Table of Contents Author Guidelines Submit a Manuscript
Journal of Chemistry
Volume 2014, Article ID 842495, 5 pages
Research Article

Preparation and Magnetic Properties of Anisotropic (Sm,Pr)Co5/Fe Nanocomposites Particles via Electroless Plating

Provincial Key Laboratory of Applied Chemistry, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, China

Received 8 November 2013; Revised 10 January 2014; Accepted 10 January 2014; Published 16 February 2014

Academic Editor: Lavinia Balan

Copyright © 2014 Shi Wang et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


Anisotropic (Sm,Pr)Co5/Fe nanocomposites particles were prepared by electroless plating iron on the surface of (Sm,Pr)Co5 nanoflakes after being prepared by ball milling for 4 h. A uniform and continuous coating layer was obtained due to the addition of complexing agent and the particle size of the reduced Fe particles was in the range of 10~20 nm. When the nominal addition of Fe was 15 wt%, the nanocomposites show enhanced remnant and saturation magnetization:  emu/g,  emu/g compared to the noncoated nanoflakes with  emu/g,  emu/g, while the coercivity drops from 10.33 kOe to 8.89 kOe. The effect of Fe content on the magnetic properties of the magnets is also discussed.

1. Introduction

Nanocomposite magnetic materials have drawn extensive attention since they were reported by Coehoorn et al. [1] in 1988. The theoretical maximum magnetic energy product, (BH)max, of anisotropy nanocomposite permanent magnets material can be as high as 1090 kJ/m3 (137 MGOe) [2], which is much higher than that of any single-phase permanent magnets. However, until now, (BH)max of the nanocomposite magnets is still much lower than the theoretical value. An important factor restricting the development of the (BH)max is the microstructure of theoretical models which is difficult to control. Generally speaking, an efficient exchange coupling needs to meet two conditions: (i) the size of the soft magnetic phase should be scaled to double domain wall width of the hard magnetic phase and (ii) soft magnetic phase should be uniformly distributed. So far, most of the nanocomposite magnets are fabricated following the conventional top-down routes, for example, high-energy mechanical milling, and melt spinning, but they are all isotropic materials with low (BH)max [312]. The other “bottom-up” approach has actually attracted more attention, since it allows for the nanoparticles to be distributed uniformly and for the hard phase to be aligned and form an optimum structure so as to ensure efficient exchange coupling. A number of attempts have been made to synthesize nanocomposite magnetic materials via the bottom-up way. Zeng et al. [13] used simple mechanical blending of Fe nanoparticles with Sm-Co permanent magnet powders, but the magnetic soft phase tended to agglomerate which led to the reduction in exchange coupling. Marinescu et al. [14] reported the use of a chemical deposition method to fabricate Sm-Co/nano-Fe composite, yielding relatively good magnetic properties. Zeng et al. [15] reported the fabrication of FePt-Fe3Pt nanocomposites using nanoparticle self-assembly with (BH)max of the nanocomposites exceeding the single phase by over 50 percent. However, although the particle size can be reduced to a certain degree, the agglomeration is inevitable.

In this paper, the electroless plating technique was applied to fabricate the (Sm,Pr)Co5/Fe nanocomposites materials. The addition of complexing agent can control the deposition rate of the iron to form a continuous and uniform coating layer. The effect of the Fe content on magnetic properties was also investigated.

2. Experiment

The (Sm0.58Pr0.42)Co5 powders were milled mechanically for 4 h using a SPEX 8000 high-energy ball mill. The initial adding amount of the (Sm0.58Pr0.42)Co5 powders was 2 g and the ball to powder ratio was 10 : 1 and the diameter of the steel ball is about 12 mm. During the process, heptane was used as the solvent with oleic acid used as the surfactant; the content in total mass was 10 wt.% and 55 wt.%, respectively. The synthesis of (Sm,Pr)Co5/Fe nanoparticles was carried out under Argon atmosphere in a three-necked bottle. The following chemicals were used to synthesize the composite nanoparticle: (Sm,Pr)Co5 (0.12 g), FeSO4·7H2O (0.1 g), C6H5Na3O7·2H2O (0.6 g), and NaBH4 (0.0625 g). In the first step, all the reagents except the reducing agent (NaBH4) were dissolved in deionizer water and then diluted to 100 mL inside the container. Polyvinylpyrrolidone was added as surfactant to protect the particles from oxidation and avoid the soft magnetic phase aggregation [16]. In the end, NaBH4 was dissolved in the deionizer water and then poured into the bottle slowly under the condition of continuous ultrasonic and mechanical stirring. The final chemical equation can be described as follows:

After reacting for 40 min, the powders were collected via magnetic separation and were washed by ethanol for several times. The composite powders were dried in a vacuum environment for further investigation.

