JOURNAL OF APPLIED PHYSICS 103, 07E120 2008

Fe-nanoparticle coated anisotropic magnet powders for composite permanent magnets with enhanced properties
M. Marinescua and J. F. Liu
Electron Energy Corporation, Landisville, Pennsylvania 17538, USA

M. J. Bonder and G. C. Hadjipanayis

University of Delaware, Newark, Delaware 19716, USA

Presented on 7 November 2007; received 21 September 2007; accepted 16 October 2007; published online 29 January 2008 Utilizing the chemical reduction of FeCl2 with NaBH4 in the presence of 2:17 SmCo powders, we synthesized composite Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4/nano-Fe anisotropic hard magnetic powders. The average particle size of the hard magnetic core powder was 21 m while the soft magnetic Fe nanoparticles deposited uniformly on the core powder had a particle size smaller than 100 nm. Different reaction protocols, such as immersion of the hard magnetic core powder in each reagent, the use of microemulsion micelle technique, or doubling the weight ratio of FeCl2 to core powder, led to different degrees of magnetic coupling of the hard and soft magnetic components of the composite powder. A reaction time of 180 s led to deposition of 3.5 wt % Fe nanoparticles and improved magnetic properties of the composite powder compared to the uncoated Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 powder. The respective magnetic hysteresis parameters were 4 M 18 kOe = 11.3 kG, 4 M r = 11 kG, and iHc 20 kOe with a smooth demagnetization curve. 2008 American Institute of Physics. DOI: 10.1063/1.2830956
I. INTRODUCTION

The most important criteria for efcient exchange coupling in nanocomposite permanent magnets are i the size of soft magnetic phase should be scaled to double domain wall width of the hard magnetic phase1 and ii soft magnetic phase should be uniformly distributed. So far, most of the efforts to obtain such hard/soft nanocomposite magnets followed top down metallurgical routes, i.e., development of the nanostructure through rapid solidication or high-energy mechanical milling. Both techniques provide certain degree of control over the microstructure, but they produce crystalographically isotropic materials with low maximum energy product BH max.2 Recently, more attention has been given to the bottom up approach, which assembles composite material from anisotropic building blocks. There were a number of attempts38 to explore simple mechanical blending of Fe nanoparticles with more coarse anisotropic hard magnetic powders. Some of these efforts, in particular, blending of the needle-shaped Fe particles with SmCo permanent magnet powder,7 yielded fairly good magnetic properties. In general, however, mechanical blending of a relatively coarse powder with an ultrane one tends to result in agglomeration of the latter5 and the consequent reduction in exchange coupling. On the other hand, coating of hard magnetic particles with a layer of soft magnetic material may prevent agglomeration of the latter and allow better control over its size. Liu et al.10 explored various coating techniques of depositing Fe on Nd FeB particles subsequently subjected to consolidation and hot plastic deformation die upsetting and reported signicant improvement in BH max compared to the blending apa

proach. Zeng et al.9 published results on the coating of SmCo particles with Co layers using electroless deposition. This article presents our experimental results on the synthesis and properties of composite anisotropic hard magnetic Sm-Co/nano-Fe powders. These composite powders are candidate precursors for permanent magnets with enhanced magnetic performance for high temperature applications.
II. EXPERIMENT

Composite SmCo/nano-Fe powders were synthesized by depositing Fe nanoparticles on anisotropic Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 hard magnetic powder. The hard magnetic powders were produced by jet milling the consolidated aligned magnets. The magnets were not magnetized and the average particle size after jet milling was 21 m. The Fe nanoparticle synthesis employed wet chemistry according to the reaction FeCl2 + NaBH4 + H2O Fe B + NaCl + H2 + H2O. 1

Electronic mail: mmarinescu@electronenergy.com.

