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Journal of Magnetism and Magnetic Materials 320 (2008) 617621 www.elsevier.com/locate/jmmm

Magnetic after-effect in NiMnSb Heusler alloy


S. Chatterjeea, S. Giria, S. Majumdara,, S.K. Deb
a b

Department of Solid State Physics, Indian Association for the Cultivation of Science, 2A & B Raja S. C. Mullick Road, Kolkata 700 032, India Department of Materials Science, Indian Association for the Cultivation of Science, 2A & B Raja S. C. Mullick Road, Kolkata 700 032, India Received 25 January 2007; received in revised form 15 June 2007 Available online 2 August 2007

Abstract The ferromagnetic Heusler-type alloy Ni50 Mn35 Sb15 exhibits well dened shape memory behaviour. We have investigated the transport and magnetic properties of this alloy across the martensitic transformation. Pronounced thermo-magnetic irreversibility between zero-eld-cooled and eld-cooled susceptibility data was observed below the martensitic transition temperature. We observe signicant magnetic after-effect in magnetisation in both austenite and martensitic phases. However, a clear change in the nature of relaxation is observed as the sample is cooled across the martensitic transition temperature. These observations can be explained on the basis of complex domain dynamics in presence of rich micro-structure formation in the martensite. r 2007 Elsevier B.V. All rights reserved.
Keywords: Shape memory alloy; Magnetically ordered materials

1. Introduction The functional behaviour of shape memory alloy (SMA), based on the shape memory, super-elastic, and pseudoelastic effects, is related to a rst-order displacive and diffusionless transition called martensitic transformation (MT), which occurs between the high temperature austenitic and the low temperature martensitic phases [1]. In order to accommodate elastic strains, martensite is generally developed with micro-structures, known as twin variants. These are basically crystallographic domains that exists in the martensite. Presently, the ferromagnetic (FM) version of SMAs attracted a great deal of attention as smart materials. Ferromagnetic shape memory alloys (FSMAs) [2] exhibit both a reversible MT and ferromagnetism, and one can control the shape by applying magnetic eld in addition to conventional control by temperature (T) and stress. The rearrangements of the magnetically anisotropic twin variants under an applied eld are mainly responsible for the change in shape in FSMA.

The MT along with the formation of rich microstructure not only affects the mechanical properties of FSMA, it also inuences the FM behaviour of the system. The micro-structure strongly alters the magnetic domains in the martensite [3]. Investigation of the time evolution of isothermal magnetisation, popularly known as magnetic relaxation, can provide insight of the magnetisation process of a ferromagnet. Particularly, it is linked with the dynamics of the irreversible magnetisation. In their seminal work, Street and Woolley [4,5] propose that the magnetic relaxation in a ferromagnet arises due to the thermally activated domain orientation across the distribution of energy barriers. Here we have investigated the magnetic relaxation behaviour of the FSMA, Ni50 Mn35 Sb15 at different xed temperatures. This alloy has FM transition above room temperature and the MT is observed below 200 K. In our investigation, we observe an interesting change in the magnetic relaxation behaviour recorded in the FM state across the MT. 2. Experimental details The polycrystalline sample of Ni50 Mn35 Sb15 was prepared by arc melting the constituent elements in argon atmosphere. The ingot was homogenised at 900  C for 43 h,

Corresponding author. Tel.: +91 33 24734971; fax: +91 33 24732805.

E-mail address: sspsm2@iacs.res.in (S. Majumdar). 0304-8853/$ - see front matter r 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2007.07.023

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followed by a quenching in ice water. The sample was characterised by X-ray powder diffraction and no impurity phase was detected. The lattice parameter for the room temperature cubic L21 phase was found to be a 5:99 A. The composition of the NiMnSb alloy was checked by energy diffraction X-ray spectroscopy (EDS). Resistivity (r) of the sample was measured by standard four-probe method in the temperature range 77300 K. The magnetisation (M) was measured using a commercial Quantum Design MPMS XL (Ever Cool model). 3. Results The variation of r against T, shown in Fig. 1, is associated with a clear thermal irreversibility between 222 and 130 K. During heating from 77 K, a sharp change in the r value is observed around 160 K. On the other hand, during cooling from 300 K, a sharp rise in the r occurs around 208 K. The thermal hysteresis indicates a rst order phase transition, and comparing the previous work on this sample [6], we can identify this transition as the martensitic transition. Outside the thermal hysteresis region, this sample shows pure metallic behaviour, i.e., dr=dT40. Fig. 2 shows the T-dependence of dc magnetic susceptibility (w M=H) recorded in zero-eld-cooled (ZFC) and eld-cooled (FC) conditions. The ZFC and the FC states were achieved by cooling the sample down to 50 K in zero eld and at an applied magnetic eld (H) of 100 Oe, respectively, and the data were recorded for increasing T only. We do not observe any signature of paramagnetic to FM transition up to 300 K, as the Curie point of the sample is above room temperature. FC w shows a sudden increase around 200 K, which clearly indicates the MT. Outside the region around MT, FM w shows almost temperature independent behaviour, signifying FM nature of the