The coating morphology and composition of the powders were characterized by scanning electron microscopy (SEM) equipped with an energy dispersion X-ray spectrometer (EDS). The crystal structure was determined by X-ray diffraction (XRD) using the Cu Kα radiation, with the diffraction angular range from 2θ = 25° to 90°. The magnetic properties were investigated by a vibrating sample magnetometer (VSM). The powders were aligned under a 4 kOe field and solidified with epoxy resin for the VSM and XRD measurements.

3. Results and Discussion

SEM images of noncoated powders and coated nanocomposites are shown in Figure 1. The typical SEM image of (Sm,Pr)Co5 powders is presented in Figure 1(a). It can be seen that after ball milling for 4 h, powders’ agglomeration is still obvious and the particles have a flaky-like structure. The thickness of the nanoflakes is about 50~100 nm, with the length range from 0.5 to 8 μm. The nanoflakes provide a large specific surface area for further coating. Figures 1(b) and 1(c) show the SEM micrographs of the (Sm,Pr)Co5/Fe nanocomposites at different magnifications. From Figure 1(b), the flakes are coated with a large amount of nanoparticles, but a few of the nanoparticles are also aggregated separately. The inset Figure 1(c) shows the much greater magnification of nanocomposites; a layer of continuous nanoparticles is coated on the surface and the particles’ size is about 10~20 nm. The iron layer distributes uniformly and not simply stacks together. The elemental composition and mass fraction of the nanocomposites are revealed by the energy dispersive X-ray spectroscopy. Figures 1(d) and 1(e) show the energy spectrum of (Sm,Pr)Co5 and (Sm,Pr)Co5/Fe, respectively. The mass fraction of iron is 11.5%, which indicates that the nanocomposites have a relatively high content of soft phase. However, the iron coating content relative to the composite powder stoichiometry was 15% in mass. The content is still lower than the nominal content we initial added, which implies that the iron particles are not fully deposited on the surface of (Sm,Pr)Co5 and fewer iron particles nucleate and grow directly in the solution. It is worth mentioning that the oxidation is inevitable during the process of ball milling and electroless plating, which would lead to a decrease in magnetic properties.

Figure 1: SEM micrographs and EDS spectrum of (Sm,Pr)Co5 powders and (Sm,Pr)Co5/Fe nanocomposites. (a) (Sm,Pr)Co5 powders after ball milling for 4 h; ((b) and (c)) (Sm,Pr)Co5/Fe nanocomposites for different magnifications; ((d) and (e)) EDS spectrum of (Sm,Pr)Co5 and (Sm,Pr)Co5/Fe nanocomposites and the element mass percentage.

Figures 2(a) and 2(b) shows the XRD patterns of the sample of (Sm,Pr)Co5 nanoflakes nonaligned and aligned, respectively. The diffraction peaks can be indexed as the standard SmCo5 (JCPDS NO.35-1400). After magnetic alignment, the (002) peak becomes dominant, indicating a strong c-axis crystallographic alignment [16]. The results are consistent with the report of Cui et al. [17, 18]. But there are no obvious diffraction peaks of iron in the XRD pattern of (Sm,Pr)Co5/Fe nanoflakes (Figure 2(c)). The possible reason was that the iron grain was too small or partly crystallized, so the intensity of the iron diffraction peak was weak and partly covered by the (Sm,Pr)Co5 peaks. Therefore, (Sm,Pr)Co5/Fe nanocomposites were annealed by vacuum at 450°C for 10 minutes. Figure 2(d) shows the XRD pattern of (Sm,Pr)Co5/Fe nanocomposites after annealing treatment. The iron diffraction peaks could be indexed (JCPDS NO.06-0696), which proved the existence of iron. Oxidation of (Sm,Pr)Co5 occurred during the annealing process due to the remain surfactant being removed incompletely. Moreover, the main diffraction peaks of Fe-B compounds cannot be indexed which proves the nonexistence of the Fe-B compounds and the particle layer is Fe nanoparticle coated on the (Sm,Pr)Co5 surface.

