JOURNAL OF APPLIED PHYSICS 99, 08E912 共2006兲

Magnetic nanoparticles produced by surfactant-assisted ball milling

V. M. Chakka, B. Altuncevahir, Z. Q. Jin, Y. Li, and J. P. Liua兲
Department of Physics, The University of Texas at Arlington, Arlington, Texas 76019
共Presented on 1 November 2005; published online 24 April 2006兲
Nanoparticles of Fe, Co, FeCo, SmCo, and NdFeB systems with sizes smaller than 30 nm and
narrow size distribution have been successfully prepared by ball milling in the presence of
surfactants and organic carrier liquid. It has been observed that the nanoparticles prepared by milling
Fe and FeCo powders were close to spherical in their shapes, whereas those of Co, SmCo, and
Nd–Fe–B showed elongated rod shapes. The nanoparticles showed superparamagnetic behavior at
room temperature, except for the SmCo nanoparticles that were ferromagnetic. Nanoparticles of all
types showed ferromagnetic behavior at low temperatures. The compositions of nanoparticles
prepared by milling the SmCo, NdFeB, and FeCo powders were found to be deviated from the
starting powders. © 2006 American Institute of Physics. 关DOI: 10.1063/1.2170593兴

I. INTRODUCTION weight ratio of 5:1 was used. The amount of surfactant used
was ⬃10% – 12% by weight of the starting powder.
One of the approaches for preparation of magnetic nano-
Samples for magnetic measurements were prepared by
particles is by surfactant-assisted ball milling, a technique
embedding the nanoparticles in epoxy inside the glove box.
used for making magnetic fluids.1–3 Surfactants aid in
Magnetic measurements at room temperature were per-
achieving smaller particle sizes during milling and dispersing
formed using an alternating gradient magnetometer with
the fine particles when appropriate solvents are used.4–6
measuring field up to 14 kOe, and at 5 K using a supercon-
However, the size distribution of the particles obtained by
ducting quantum interference device 共SQUID兲 with measur-
ball milling can be quite wide compared with the chemical
ing field up to 70 kOe. Structural and morphological charac-
methods. The chemical methods, nevertheless, have had lim-
terizations were performed using transmission electron
ited success in the synthesis of hard magnetic nanoparticles
microscope 共TEM兲, and x-ray diffractometer. Compositional
of rare-earth compounds.7,8 Traditionally, surfactant-assisted
characterizations were performed using energy dispersive
ball milling technique has been used mainly for preparing
x-ray and inductively coupled plasma.
ferrite nanoparticles, and not many studies have been con-
ducted on the preparation of nanoparticles of different mate-
rials, except a few.9,10 In this study, systematic efforts have III. RESULTS AND DISCUSSIONS
been made to prepare and study the properties of the nano- When surfactant was used along with heptane during
particles prepared by milling soft and hard magnetic materi- milling a colored liquid 共Fig. 1兲 was obtained along with
als including Fe, Co, FeCo, SmCo, and NdFeB by surfactant- coarse particles 共referred to as slurry兲 which sedimented at
assisted ball milling. The milling parameters have been the bottom of the milling vial. The colored liquids contained
controlled carefully and nanoparticles with desired morphol- dispersion of nanoparticles smaller than 30 nm in all cases.
ogy have been obtained.

II. EXPERIMENTS
The starting powders had particle sizes from
⬃10 to 45 ␮m 共−325 mesh兲. Commercially available Fe
powders with 98% purity and Co powders with 99.5% purity
were used. Alloy powders of Sm–Co 共1:5 and 2:17兲, NdFeB
共2:14:1兲, and FeCo were prepared by arc melting followed
by grinding. Milling process and handling of the starting
powders and the milled particles were carried out in an
oxygen-free inert environment 共argon gas兲 inside a glove
box. Heptane 共99.8% purity兲 was used as a solvent and oleic
acid 共90%兲 and oleyl amine 共⬎98% 兲 were used as surfac-
tants during milling. High energy Spex 8000M mill with the
milling vial and the balls made of 440C hardened steel were
used for preparing the nanoparticles. The milling durations
used were typically from 1 to 50 h, and ball to powder

a兲
Author to whom correspondence should be addressed; electronic mail: FIG. 1. Typical color of liquids obtained after milling without 共left兲 and
[email protected] with surfactants.

