phases namely, L21 and � have the same space group, the phases could be delineated by using the composition difference between them. This was achieved by performing simultaneous EDS and EBSD analyses. Fig.7a displays the steps involved in constructing the phase map from the elemental chemical maps. Fig.7b shows the resultant phase map that contains 19% �-phase. Combined Inverse Pole Figure (IPF) map for L21 and �-phases is displayed in Fig.7c. Precipitates of �-phase were extracted from data for independent analysis and the corresponding IPF map is depicted in Fig.7d. It displays predominantly (111) texture and the presence of extensive twinning as was detected earlier by optical microscopy. The following ODF sections were analyzed for the presence of typical fibres observed in fcc system: phi2 00, 450 and 650. The analysis reveals weak Goss component (�)�{110}<001>�and strong {112}<110> A component (�)�in this alloy. These components are marked on the corresponding ODF sections displayed in Fig.7e. EBSD analysis also showed that the substructure of the � phase contains <111> twins. On the other hand, it was not possible to clearly establish the texture of the L21 phase as the grains were large and did not yield statistically meaningful data. However, it could be seen from the inverse pole figures that microstructure predominantly consists of grains with ND and RD close to {101} and {111} poles. More interestingly, the existence of the grain boundary phase �’ is evident in the EBSD orientation map. EBSD analysis showed that, like � phase, the grain boundary phase also contains <111> twins. From this it is inferred that the �’ phase might have

(b) (a)

(c)

Fig. 7. a. Elemental chemical maps are used to obtain the phase map; b Phase map shows L21 and �-phase; c. Combined IPF map; d. Isolated IPF map of �-phase shows predominantly (111) texture and extensive twinning; e. ODF sections showing weak Goss (�) and strong A(�) components.

(d) (e)

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4. Summary

The current study has chosen the alloy composition Ni55Fe19Ga26 that shows both the structural and magnetic transition above room temperature. In this case, NM martensite is the major phase, since Tc is lower than Ms. The overlap between Tc and the martensitic transformation explains the presence of a small amount of 14M martensite in this alloy. The effect of aging on this alloy, in general, agrees well with the literature. It is, however, noticed that 873 K aging does not suppress Ms as much as 1023 K aging, even though the ordering is known to reduce the driving force for martensitic transformation [11]. This could be explained in terms of solute redistribution. Increasing aging temperature resulted in increase in Fe and Ga contents of L21 and that led to the reduction in Ms. This effect of Fe and Ga contents on Ms has been reported earlier by Oikawa et al [10].

This alloy has shown excellent hot-rollability and the effect of deformation of both L21 matrix and �-phase precipitates is clearly manifested in the microstructure. Grains of L21 phase have grown on hot-rolling whereas �-phase precipitates have shown elongation, fragmentation and extensive twinning. However, not much flattening of �-phase precipitates is noticed. The proportion of the ductile �-phase in this alloy is found to be around 19%. Interestingly, even though the disordered �-phase is the one that imparts ductility to this alloy, micro hardness measurements at room-temperature show small difference between the martensite (234.6 ± 6.5) and the �-phase�(228 ± 10.2). On the other hand, L21 matrix (285.4 ± 4.4) in the aged sample is found to be considerably harder than the �-phase precipitates (248.5 ± 14.4). However, since the rolling temperature is higher than the B2-L21 transition temperature, the sample is effectively deformed in B2 phase. It is, thus inferred that the good rollability may be in part due to the good high temperature ductility of the B2 phase. In fact, a number of B2-ordered alloys show reasonable hot-deformability, NiTi being one such example. Also, the grain boundary �’-phase that transforms into disordered �-phase at the rolling temperature could be another reason for the excellent hot rollability of this material. Earlier, Ishida et. al. [2] reported similar role of grain boundary �-phase in Ni-Al-Fe system. Hot-hardness experiments comparing the relative softening behaviour of L21 and �-phase may help resolve this aspect.

References

[1] K. Ullakko, J. K. Huang, C. Kanter, V. V. Kokorin and R. C. O’Handley, “Large magnetic�field�induced strains in Ni2MnGa single crystals”, Appl. Phys. Lett. 69 (1996) 1966

[2] K. Ishida, R. Kainuma, N. Ueno and T. Nishizawa, “Ductility Enhancement in NiAI (B2)-Base Alloys by Microstructural Control”, Metall. Trans. A 22A (1991) 441

[3] R. Kainuma, M. Ise, C.-C. Jia, H. Ohtani and K. Ishida, “Phase equilibria and microstructural control in the Ni-Co-Al system”, Intermetall. 4 (1996) S151

[4] K. Oikawa, T. Ota, T. Ohmori, Y. Tanaka, H. Morito, A. Fujita, R. Kainuma, K. Fukamichi and K. Ishida, “Magnetic and martensitic phase transitions in ferromagnetic Ni–Ga–Fe shape memory alloys”, Appl. Phys. Lett. 81 (2002) 5201

[5] Y. Li, C. Jiang, T. Liang, Y. Ma and H. Xu, “Martensitic transformation and magnetization of Ni–Fe–Ga ferromagnetic shape memory alloys”, Scripta Mater. 48 (2003) 1255–1258

[6] R. F. Hamilton, C. Efstathiou, H. Sehitoglu and Y. Chumlyakov, “Thermal and stress-induced martensitic transformations in NiFeGa single crystals under tension and compression”, Scripta Mater. 54 (2006) 465

[7] R. Santamarta, J. Font, J. Muntasell, F. Masdeu, J. Pons, E. Cesari and J. Dutkiewicz, “Effect of ageing on the martensitic transformation of Ni–Fe–Ga alloys”, Scripta Mater. 54 (2006) 1105

[8] Z. H. Liu, H. Y. Wang, S. Y. Yu, X. F. Dai, J. L. Chen, G. H. Wu and Y. Liu, “Phase equilibrium of ferromagnetic shape memory alloy Co39Ni33Al28”, Scripta Mater. 54 (2006) 1299

[9] K. Koho, O. Soderberg, N. Lanska, Y. Ge, X. Liu, L. Straka, J. Vimpari, O. Heczko and V. K. Lindroos, “Effect of the chemical composition to martensitic transformation in Ni–Mn–Ga–Fe alloys”, Mater. Sci. Eng. A 378 (2004) 384

[10] K. Oikawa, T. Omori, Y. Sutou, H. Morito, R. Kainuma and K. Ishida, “Phase Equilibria and Phase Transition of the Ni-Fe-Ga Ferromagnetic Shape Memory Alloy System”, Metall. & Mater. Trans. A, 38A, (2007) 767

[11] H.C. Ling and W.S. Owen, “A model of the thermoelastic growth of martensite”, Acta Metall. 29 (1981) 1721

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