Figure 2: XRD patterns of (Sm,Pr)Co5 nanoflakes: (a) nonaligned; (b) magnetically aligned; (c) (Sm,Pr)Co5/Fe nanocomposites magnetically aligned; (d) (Sm,Pr)Co5/Fe nanocomposites annealed at 450°C.

The magnetic properties of composite (Sm,Pr)Co5/Fe nanoflakes with different iron contents are shown in Figure 3. The nanocomposites were measured in the direction parallel to the c-axis. It can be seen that the remnant magnetization shows a trend of first increasing then decreasing with the content of iron increases and reaches the maximum value when the iron content is 15% in weight. Although the saturation magnetization increases gradually with the increase of iron content as we expect, the coercivity drops dramatically. Figure 4 shows the magnetic hysteresis loops of the (Sm,Pr)Co5 nanoflakes and the (Sm,Pr)Co5/Fe nanocomposites with 15 wt.% Fe content. The magnetic properties of (Sm,Pr)Co5/Fe nanocomposites nonannealing are shown below:  emu/g,  emu/g, and  kOe; the magnetic properties of (Sm,Pr)Co5 nanoflakes are presented as a reference:  emu/g,  emu/g, and  kOe. However, the magnetic hysteresis loop of (Sm,Pr)Co5/Fe is not smooth and there is an obvious collapse in the second quadrant, which indicates that the exchange coupling effect between the magnetically soft and hard phase is not strong. The possible reasons for this may be that the particle size and the distribution of the soft phase are not precise enough to achieve the requirements of the theory.

Figure 3: Magnetic properties of (Sm,Pr)Co5/Fe nanocomposites with different Fe contents.
Figure 4: Magnetic hysteresis loops of aligned (Sm,Pr)Co5 nanoflakes and (Sm,Pr)Co5/Fe nanocomposites.

4. Conclusion

In summary, we prepared (Sm,Pr)Co5/Fe nanocomposites via electroless plating. The addition of a complexing agent effectively controls the coating morphology, to obtain a continuous and uniform Fe layer. The nanocomposites show enhanced magnetic properties when the nominal addition of Fe was 15 wt.%,  emu/g,  emu/g, and  kOe compared to the properties of uncoated nanoflakes  emu/g,  emu/g, and  kOe. The coercivity drops dramatically with the increase of Fe content, and also the magnetic hysteresis loop of the nanocomposite shows an obvious collapse in the second quadrant.

Conflict of Interests

The authors declare that there is no conflict of interests regarding the publication of this paper.