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08E912-2 Chakka et al. J. Appl. Phys. 99, 08E912 共2006兲

rods for the 5 h-milled sample. With increasing milling time,

the percentage of elongated nanorods increased. For the
sample prepared by milling for 10 h, the aspherical particles
with size ranging from 2 to 8 nm were obtained. Elongated
rods with width of 2 – 3 nm and lengths from 10 to 18 nm
共aspect ratios 5–9兲 were also obtained. Such elongated nano-
structures have not been observed in the case of nanopar-
ticles prepared by milling Fe and FeCo powders.
The TEM images 关as shown in Figs. 2共c兲 and 2共d兲兴 of the
nanoparticles prepared by milling SmCo5-based powders
clearly show that the morphology of the nanoparticles varies
with increased milling time. The 5 h-milled sample was
found to be the nanoparticles with size ranging from
3 to 13 nm, which were mostly irregular and aspherical with
a very small percentage of elongated particles. When the
milling time was increased to 15 h, elongated rod-shaped
nanoparticles were seen along with other irregular particles.
The percentage of these nanorods increased further in the
25 h-milled sample. Typically rods with length from
7 to 20 nm and width from 3 to 6 nm were present. The as-
pect ratios of the nanorods varied from ⬃1.5 to 5. In addi-
FIG. 2. TEM images of the nanoparticles prepared by milling Fe powders tion, as shown in Fig. 2共d兲, the rod-shaped nanoparticles tend
for: 共a兲 1 h and 共b兲 5 h, and by milling SmCo5-based powders for 共c兲 5 h to align parallel to each other on the TEM grid. Similar na-
and 共d兲 25 h.
norod formations were also found in the case of nanopar-
ticles prepared by milling Sm2Co17 and Nd2Fe14B-based
When surfactants were not added to heptane, the solvent re- powders with oleic acid.
mained clear after milling because there were no nanopar- The mechanism of ball milling is fairly complex and
ticles dispersed in the liquid. does not lend itself easily to rigorous theoretical analysis due
TEM images of the nanoparticles prepared by milling Fe to its dynamic nature. The nanorods could be produced by
powders for different durations 共1, 5, 15, 25, and 50 h兲 using fracture along some preferred crystalline orientation or an-
oleic acid as surfactant showed spherical or aspherical nano- isotropic growth of the nanoparticles during the milling. In-
particles in sizes ranging from 3 to 9 nm 关Fig. 2共a兲兴. There crease in the temperatures locally inside the milling vial may
was no significant change in morphology of the nanopar- facilitate the growth. Materials with hexagonal- 共for SmCo5,
ticles with increase in milling time up to 50 h. Figure 2共a兲 Sm2Co17, Co兲 and tetragonal 共for Nd2Fe14B兲 structures have
shows nanoparticles with very narrow size distribution a preferred orientation for fracture which are the close-
共4 – 6 nm兲 obtained by milling Fe powders obtained from a packed planes 关共0001兲 for hcp兴, and form plate-like
different vendor for 1 h and by using stainless steel 共316 SS兲 structures,11 which upon further milling would result in the
balls instead of hardened steel balls. As seen in Fig. 2共a兲, the formation of elongated nanoparticles. This may also explain
nanoparticles can self assemble into a regular pattern which the absence of elongated structures in the case of Fe and
can be achieved by controlled evaporation of the solvent FeCo which have bcc 共body centered cubic兲 structure.
after depositing the nanoparticle dispersion liquid on the In the case of nanoparticles prepared by milling FeCo
TEM grid. and SmCo5, an overall deficiency of Co was observed 共for
Similarly, TEM images of nanoparticles prepared by example FeCo0.42, SmCo1兲. Similarly, in the case of nanopar-
milling FeCo powders showed ultrafine spherical nanopar- ticles from Sm2共CoFe兲17 powders, deficiency of both Co and
ticles with a narrow particle size distribution ranging from Fe, and in the case of nanoparticles prepared by milling
1.7 to 4.0 nm for samples prepared using oleic acid. The nar- Nd2Fe14B powders, deficiencies of both Fe and B 共for ex-
row size distribution and ultrafine particle sizes are the great ample Nd2Fe2.12B0.2兲 were observed. The possible mecha-
advantages of this technique as compared with other physical nism for the deficiencies could be the phase decomposition
methods for nanoparticle preparation. due to the precipitation of Co/ Fe/ B atoms in the starting
While all the materials studied were found to be compat- material under the impact of the balls leading to the forma-
ible with both oleic acid/oleyl amine as surfactants and hep- tion of Co/ Fe/ B deficient phases, which has also been ob-
tane as solvent, only in the case of Co does oleic acid not served by other groups.12,13 The nanoparticles could be pro-
work well with the particles. Milling of Co particles with duced from different regions of the material followed by
oleic acid resulted in a jelly-like mass, not a liquid with possible surfactant selective dispersion of nanoparticle spe-
nanoparticle dispersion, which makes separating the nano- cies explaining the formation of nanoparticles with overall
particles from the solution difficult. A liquid with nanopar- composition deficiency and inhomogeneity.
ticle dispersion could be obtained by milling with oleyl In the case of nanoparticles prepared by milling Fe, Co,
amine and the morphology of the nanoparticles showed and FeCo, superparamagnetic behavior was observed at
mostly aspherical nanoparticles with a few elongated nano- room temperature. Magnetic measurements at 5 K using
08E912-3 Chakka et al. J. Appl. Phys. 99, 08E912 共2006兲