Fig. 2. Field-cooled and zero-eld-cooled dc susceptibility (w M=H) data of Ni50 Mn35 Sb15 at 100 Oe of applied eld. The inset shows the isothermal magnetisation versus eld data at 240 and 40 K.

Fig. 1. Resistivity as a function of temperature for both heating and cooling legs (indicated by arrows). The region of thermal hysteresis denotes the martensitic transition.

material. As evident from the low eld dc susceptibility data, the magnitude of M in the martensitic phase is less than that of austenitic phase. We observe about 35% decrease in FC w as the system transforms into martensite phase from the austenite phase. The ZFC and the FC susceptibilities show large deviation from each other below the martensitic transition temperature. This magnetic irreversibility signies some kind of hindrance for domains to get aligned in the direction of the applied magnetic eld. We have recorded M versus H isotherms both above (240 K) and below (40 K) the MT (see inset of Fig. 2). The sample was found to be very soft ferromagnet, with vanishingly small remnant magnetisation. The saturation magnetisation (M sat ) at 40 K was found to be larger than that of at 240 K, which is clearly due to the T-dependence of M sat . However, at low eld, we observe a crossover (indicated by an arrow) between the 240 and 40 K data. This is due to the fact that the slope of the MH isotherm below saturation is less at 40 K as compared to the 240 K curve, and it is in line with the stronger magneto-crystalline anisotropy observed in the martensitic phase [7]. To shed more light on the magnetic irreversibility and non-equilibrium behaviour, we performed careful investigation of magnetic relaxation of the material at different temperatures, above and below the MT. For relaxation measurements, the sample was cooled from room temperature to desired temperatures of measurement in zero eld. Subsequently, the observation of magnetic relaxation was made by measuring M as a function of time after applying a magnetic eld of 250 Oe (Fig. 3).

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Fig. 3. Time dependence of magnetisation of Ni50 Mn35 Sb15 at 250 Oe of applied eld at different temperatures. The solid lines represent the ttings with Eq. (2).

For FM, often a logarithmic relaxation behaviour is observed [8], Mt M 0 S ln t. (1)

Here, M 0 is the initial magnetisation. As seen from Fig. 3, the sample does not show a simple logarithmic behaviour in any temperature. Recently, Sirena et al. proposed a two term relaxation process in case of FM La0:6 Sr0:4 MnO3 sample [9]. This is characterised by a simple Debye like relaxation term ($ expt=t) , and a logarithmic term i.e., Mt M 0 S1 expt=t S2 lnt. (2)

We get a much better t of our relaxation data using Eq. (2), as shown by the solid lines in Fig. 3. A logarithmic term in the relaxation occurs due to the activation of domains with a at distribution of energy barriers. On the other hand, an exponential relaxation signies activation across barriers with identical height E B , which is related to the time constant, t / exp E B =kB T. The coefcients S 1 and S 2 denote the relative strengths of exponential and logarithmic terms. In our analysis, we nd an interesting correlation between these coefcients and the structural phase of the system. We have extracted the coefcients S 1 and S2 by tting Eq. (2) to our relaxation data recorded at different temperatures. At the highest temperature of relaxation data (240 K), where the system is purely austenite, we nd that the exponential term hugely dominates in the relaxation behaviour, with a negligibly small value of the coefcient of the logarithmic term. However as the system was cooled down below the transition temperature, the coefcient of the logarithmic term starts to rise. At the lowest temperature of measurements, where the sample is

Fig. 4. Variation of various parameters of Eq. (2) with temperature as obtained by tting our experimental data depicted in Fig. 3.

