Materials Letters 58 (2004) 636 640 www.elsevier.

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Effects of Mn doping on structural and magnetic properties in NdFeB nanocomposites

Guozhi Xie a,*, Shilong Yin b, Fengming Zhang c, Pinghua Lin a, Benxi Gu c, Mu Lu c, Youwei Du c, Zuanru Yuan d
a College of Civil Engineering, Hohai University, Nanjing 210024, China Department of Mathematics and Physics, Hohai University, Nanjing 210024, China c National Laboratory of Solid State Microstructures, Physics Department of Nanjing University, Nanjing 210093, China d Modern Analytical Center, Nanjing University, Nanjing 210093, China b

Received 26 March 2003; accepted 24 June 2003

Abstract The magnetic and structural properties of nanocomposite Nd9Fe85 xMnxB6 (x = 0,0.5,1) have been investigated. It was found that the addition of manganese in the Nd9Fe85B6 could promote crystallization and enhance the hard magnetic properties of the material. Thermomagnetic analysis (TMA) measurement indicated that the doping of Mn reduces the Tc of the Nd2Fe14B phase and raises that of a-Fe phase in the system. From the radial distribution curves around Fe atoms of Extended X-ray absorption fine structure (EXAFS), it has been demonstrated that for both the as-spun Nd9Fe85 xMnxB6 (x = 0,0.5,1) samples with lower x value and the annealed samples, the EXAFS curves appear to be similar to that of a-Fe. D 2003 Elsevier B.V. All rights reserved.
PACS: 75.50.Bb; 76.80; 61.10.Ht Keywords: Nanocomposite materials; Coercivity; Exchange coupling; X-ray absorption fine structure; Microstructure

1. Introduction Nanocomposite magnets consisting of magnetically hard and soft phases have attracted much attention for potential permanent magnet development [1 3]. In nanocomposite magnets, both the hard and soft magnetic phases are in the nanoscale range so that the magnetic moments of adjacent grains are exchange coupled [3]. Therefore, an enhanced remanence (Mr/Ms higher than 0.5, which is expected for randomly distributed uniaxial domains) and a reasonable coercivity (lower than that of the hard phase alone) can be obtained in nanocomposite magnets. As elemental addition has been experimented to obtain the desired well-coupled interface between soft and hard phases, it is thought as a useful method for the fabrication of a well-performing nanocomposite [3 6]. Doping with antiferromagnetic elements, such as Cr, etc., has also been studied [6 8]. It has been found that the presence of chromium in NdFeB not only influences the kinetics of phase formation but also reduces
* Corresponding author. Tel.: +86-25-3787972; fax: +86-25-3787972. E-mail address: guozhixie@yahoo.com.cn (G. Xie). 0167-577X/$ - see front matter D 2003 Elsevier B.V. All rights reserved. doi:10.1016/S0167-577X(03)00584-6

the magnetization and Curie temperatures of the constituent phases. As another antiferromagnetic doping element, manganese has been studied in cast ingots treated under certain temperature for several hours [9 11]. It has been reported that both the grain size and structures of nanocrystals of the materials have strong effects on their magnetic properties [12]. In the present work, we studied the dependence of structural and magnetic properties of melt-spun Nd9Fe85B6based nanocomposites on the Mn addition.

2. Experimental The ingots of Nd9Fe85 xMnxB6 (x = 0, 0.5, 1) were prepared using FeB alloy (B 24.99% wt%), Nd of 99.8% in purity, Fe of 99.5% in purity, and Mn of 99.8% in purity, respectively. The ingots were initially alloyed by arc melting three times to obtain homogeneous composition, and melt spun with a molybdenum wheel at a linear speed of 20 m/s in argon atmosphere. The as-spun ribbons were annealed at 700 jC for 5 min. The crystallization behaviors were monitored by differential thermal analysis (DTA) at a

