Scripta mater. 44 (2001) 23932397 www.elsevier.

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A NEW FERROMAGNETIC SHAPE MEMORY ALLOY SYSTEM

Manfred Wuttig, Jian Li and Corneliu Craciunescu
Department of Materials Science and Engineering, University of Maryland, College Park, MD, 20742-2115, USA (Received December 14, 2000) (Accepted January 10, 2001)
AbstractIt is shown that the alloys Co2Ni1xGa1x, x 0.06, 0.09, 0.12, 0.15, are ferromagnetic shape memory alloys. In the as-solidified state their martensite start temperatures vary in the range 20 CT60 C as the concentration parameter x decreases. The high and low temperature phases are body centered cubic and orthorhombic and/or monoclinic, respectively, The transformation hysteresis, i.e. the difference between the martensite and austenite start temperatures, equals approximately 30 degrees. The saturation magnetization of the alloys resembles that of nickel while their coercive force is of the order of 100mT. 2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Keywords: Phase transformation; Shape memory; Microstructure; Internal friction; Ferromagnetic hysteresis

Introduction The materials science and engineering of Ferromagnetic Shape Memory Alloys (FMSMAs) is a relatively young field. One of the initial topics was the change of the martensite start temperature as a function of the magnetic field in ferrous alloys [1], not necessarily FMSMAs. The recognition that a reversible domain reorientation in a magnetic field will cause a large magnetostrictive strain of the order of the FMSMA transformation eigenstrain lead to the recent explosion of the field. At this time three alloy systems are actively investigated, NiMnGa, FePd and FePt. The latter two are long known to be SMAs [2,3,4,5,6] and were re-investigated to study their magnetostriction [7,8]. The martensitic transformation in NiMnGa was discovered in 1984 [9]. Its SMA character was recognized later [10]. The attention to its magnetostrictive properties is more recent [11,12,13,14,15,16]. FMSMAs can potentially be used as thermo-mechanically controlled actuators. Two possible FMSMA actuation mechanisms exist. The first utilizes the shift of the transformation temperature by an external magnetic field. This mechanism operates only in the vicinity of the transformation temperature. The second mechanism utilizes the redistribution of the simultaneously elastic and magnetic domains by an external magnetic field [17]. It is operative at any temperature below the transformation temperatures. Its power is limited by the magnetic energy density of the alloy. Co-based FMSMAs are thus good candidates for FMSMA magnetostrictors. This paper reports on a new Co-based FMSMA family with compositions in the vicinity of the Heusler composition Co2NiGa.

1359-6462/01/$see front matter. 2001 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved. PII: S1359-6462(01)00939-3

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Figure 1. Conceptual position of several alloy systems in the Martensite, Ferromagnetic and Special Lattice Relationship groups. Alloys in the overlap group of all three are FMSMAs.

Search for a New FMSMA Diffusionless, i.e. martensitic, transformations occur at certain critical average electron concentrations. For instance, the martensitic transformations in Cu-based alloys systems occur at s 1.4 [18] while those in Fe-based alloys occur at sd 8.5 [19]. The martensitic transformation in NiMnGa Heusler alloys occurs at an average valence electron concentration of approximately 7.3 [20]. Their saturation magnetization falls on the known Bethe-Slater plot only if all outer electrons are counted, i.e. s p d 10 [21]. Not all martensites are SMAs and those that are fulfill certain special relationships between the lattice parameters of the austenite and martensite phases [22]. This is schematically indicated in Fig. 1. In its simplest form a search for new Co-based FMSMAs can thus start by identifying a potential Co-based Heusler alloy with an average valence electron concentration of approximately 7.3. Of those CoNiGa is similar to NiMnGa in that s p d 10. Thus Co2Ni1-xGa1x alloys may be ferromagnetic and display SMA characteristics. This is the case and this letter reports on them. Experimental Four alloys of nominal composition, Co2Ni1-xGa1x, x 0.06, 0.09, 0.12, 0.15, were prepared by arc melting. Their microstructures were determined using a polarized light microscope equipped with a heating stage and shape recovery experiments were run on the alloys Co2Ni0.85Ga1.15 and Co2Ni0.88Ga1.12. In addition, the internal friction and modulus defect, M/M [M(T1) M(T2)]/ M(T1), were determined in the temperature range 50C T 200C using an already described apparatus [23]. Room temperature magnetization curves were determined as well using a standard vibrating sample magnetometer, VSM. The as-solidified Co2Ni0.88Ga1.12 and Co2Ni0.85Ga1.15 polycrystals displayed full shape recovery upon heating after having been manually deformed at room temperature. During sample preparation it was noticed that the CoNiGa FMSMAs are not nearly as brittle as their NiMnGa counterparts. Other experimental results are displayed in Figs. 2 to 4. Figure 2 shows the room temperature martensitic microstructure of as-solidified polycrystalline Co2Ni0.85Ga1.15. Modulus defect and internal friction data of three as-solidified polycrystalline alloys are displayed in Fig. 3. Figure 4, finally, displays magnetic data. Preliminary XRD data indicate that monoclinic and/or orthorhombic martensite forms reversibly from a bcc high temperature phase.

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Figure 2. Room temperature microstructure of an as-solidified Co2Ni0.85Ga1.15 alloy.

Discussion The microstructure displayed in Fig. 2 is typical of a SMA martensite as the domain boundaries are straight indicating only elastic distortions in the product phase. The modulus defect and internal friction data displayed in Fig. 3 point toward a SMA-type martensitic transformation as well [24,25,26]. They suggest MS temperatures between slightly below room temperature and 60C with a hysteresis of about 30C. The M/M vs. T characteristic of the alloy Co2Ni0.85Ga1.15 further suggests a sequence of two martensitic transformations. The internal friction data in the martensitic phase resemble those of NiTi indicating a high mobility of the boundaries. It was noted that heating to 850C and subsequent quenching to room temperature lowered the MS temperature, particularly in the Ga rich alloys. The magnetization curve of Co2Ni0.88Ga1.12 is presented in Fig. 4. It can be seen that the saturation magnetization in the quenched state is comparable to that of nickel, as expected, and that the coercive force equals approximately 200 mT. Furthermore, the saturation magnetization depends on the state of the alloy. This agrees with previous observations on the ferromagnetic properties of Co2Ni1-xGa1x, 1 0.3 [27]. These indicated that the quenched alloys are ferromagnetic for x 0.5 and that the saturation magnetization depends on the composition as well as the state of anneal. They also showed that the alloys possess an ordered B2 structure.

Figure 3. Temperature dependence of modulus defect, M/M, and damping of three as-solidified CoNiGa alloys, Co2Ni0.9Ga1.09, EEE Co2Ni0.88Ga1.12, Co2Ni0.85Ga1.15. Open and closed symbols denote decreasing and increasing temperature variations.

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Figure 4. Magnetization curves of Co2Ni0.88Ga1.12 determined at room temperature, as-solidified, annealed 3 hrs at 850C and quenched.

In summary, all experimental evidence presented in this paper indicates that CoNiGa alloys form a new ferromagnetic shape memory alloy family. This statement is substantiated by the

visual observation of full shape recovery of the alloys upon heating, typical SMA microstructure displayed in Fig. 2, reversible change of the crystal structure upon heating and cooling, minimum of the elastic modulus occurring at the same temperature, MS, as the sharp rise of the internal friction and by the, nickel-like saturation magnetization of the alloys. Acknowledgments

This study was supported by the Office of Naval Research, contracts No. N000149910837 and N000140010849. References
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