milling time dependence of the remanence ratio and satura-

tion magnetization is necessary to understand this effect.

IV. CONCLUSION
In summary, interesting experimental findings related to
the particle size, shape, composition, and magnetic proper-
ties have been observed. Elongated rod-like nanoparticles
were obtained by milling SmCo, NdFeB, and Co materials
which are useful for fabrication of anisotropic nanostructured
magnets. The compositions of the nanoparticles were found
to deviate from that of the starting material and its optimiza-
tion would be necessary. While better understanding is
needed of the nanoscale mechanisms governing nanoparticle
formation during surfactant-assisted ball milling of different
materials, this method may become a versatile technique ap-
FIG. 3. Slope-corrected low-temperature 共5 K兲 magnetization curves of plicable for preparation of rare-earth based magnetic nano-
nanoparticles prepared by milling SmCo5 based powders with oleic acid for
5, 15, and 25 h 共see Ref. 14兲. particles.

ACKNOWLEDGMENTS
SQUID showed some hysteresis with coercivities up to
400 Oe, and an unsaturated loop even at 70 kOe, implying a This work is supported by DoD/MURI under Grant No.
combination of superparamagnetic and ferromagnetic behav- N00014-05-1-0497 and DoD/DARPA through ARO under
ior at 5 K. Grant No. DAAD-19-03-1-0038. The authors are grateful to
Magnetic properties of the nanoparticles prepared by Dr. Jin Liu of Electron Energy Corp., and Dr. L. Li of Car-
milling SmCo5- and Sm2Co17-based powders showed hyster- penter Technologies for providing them with the rare-earth
esis at room temperature with low coercivities 共⬍100 Oe兲 alloy and FeCo alloy powders for this research.
and very low remanence ratio 共M r / M s兲 of less than 0.1. At
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Slope correction has been made to each hysteresis curve with the assump-
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with increasing milling time. Further investigation on the was then normalized using its saturation moment value.