Journal of Nanoparticle Research (2005) 7: 675679 Springer 2005

DOI 10.1007/s11051-005-5467-4
Brief communication

Synthesis and stabilization of FeNdB Nanoparticles for biomedical applications

Yousef Haik1,2,*, Jhunu Chatterjee1 and Ching Jen Chen1

1
Center for Nanomagnetics and Biotechnology, Florida State University, Tallahassee, FL, USA; 2Department
of Mechanical Engineering, United Arab Emirates University, Al Ain, UAE; *Author for correspondence
(E-mail: haik@eng.fsu.edu or yhaik@uaeu.ac.ae)

Received 20 July 2004; accepted in revised form 13 April 2005

Key words: ironneodymiumboron particles, magnetic nanoparticles, silica coated particles, biomedical
applications

Abstract

Stable composition of Iron Neodymium Boron nanoparticles are formed by a chemical method. Con-
ventional borohydride reduction method was used. The particles are in the size range of 30100 nm. Silica
coating was applied to stabilize and prepare the particles for in vitro applications such as cell separation and
diagnostics. Morphology of particles has been studied along with the structure and magnetic properties.

Introduction particles containing boron by purely chemical

Synthesis of inorganic alloys with magnetic prop-
erties has been a matter of tremendous interest
amongst the materials scientist for several years.
There are dierent conventional methods to syn-
thesize these particles. Usually the magnets of
FeNdB type are synthesized by powder metal-
lurgical (Sagawa et al., 1984) or by rapid quench-
ing process (Koon & Das, 1984; Croat et al., 1984;
Sellmyer et al., 1984). These methods are expen-
sive as high purity metals are required to be used
as starting materials. Reductiondiusion tech-
nique has also been used to fabricate FeNd B
magnets (Okajima et al., 1987). Another method
involving both spray drying and reductiondiu-
sion process is reported using salt mixtures of iron
and neodymium and boric acid (Dong et al.,
2001). This method is less expensive as rare earth
metal oxide can be used here as starting materials
instead of pure metals and also mechanical milling
can be avoided. Considerable attention has been
given in recent years to make magnetic alloy
route which involves reduction of metal salts by
sodium borohydride (Yiping et al., 1989; Wells
et al., 1989; Corrias et al., 1990). Chemical route
also gives the possibility to obtain alloy of ne
particles in desired composition with homogeneity
and ne morphology (Ohmori & Matizevic, 1992;
Zysler et al., 2001). Additionally, synthesizing
magnetic alloy particles in non interacting medium
such as in dispersion gives the opportunity to
study the magnetic properties of the particles in
dierent environments.
Here we report synthesis of nanosized FeNdB
particles via chemical route using salts of iron and
neodymium. A borohydride reduction method was
used for the synthesis and ultrasonication was done
further to have homogeneous sized particles in
nanometer range (30100 nm). These particles are
extremely susceptible to oxidation. In order to
minimize the oxidation eect, these particles are
passivated overnight under a continuous ow of
oxygen and nitrogen. These particles are further
coated with silica by conventional precipitation
676
process and are designed for biomedical applica-
tions. Silica coated particles are well known for
their capacity to chemically attach with proteins
and many other biological molecules. Morphology
and sizes of all the particles are determined
by scanning transmission electron microscopy.
Magnetic properties have been studied using a
Superconducting Quantum Interference Device
(SQUID) magnetometer.
Experimental
Neodymium chloride, ferrous sulphate, sodium
borohydride, tetraethyl orthosilicate, and ammo-
nia (0.2 M in propane) were obtained from Sigma
Chemical Company. Three dierent concentra-
tions [0.041 (M)] of the salt solutions were made
with ferrous sulphate and with neodymium chlo-
ride (80% Fe and 20% Nd).
A 25 ml solution of the salt mixture was made at
pH 6, and it was slowly added to a 25 ml sodium
borohydride solution at pH 13 in an argon atmo-
sphere for about half an hour and the reaction was
carried out at 0C. Concentration of sodium
borohydride used was varied from 0.5 M to 0.8 M.
A black precipitate was obtained. The precipitate
was sonicated at 0C for 30 s. It was washed with
water to remove residual ions and then with ace-
tone to remove water and then dried in vacuum. In
another set of experiment silica coated FeNdB
particles were formed. In this method, about
0.45 M of ammonia was added to the black pre-
cipitate which was formed earlier. The mixture was
put at 40C in a constant temperature bath for
10 min to stabilize the system and then tetraethyl
orthosilicate (0.02 M) was added to it. These silica
precipitations were done for 3 h, 8 h and 20 h.