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in the martensitic phase, the logarithmic term becomes comparable with the exponential term. A purely logarithmic relaxation of M will result in a linear nature in the plot where time is in a logarithmic scale (as in Fig. 3). We nd that as the temperature is increased, the deviation from linear behaviour is more apparent in Fig. 3, suggesting a decreasing trend of the logarithmic term. Quantitatively, this behaviour is quite clearly visible in the S2 =S1 plot in Fig. 4. The signature of the MT is also apparent in the temperature dependence of the coefcients S1 , S2 and the relaxation time, t. We see a characteristic dip in the value of t near the MT. In addition, the magnitudes of S 1 and S 2 increase near the MT. 4. Discussion In this work we aimed to probe the evolution of magnetic behaviour across the martensitic transition in the alloy with nominal composition Ni50 Mn35 Sb15 . The compound shows FM behaviour throughout the temperature range of measurements (below 300 K). We observe a large divergence between ZFC and FC susceptibilities below the martensitic transition temperature ($175 K). This type of deviation often occurs even in a pure FM material due to pinning of magnetic ux at the defects sites, like grain boundaries. MT is associated with the formation of large number of twin variants. Imaging studies show that in low magnetic eld ($ few hundred Oe) each variant contains many small magnetic domains [3]. Even at high eld, the maximum size of a magnetic domain cannot exceed the size of a twin variant. As a consequence, the number of magnetic domains are large in the martensite. The martensite has high magneto-crystalline anisotropy due to lower crystal symmetry (orthorhombic in the present case [13]). These large number of domains in presence of strong magneto-crystalline anisotropy is responsible for the difference between FC and ZFC states just below the MT. In the FC state the domains are created favourably according to the external eld. While, the ZFC through MT produces randomly oriented domains which largely remains pinned by the twin variants. Since twin variants are created only in the martensite phase, a greater deviation between ZFC and FC w is observed only below the MT. Interestingly, although the system is in a pure FM state, the ZFC w increases with increasing T in the martensite. This is due to the fact that as T is increased in the ZFC measurement, thermal energy helps the pinned magnetic domains to orient favourably along the applied H and wT increases with increasing T. Now let us look at the magnetic relaxation behaviour of the sample. It is clear from our investigation that the nature of the time relaxation of M is different in the martensitic and austenitic phases. A simple exponential decay of M at high temperature gradually acquires logarithmic-type relaxation component in the martensite. The magnetic after-effect in ferromagnets is closely related to the domain dynamics of the system. It is therefore expected that the

evolution of M with time in the martensite is inuenced by the twin variant induced magnetic domain formation along with the magneto-crystalline anisotropy as discussed above. In absence of any magnetic eld, the magnetic domains are randomly oriented in a minimum energy conguration. This is a metastable conguration [8], and in an applied magnetic eld, the domains try to orient favourably to the direction of the eld. In that process, each magnetic domain evolves across an energy barrier through thermal activation and the magnetisation tend to attain the stable state value. For a simple system, one would expect an exponential time evolution of M. However, for a composite system, logarithmic relaxation is observed as an average law for large number of exponentially relaxing components. In case of some transition metals based Heusler type FSMAs, reasonably large magnetic domains ($110 mm) were observed in the high temperature austenitic phase [1012]. If this is also true for the present Ni50 Mn35 Sb15 compound, a single barrier exponential type relaxation is possible. Whereas, martensite with micro-structure is recognised with complex magnetic domains comprising large number of ner patterns (o0:1 mm) [3,11,12]. These large number of randomly oriented domains, which are pinned in presence of twin variant interface and magneto-crystalline anisotropy, constitute a distribution of energy barriers. Therefore a fraction of logarithmic-type relaxation is justiable in the martensitic phase. The anomaly observed in the tting parameters S 1 , S 2 , and t (see Eq. (2)) near the MT is quite interesting. Being a disordered inuenced rst order phase transition, MT occurs through nucleation and growth. As a result an intermediate phase is formed around the transition region where both austenite and martensite can coexist [14]. This intermediate region is the region of thermal hysteresis in the rT data. The domain dynamics of this intermediate phase will be supposedly different due to the presence of martensiteaustenite interface. This would possibly inuence the temperature evolution of the tting parameters near MT. 5. Summary and conclusion We observe interesting correlation between the magnetic relaxation and the martensitic phase transition in case of NiMnSb SMA. The signature of MT is present in the magnetic viscosity parameters used to t the relaxation data. A clear transformation from a logarithmic to an exponential dominated relaxation behaviour is observed as the sample is heated from martensite to austenite. We observe a strong thermo-magnetic irreversibility between ZFC and FC susceptibilities, which presumably originate from the pinning of the FM domains and magnetic anisotropy. We believe that the nature of the FM domains, inuenced by the martensitic micro-structures, has a greater role in the observed magnetic after-effect and the thermo-magnetic irreversibility. Further investigations

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based on microscopic imaging of magnetic domains as a function of temperature can shed more light on the interesting magnetic behaviour of this composition. Acknowledgement We thank Unit on Nanoscience and Technology of IACS for helping us in magnetic measurements. References
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