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heating rate of 10 jC min 1. The phase identification was carried out by X-ray diffraction (XRD) using Cu Ka radiation. The hysteresis loops were measured in a vibrating sample magnetometer (VSM) with a maximum field of 20 kOe along the long axis so that the demagnetization factors can be ignored. The magnetic phases and the corresponding Curie temperatures (Tc) were determined by a thermal gravimetric analyzer (TGA) with a heating rate of 20 jC min 1 in conjunction with an externally applied magnetic field of 50 Oe, conventionally known as thermomagnetic analysis (TMA). The XAFS spectra of the Fe K-edges were measured at the U7C beam-line of National Synchrotron Radiation Laboratory (NSRL) and the 4W1B beam-line of Beijing Synchrotron Radiation Facility (BSRF). The monochromator is two flat Si (111) crystals with a fixed exit. Its energy differentiate rate is about 2eV. Data were collected in transmission mode at room temperature.
Fig. 2. Comparison of the hysteresis loops of Nd9Fe85 xMnxB6 (x = 0,0.5,1) sample quenched at 20 m/s and annealed at 700 jC for 5 min (a) Nd9Fe84MnB6, (b) Nd9Fe84.5Mn0.5B6 and (c) Nd9Fe85B6.

3. Results and discussion The XRD patterns for the as-spun and annealed Nd9 Fe85 xMnxB6 (x = 0,0.5,1) samples are shown in Fig. 1. The XRD patterns of the as-spun samples shown in Fig. 1(a) reflect obviously different characteristic for each sample. For the Mn-free as-spun sample, it can be seen that the XRD patterns are mainly composed of amorphous hump from 30j to 50j, overlapped with which some wide and weak diffraction peaks. On the other hand, for the Mn doping as-spun samples, the strength of amorphous hump decreases by about two-thirds as that of the Mn-free sample. The diffraction peaks for Nd2Fe14B and a-Fe phase appeared for all samples. The optimal crystal structure is observed in the Mn doping sample for x = 1. The intensity of diffraction peak at about 44.7j, which is for the crystal plane (110) of a-Fe phase in the Nd9Fe84MnB6 sample, is as twice as that in the Nd9Fe84.5 Mn0.5B6 sample. Furthermore, it can be found that there are 19 diffraction peaks for the Nd2Fe14B phase in the as-spun

Fig. 1. XRD spectra of Nd9Fe85 xMnxB6 (x = 0,0.5,1) sample quenched at 20 m/s (a) as-spun; (b) annealed at 700 jC for 5 min.

Nd9Fe84MnB6 sample. It is clear that the amount of crystal phase in the as-spun samples increases with increasing Mn content, which suggests that Mn addition improves crystallization tendency of the ribbons. Different results are obtained from the XRD patterns for the annealed Nd9Fe85 xMnxB6 (x = 0,0.5,1) samples, as shown in Fig. 1(b). It can be seen that the three XRD patterns of the annealed samples have almost the same shape. It is shown that nearly the same crystal structure for Nd2Fe14B and a-Fe phase in annealed samples was obtained. From Fig. 1(a) and (b), it can be deduced that the addition of Mn has a strong effect on the microstructure of the as-spun NdFeB nanocmposites. A certain amount of manganese added to Nd9Fe85B6 magnets could promote crystallization for Nd2Fe14B and a-Fe phase. After annealing, the effect of Mn addition almost disappeared. The hysteresis loops of as-spun and annealed (at 700 jC for 5 min) samples were measured, respectively, as shown in Fig. 2. It can be seen that for each as-spun sample, there are two separate phases and the very low iHc indicates the lack of exchange coupling between the soft and the hard magnetic phases in the sample. However, after the samples were annealed at 700 jC for 5 min, the corresponding hysteresis loop for each sample becomes a typical one for ferromagnetic materials. The smooth feature of the loop for each sample indicates that there is a uniform and a well-coupled microstructure inside the sample. The coercivity, saturation magnetization and (BH)max of samples a, b, and c are 5002.5 Oe, 133.9 emu/g, 10.6 MGOe; 4749.5 Oe, 138.1 emu/g, 11 MGOe and 4266.5 Oe, 133.5 emu/g, 10.5 MGOe, respectively. The coercivity is enhanced obviously by Mn addition. As coercivity is sensitive to the crystal structure of material, the addition of Mn must be useful to enhance the crystal structure in annealed samples.