Characterization
Transmission electron microscopy was done using
a JEOL STEM 2010 microscope to obtain the
morphological characteristics of the alloy particles
and wide angle X-ray crystallography (Siemens
wide angle X-ray diractometer) was performed to
obtain the structural information. Compositions
of the alloy material were obtained by inductively
coupled plasma atomic emission spectroscopy
(ICP). Analysis was done at the Galbraith Labo-
ratories Inc. USA. Magnetic properties of the
particles were measured by a SQUID magnetom-
eter (MPMS 5 Quantum Design, California).
Results and discussion
Borohydride reduction process to obtain transi-
tion metal alloy was rst described by Schlesinger
(Schlesinger et al., 1953). Though real mechanism
of the reaction is still unknown but it seems that
hydride ions in an aqueous solution of a borohy-
dride acts as strong reducing agent and it converts
the metallic salt into the metallic state. The alloy
thus formed was sonicated to maintain the parti-
cles in nanosized. But the stabilization of the alloy
is most challenging. There are dierent ways such
as passivation and annealing to stabilize the alloy
particles (Zysler et al., 2001). It has been found
that the stability of the FeNdB particles is also
composition dependent.
The ICP analysis of particles showed the stoi-
cheometric composition of three alloy as
Fe5.6NdB2, Fe5.4NdB9, Fe5.2NdB13.7. For the sake
of simplicity the samples are designated as FNB1,
FNB2 and FNB3, respectively. The composition
of the alloy is strongly dependent on the reaction
conditions (Corrias et al., 1990; Shen et al., 1993;
Bender et al., 1991). Wide angle X ray diracto-
gram showed (Figure 1) that the particles had
amorphous nature irrespective of their composi-
tion. It has been conrmed by the electron dif-
fraction pattern which showed clear amorphous
hallow. It has been reported that when the
reduction reaction is carried below their glass
transition temperature these particles are amor-
phous in nature (Lin et al., 1997). Phase trans-
formation (from amorphous to crystalline) is
possible by annealing (Lin et al., 1997). Fig-
ure 2(a, b and c) show the TEM micrograph for
FNB 1, FNB2 and FNB 3, respectively. The par-
ticles are mostly in the size range of 50200 nm. By
placing the electron beam exactly on these spher-
ical particles, peaks for iron and neodymium has
been observed. Figure 3 is the silica coated Fe
NdB particles. From the micrograph it is
observed that the cluster of the particles have been
coated with silica instead of individual particles. It
is almost impossible to obtain individual particles
as they have a tendency to agglomerate as soon as
they are formed and before starting of any silica
coating.
 677

Figure 1. WAXS diractogram for silica coated FeNdB particles.

Figure 2. (a) TEM micrograph and EDS pattern for FNB1 particles (b) TEM micrograph for silica coated FNB2 particles (c)
TEM micrograph for silica coated FNB3 particles.
678
Figure 3. TEM micrograph for FeNdB particles coated
with silica.
A temperature dependence of magnetization for
these alloys is shown in the Figure 4. No blocking
temperature was observed as the particles have
distribution in sizes. Due to wide distribution in
particle sizes as observed in TEM micrograph,
there might be an overlap of blocking tempera-
tures for particles with dierent sizes and so it
could not be determined. No Curie temperature is
observed within 300C. The hysterics plots
(Figure 5) at 300 K for all samples showed
Figure 4. Temperature vs. magnetization plot for FeNdB particles.
superparamagnetic nature as there is almost no
remanent magnetization. Coercivity of these sam-
ples are negligible (6 Oe-20Oe) compared to
Fe2Nd14B alloy particles (6 KOe) produced by
reduction diusion method (Dong et al., 2001).
The saturation magnetization is in the range of
6 emu/gm to 24 emu/gm. The magnetic moment
of the sample with higher borohydride concen-
tration (FNB1) is much lower compared to the
other. The concentration of the salt solution was
1(M) and the sodium borohydride concentration
was 0.8(M) for FNB1. Composition of the mate-
rial is certainly playing an important role in terms
of their stability and nally it has impact on
magnetic property as observed from the hysterisis
plot.
Conclusions
FeNdB particles are synthesized using borohy-
dride reduction method along with ultrasonica-
tion. The stability of these particles is achieved by
passivation with a ow of nitrogen and oxygen.
Stability and magnetic property of these particles
are composition dependent. Particles are coated
with silica for their potential use in biomedical
research. These particles are in the size range of
2060 nm. These particles are amorphous in nat-
ure and they have superparamagnetic properties.
 679