The hard magnetic powder was immersed in the reaction solution and acted as a substrate onto which the Fe nanoparticles formed and deposited. The amount of nanoparticle coating was modied by varying the time allowed for the reaction i.e., 33 and 180 s and the mass fraction of FeCl2 to SmCo powders i.e., 1.5:6 and 3:6 while keeping the molar ratio of the reaction reagents FeCl2 : NaBH4 at the optimal 1.7:1 for nanoparticle saturation magnetization.11 The experiments were done under different reaction protocols: i immersion of hard magnetic powder in each of the reagent solutions and ii microemulsion micelle technique by adding Si oil.12 An idealized sketch of the core powder coated with Fe nanoparticles through these deposition processes is given
2008 American Institute of Physics

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FIG. 1. a Synthesis of Fe nanoparticles on the surface of the substrate powder within the reaction volume. b More uniform Fe-nanoparticle coating of the substrate powder by using the microemulsion technique with the formation of micelles.

in Fig. 1. After the reaction ceased, the powders were collected with a magnet, washed, and sieved to remove unwanted by-products and free nanoparticles. The composite powders were characterized by x-ray diffraction XRD using the Cu K radiation, scanning electron microscopy SEM with a JEOL JSM-6330F instrument equipped with an energy dispersive x-ray EDX detector, and magnetic measurements were done with a Lakeshore vibrating sample magnetometer VSM . Alignment and magnetization of the uncoated and composite powder was done by using pulse magnetizers with an applied eld of 100 kOe. The magnetic measurements hysteresis were performed on powders aligned and xed in wax by using a demagnetization factor of 0.12, derived from previous measurements on Ni powder. The magnetization values in kilogauss unit were calculated considering the ideal density.

FIG. 2. SEM micrograph of a composite Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4/ nano-Fe powder. Inset shows Fe nanoparticles attached to the surface of the substrate core particle.

III. RESULTS AND DISCUSSION

Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 anisotropic powders not magnetized were immersed in a FeCl2 solution in ethanol, and upon the addition of a solution of NaBH4 in distilled water, Fe precipitated within the whole volume, including the surface of the SmCo powder, in accordance with Eq. 1 . In contrast, the immersion of SmCo powder in the solution of NaBH4 in distilled water resulted in a substantial corrosion that decreased dramatically the particle size and, moreover, Fe nanoparticles generated by the reaction 1 did not attach to the SmCo powders. Figure 2 presents the SEM micrograph of Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4/nano-Fe composite powder synthesized by immersing the core powder in FeCl2 solution and allowing the reaction 1 to take place, and then washing in ethanol three times. One can see that the Fe nanoparticles with a particle size below 100 nm distribute fairly uniform on the surface of the core powder. However, some additional free clusters of Fe nanoparticles were still present. The Fe nanoparticles on the core SmCo powder determine a Gaussian prole in the XRD pattern of Fig. 3, which superimposes with the peaks for 2:17 SmCo phase obtained for the uncoated core. EDX analyses of an area of 1200 900 m2 of compacted powder showed that the Fe nanoparticles, derived as the excess of Fe compared to the core powder, were in the amount of 2.5 wt % for the composite powder synthesized in a 33 s reaction time, 3.2 wt % for

33 s reaction time with added Si oil, 3.5 wt % for a reaction time of 180 s, and 3.5 wt % for double reactants protocol. The demagnetization curves of composite Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4/nano-Fe powders synthesized under different deposition protocols are compared in Fig. 4 with the uncoated powder. The hysteresis magnetic parameters of the uncoated powder are the following: remanent magnetizatio 4 M r = 10.7 kG, magnetization at an applied eld of 18 kOe 4 M 18 kOe = 10.9 kG, and intrinsic coercivity iHc 20 kOe. We obtained that 4 M 18 kOe increases with all Fe nanoparticle coating protocols, as expected, and the amount of increase can be related with the amount of Fe nanoparticles. For a 33 s reaction time, the composite particles have 4 M r = 10.7 kG, 4 M 18 kOe = 11.2 kG, and iHc 20 kOe. By allowing a longer time 180 s for the reaction, we obtained composite powder with 4 M 18 kOe = 11.3 kG. The remanence increases also to 4 M r = 11 kG and the smooth prole of the demagnetization curve is well preserved. The microemulsion technique consists in the formation of oil micelles within the reaction bath, and, therefore, a localized synthesis of Fe nanoparticles occurs within

FIG. 3. XRD of uncoated Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 powder a and composite with average particle size of 21 m Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4/nano-Fe powder synthesized by coating with a 33 s reaction time b .