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Shown in Fig. 3 is the dependence of yM [yM = md(H) (1 2mr(H))] on the applied magnetic field, H, with md, the reduced magnetization, and mr, the reduced remanence [13,14], for the annealed samples. From the figure, it can be seen that for each of the samples, the value of yM firstly increased to a peak, then decreased rapidly around the coercivity. It is believed that when the applied field exceeds the coercivity, the magnetostatic effect is larger than the effect of exchange coupling, which caused a drop for yM to a small negative value. Moreover, the higher positive yM values were obtained for samples with Mn addition. According to the Wohlfarths analysis [15], higher positive yM peaks indicate stronger exchange coupling interactions between the magnetically hard and soft phase. This is consistent with the increase of coercivity as has been illustrated in Fig. 2. As shown in Fig. 4, TMA scans were used to study the Curie temperatures of the annealed Nd 9 Fe 85 x Mn x B (x = 0,0.5,1) samples. From the two peaks in each curve of the figure, it can be thought that there is only two magnetic phases in each sample. The first peak at the lower temperature represents the transition of the Nd2Fe14B phase, and the second one at higher temperature represents the transition of the a-Fe phase. It can be seen that the Curie temperature (Tc) of the Nd2Fe14B phase decreased from 313 to 303 jC when x was increased from 0 to 1, while the Curie temperature of the a-Fe phase rose from 742 to 788 jC. It can be deduced that the doping of Mn may cause some sort of additional interactions in the Nd2F14B or a-Fe phase and the intrinsic properties of the magnetic system are changed. This decrease of Tc for Nd2Fe14B phase with the increase of Mn content agrees well with the results reported by Abache and Oesterreicher [10], Cheng et al. [11] and Sun and Murray [12]. Cheng et al. [11] assumed that the reduction of Tc in Nd2Fe14B phase is related to the increased antiferromagnetic interactions due to the doping of Mn. According to Chens explanation [16], when the temperature was higher than the Tc of the first phase, only one ferromagnetic phase (a-Fe or Fe (Co) phase) existed in the magnets, so the exchange-coupling effect disappeared completely and the Curie temperature did

Fig. 4. TMA scans of the annealed Nd9Fe85 xMnxB6 (x = 0,0.5,1) samples (a) Nd9Fe84MnB6, (b) Nd9Fe84.5Mn0.5B6 and (c) Nd9Fe85B6, also showing the existence of two magnetic phases, i.e. 2:14:1 and a-Fe, and the contrary change of Tc to them.

not change with the Co doping. However, in the annealed Nd9Fe85 xMnx B (x = 0,0.5,1) samples, the Tc of a-Fe increases with the increase of Mn doping concentration. It is noted that the Tc of the a-Fe phase in the annealed Mn-free sample is 742 jC, which is lower than that for pure a-Fe phase (770 jC). This difference is due to the nanocrystallite structure for a-Fe phase in the Mn-free sample. This result is consistent with the reports that nanocrystal material has lower Tc in comparison to the conventional material with large grain size [17,18]. It should be mentioned that the Tc of a pure a-Fe sample, the same a-Fe composition for the preparation of Nd9Fe85 xMnxB (x = 0,0.5,1) nanocomposites, measured at the same conditions on the same equipment. In the measurement, the heating rate is 20 jC min 1 for all samples. A Tc value of 786 jC was obtained for the a-Fe sample. The higher Tc of 786 jC rather than 770 jC is believed due to the delay of

Fig. 3. Variation of yM with the external magnetic fields for the Nd9 Fe85 xMnxB6 (x = 0,0.5,1) samples annealed at 700 jC for 5 min.

Fig. 5. Fe K-edge XAFS spectra in Fe powder and Nd9Fe85 xMnxB6 (x = 0,0.5,1) samples (a) as-spun; (b) annealed at 700 jC for 5 min.