  1. R. Coehoorn, D. B. de Moojj, J. P. W. B. Duchateau, and K. H. J. Buschow, “Novel permanent magnetic materials made by rapid quenching,” Journal of Applied Physics, vol. 49, no. 8, pp. 669–670, 1988. View at Publisher · View at Google Scholar
  2. R. Skomski, “Aligned two-phase magnets: permanent magnetism of the future? (Invited),” Journal of Applied Physics, vol. 76, no. 10, pp. 7059–7064, 1994. View at Publisher · View at Google Scholar · View at Scopus
  3. R. Fischer, T. Schrefl, H. Kronmüller, and J. Fidler, “Phase distribution and computed magnetic properties of high-remanent composite magnets,” Journal of Magnetism and Magnetic Materials, vol. 150, no. 3, pp. 329–344, 1995. View at Publisher · View at Google Scholar · View at Scopus
  4. D. Goll, M. Seeger, and H. Kronmüller, “Magnetic and micro structural properties of nanocrystalline exchange coupled PrFeB permanent magnets,” Journal of Magnetism and Magnetic Materials, vol. 185, no. 1, pp. 49–60, 1998. View at Publisher · View at Google Scholar · View at Scopus
  5. P. G. McCormick, W. F. Miao, P. A. I. Smith, J. Ding, and R. Street, “Mechanically alloyed nanocomposite magnets (invited),” Journal of Applied Physics, vol. 83, no. 11, pp. 6256–6261, 1998. View at Publisher · View at Google Scholar · View at Scopus
  6. S.-Y. Chu, S. A. Majetich, M.-Q. Huang, and R. T. Fingers, “Synthesis and magnetic behavior of SmCo5(1-x)Fex nanocomposite magnets,” Journal of Applied Physics, vol. 93, no. 10, pp. 8146–8148, 2003. View at Publisher · View at Google Scholar · View at Scopus
  7. W. Li, L. Li, Y. Nan et al., “Controllable nanocrystallization in amorphous Nd9Fe85B6 via combined application of severe plastic deformation and thermal annealing,” Applied Physics Letters, vol. 91, no. 6, Article ID 062509, 2007. View at Publisher · View at Google Scholar · View at Scopus
  8. Q. Nguyen, C. N. Chinnasamy, S. D. Yoon et al., “Functionalization of FeCo alloy nanoparticles with highly dielectric amorphous oxide coatings,” Journal of Applied Physics, vol. 103, no. 7, Article ID 07D532, 2008. View at Publisher · View at Google Scholar · View at Scopus
  9. P. Saravanan, M. Premkumar, A. K. Singh, R. Gopalan, and V. Chandrasekaran, “Study on morphology and magnetic behavior of SmCo5 and SmCo5/Fe nanoparticles synthesized by surfactant-assisted ball milling,” Journal of Alloys and Compounds, vol. 480, no. 2, pp. 645–649, 2009. View at Publisher · View at Google Scholar · View at Scopus
  10. C.-B. Rong, Y. Zhang, N. Poudyal, X.-Y. Xiong, M. J. Kramer, and J. P. Liu, “Fabrication of bulk nanocomposite magnets via severe plastic deformation and warm compaction,” Applied Physics Letters, vol. 96, no. 10, Article ID 102513, 2010. View at Publisher · View at Google Scholar · View at Scopus
  11. C.-B. Rong, Y. Zhang, N. Poudyal et al., “Self-nanoscaling of the soft magnetic phase in bulk SmCo/Fe nanocomposite magnets,” Journal of Materials Science, vol. 46, no. 18, pp. 6065–6074, 2011. View at Publisher · View at Google Scholar · View at Scopus
  12. S. C. Sun, Z. Q. Qi, H. Q. Chen et al., “Effects of Al0.3Ga0.7As interlayer with pulsed atomic layer epitaxy on heterogeneous integration of GaAs/Ge grown by MOCVD,” Journal of Alloys and Compounds, vol. 590, pp. 1–4, 2014. View at Publisher · View at Google Scholar
  13. Q. Zeng, Y. Zhang, M. J. Bonder, G. C. Hadjipanayis, and R. Radhakrishnan, “Bulk SmCo5/α-Fe composite by plasma pressure consolidation,” IEEE Transactions on Magnetics, vol. 39, no. 5, pp. 2974–2976, 2003. View at Publisher · View at Google Scholar · View at Scopus
  14. M. Marinescu, J. F. Liu, M. J. Bonder, and G. C. Hadjipanayis, “Fe-nanoparticle coated anisotropic magnet powders for composite permanent magnets with enhanced properties,” Journal of Applied Physics, vol. 103, no. 7, Article ID 07E120, 2008. View at Publisher · View at Google Scholar · View at Scopus
  15. H. Zeng, J. Li, J. P. Liu, Z. L. Wang, and S.-H. Sun, “Exchange-coupled nanocomposite magnets by nanoparticle self-assembly,” Nature, vol. 420, no. 6914, pp. 395–398, 2002. View at Publisher · View at Google Scholar · View at Scopus
  16. X.-L. Wang, H.-L. He, F.-Q. Wang et al., “Preparation and magnetic properties of anisotropic (Sm,Pr)Co5/Co composite particles,” Journal of Magnetism and Magnetic Materials, vol. 324, no. 5, pp. 889–892, 2012. View at Publisher · View at Google Scholar · View at Scopus
  17. B. Z. Cui, A. M. Gabay, W. F. Li, M. Marinescu, J. F. Liu, and G. C. Hadjipanayis, “Anisotropic SmCo5 nanoflakes by surfactant-assisted high energy ball milling,” Journal of Applied Physics, vol. 107, no. 9, Article ID 09A721, 2010. View at Publisher · View at Google Scholar · View at Scopus
  18. B. Z. Cui, W. F. Li, and G. C. Hadjipanayis, “Formation of SmCo5 single-crystal submicron flakes and textured polycrystalline nanoflakes,” Acta Materialia, vol. 59, no. 2, pp. 563–571, 2011. View at Publisher · View at Google Scholar · View at Scopus