Figure 5. Applied magnetic eld vs. magnetization plot for FeNdB particles.

References Okajima Y., T. Sugita & S. Okada, 1987. US patent No

4,681,623.
Sagawa M., S. Fujimura, M. Togawa, H. Yamamoto & Y.
Bender C., S. Koch, S. Linderoth & S. Morup, 1991. In Science
Matsura, 1984. New material for permanent magnets on a
and Technology of Nanostructured Magnetic Materials.
base of Nd and Fe. J. Appl. Phys. 55, 2083.
Edited by G.C Hadjipanayis and G.A Prinz New York,
Schlesinger H.I., H.C. Brown, D.L. Mayeld & J.R. Gilbreath,
Plenum press, 559562.
1953. Procedures for the preparation of methyl borate.
Corrias A., G. Ennas, G. Leicheri, G. Marongieu & G.
J. Am. Chem. Soc. 75, 215.
Paschina, 1990. Amorphous metallic powders prepared by
Sellmyer D., A. Ahmad, G. Muench & G. Hajipanayis, 1984.
chemical reduction of metal ions with potassium borohydride
Magnetic hardening in rapidly quenched FePr and FeNd
in aqueous solution. Chem. Mater. 2, 363.
alloys. J. Appl. Phys. 55, 2088.
Croat J.J., J.F. Herbst, R.W. Lee & F. Epinkerton, 1984. PrFe
Shen J., Z. Li, Q. Yan & Y.J. Chen, 1993. Reactions of bivalent
and NdFe-based materials: A new class of high performance
metal ions with borohydride in aqueous solution for the
permanent magnets. J. Appl. Phys. 55, 2078.
preparation of ultrane amorphous alloy particles. J. Phys.
Dong X.L., B.K. Kim, C.J. Choi, K.S. Park & Z.D. Zhang,
Chem. 97, 8504.
2001. Synthesis of Nd2Fe14B powders by spray-drying and
Wells S., S.W. Charles, S. Morup, S. Linderoth, J. Wonterg-
reduction diusing process. J. Mater. Res. 16, 1083.
hem, J. Larsen & M.B. Madsen, 1989. A study of FeB and
Koon N.C. & B.N. Das, 1984. Crystallization of FeB alloys
FeCoB alloy particles produced by reduction with boro-
with rare earths to produce hard magnetic materials. J. Appl.
hydride. J. Phys: Condens. Mater. 1, 8199.
Phys. 55, 2063.
Yiping L., G.C. Hadjipanayis, C.M. Sorensen & K.J. Klabunde,
Lin J.H., S.F. Liu, Q.M. Cheng, X.L. Qian, L.Q. Yang & M.Z.
1989. Magnetic and structural properties of ultrane CoB
Su, 1997. Preparation of Nd-Fe-B based magnetic materials
particles. J. Magn. Magn. Mater. 79, 321.
by soft chemistry and reductiondiusion process. J. Alloy.
Zysler R.D., C.A. Ramos, H. Romaro & A.J. Ortega, 2001.
Compounds 249, 237.
Chemical synthesis and characterization of amorphous Fe
Ohmori M. & E. Matizevic, 1992. Preparation and properties
NiB magnetic nanoparticles. J. Mater. Sci. 36, 2291.
of uniform coated colloidal particles: VII Silica on hematite.
J. Coll. Int. Sci. 150, 594.