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annealed Nd9Fe85 xMnxB6 samples were improved in comparison with those of the as-spun samples. However, the intensities of the peaks for the annealed samples were weaker than those of the corresponding peaks for the powder Fe. For the feature of the peak at around 0.35 nm, the Mn-doped samples were more similar to the power Fe sample than the Mn-free sample. It can be presumed that the doped Mn in the range investigated improved the crystal structure of the annealed Nd9Fe85 xMnxB6 samples by favoring the formation of the configuration of Fe existing in a-Fe phase. Therefore, the magnetic properties of NdFeB nanocomposite depend upon the fine structure change caused by the doping of Mn in the materials.

4. Conclusions
Fig. 6. Radial distribution curves of Fe atoms in Fe powder and Nd9 Fe85 xMnxB6 (x = 0,0.5,1) samples (a) as-spun; (b) annealed at 700 jC for 5 min.

actual temperature to the measured value. Thus, it is believed that the doping of Mn changes the environment with which the Nd2Fe14B and a-Fe phases interact. The XAFS spectra of Fe K-edge for the as-spun and annealed Nd9Fe85 xMnxB6 (x = 0,0.5,1) samples are shown in Fig. 5. It can be observed that the intensity of each oscillation peak is lower in both as-spun and annealed NdFeB samples as compared to that of the powder Fe. From Fig. 5(a), two separate oscillation peaks in the range of 60 eV above the Fe K-edge were observed in powder Fe. However, the corresponding two oscillation peaks for the as-spun Nd9Fe85 xMnxB6 samples are almost mixed, indicating the increase of disorder degree around Fe atoms with the increase of Mn doping. From Fig. 5(b), it is noticed that the XAFS spectra of the annealed Nd9Fe85 xMnxB6 samples were almost unchanged with increase of Mn doping. Two oscillation peaks in the range of 60 eV were obviously observed in all annealed samples. The almost identical XAFS spectra for all the annealed Nd9Fe85 xMnxB6 samples suggested that after annealing, almost the same crystal structure obtained for the materials with Mn doping. To represent the radial distribution curves F(r), the Fourier transformation of Extended X-ray absorption fine structure (EXAFS) oscillation function k3v(k) (kmin = 25 nm 1, kmax = 160 nm 1) for the samples is shown in Fig. 6. As can be seen from Fig. 6(a), the intensities of the peaks of radial distribution curves for the as-spun Nd9Fe85 xMnxB6 (x = 0) are stronger than those of the other two as-spun samples Nd9Fe85 xMnxB6 (x = 0.5,1). Moreover, the curve for the as-spun Nd9Fe85 xMnxB6 (x = 0) has similar feature to that for the powder Fe. It is obvious that the doping of Mn has changed the environment and increased the disorder around the Fe atoms in as-spun samples. On the other hand, from Fig. 6(b), the three radial distribution curves for annealed samples have quite similar features and close to those of the powder Fe. It is indicated that the crystal structures in

It has been found that the manganese addition can promote crystallization and increase the coercivity of the Nd9Fe85 xMnxB6 nanocomposite. The dependence of yM on the applied field indicated that the exchange coupling interaction was enhanced by Mn doping. The decrease of Curie temperature of the Nd2Fe14B phase and the rise of that of the a-Fe phase with Mn doping are caused by the change of interaction environment of the ferromagnetic phases. EXAFS has demonstrated that a certain amount of Mn addition could improve the formation of Fe configuration in the NdFeB materials after appropriate annealing. Therefore, the existence of Mn in Nd2Fe14B/a-Fe nanocomposite has a certain influence on the structural and magnetic properties of the system. Further work on the fundamental role of the doped Mn on the system, entering the structures of the magnetic phases or existing as an independent phase, is in progress.

Acknowledgements This work was supported by the National Key Project of Fundamental Research of China (973), No. G1999064508 and the scientific research startup fund of Hohai University, No. 2003410843.

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