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FIG. 4. Magnetic hysteresis for uncoated Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 and composite Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4/nano-Fe powder synthesized by: 1 a 33 s reaction time 2.5 wt % Fe nanoparticles ; 2 idem, by using the microemulsion technique with Si oil 3.2 wt % Fe nanoparticles ; 3 a 180 s reaction time 3.5 wt % Fe nanoparticles ; 4 multiplying by 2 the weight ratio between FeCl2 and core powder 3.5 wt % Fe nanoparticles .

FIG. 5. Magnetic hysteresis for uncoated Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 powder and 1 composite Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4/nano-Fe powder synthesized by a 180 s reaction time with 3.5 wt % of Fe coating; 2 Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 powder mechanically blended with 3.5 wt % Fe nanoparticles; and 3 blended with 10 wt % Fe nanoparticles.

the micelles that incorporate the core magnet powder. This technique produced composite powder with a slightly higher 4 M r and 4 M 18 kOe and a better prole of the demagnetization curve compared to the in volume process for the same reaction time. By doubling the weight ratio of FeCl2 to the core powder, compared to the above experiments, 4 M 18 kOe does not exceed the values obtained through a longer reaction time, whereas the demagnetization curve shows a pronounced kink. We noticed that this later type of reaction produced as observed with SEM and not shown here a larger amount of free Fe nanoparticles not attached to the powder substrate and not removed after washing. Agglomeration of these free nanoparticles results in a lack of magnetic coupling with the hard magnetic core and therefore the kink on the demagnetization curve 4 in Fig. 4. One should mention that the only slight increase in the magnetization for all the presented coating protocols is strictly related to the small amount of Fe coating, determined by the specic surface area of the core powder. Smaller particle size of the core powder will allow for a larger volume fraction of the Fe nanoparticle coating. A direct comparison in terms of the magnetic hysteresis between Fe nanoparticle coating of Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 powder and mechanical blending of the same hard magnetic powder with Fe nanoparticles commercially available with average particle size of 100 nm is given in Fig. 5. The amount of added Fe was 3.5 wt % for both cases. Mechanical blending was done in hexane assisted by a surfactant oleic acid in order to disperse more uniformly the powder particles and avoid agglomeration. One can see that, even if, with the Fe addition, 4 M 18 kOe reaches the same value, the prole of the demagnetization curve is deteriorated in the case of mechanical blending. By increasing to 10 wt % the amount of Fe nanoparticles mechanically blended with the Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 powder, a high 4 M 18 kOe

of 12 kG and 4 M r of 11.3 kG were obtained although the demagnetization curve shows a magnetically uncoupled system.
IV. CONCLUSION

Anisotropic composite Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 nano-Fe powders were synthesized by depositing on anisotropic hard magnetic Sm Co0.699Fe0.213Cu0.064Zr0.024 7.4 core powder, soft magnetic Fe nanoparticles produced by the chemical reduction of FeCl2 with NaBH4. Optimized deposition conditions lead to improved magnetic properties compared to the uncoated powder.
ACKNOWLEDGMENTS

This work was supported by DoD through AFOSR Contract No. FA9550-07-C-0029. One of the authors M.M. acknowledges the contribution of Dr. A. Gabay of University of Delaware with SEM and XRD investigations and Steve Kodat of Electron Energy Corporation for the VSM measurements.
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