© Copyright 1997 by the American Chemical Society VOLUME 101, NUMBER 41, OCTOBER 9, 1997

LETTERS

Advances in the Preparation of Magnetic Nanoparticles by the Microemulsion Method

J. A. López Pérez and M. A. López Quintela

Departamento de Quı́mica-Fı́sica, UniVersidade de Santiago de Compostela,
E-15706 Santiago de Compostela, Spain

J. Mira* and J. Rivas

Departamento de Fı́sica Aplicada, UniVersidade de Santiago de Compostela,
E-15706 Santiago de Compostela, Spain

S. W. Charles
Department of Chemistry, UniVersity College of North Wales, Bangor,
Gwynedd LL57 2UW, United Kingdom
ReceiVed: June 23, 1997; In Final Form: August 21, 1997X

A method based on a microemulsion route is presented to obtain magnetic nanoparticles of different sizes,
offering several advantages with respect to other similar methods. It consists basically of the development
of a microemulsion route above room temperature. Magnetic iron oxide particles with sizes ranging from 2
to 8 nm are obtained. The as-obtained product presents defined X-ray diffraction patterns, without the
complications of working in an inert atmosphere or with extra amounts of Fe2+, thereby eliminating the need
for further steps in order to achieve good crystallization of the material.

1. Introduction in this way.6 Nevertheless, the particles are obtained with a

poor degree of crystallization, and a further process is needed
The synthesis of magnetic nanoparticles has been an area of
in order to improve it, consisting typically of annealing the
study for a long time because of the interesting practical
applications of such particles in magnetic recording, magnetic obtained particles.7 The drawback of the lack of crystallization
fluids, permanent magnets, etc.1 can also be avoided by working in an inert atmosphere or by
To synthesize such particles several methods are used.2 using large amounts of Fe2+.8
Among them, the microemulsion method has appeared as a We present here a method of synthesis based on the
powerful tool in the past decade.3 A microemulsion is an microemulsion route that eliminates the above-mentioned
isotropic and thermodynamically stable single phase formed by problems. For this purpose, the reaction does not take place at
at least three components; two of them are nonmiscible, and a
room temperature, as it did in the methods reported up to date,
third, called surfactant, has an amphiphilic behavior.4,5 Specif-
but does so at a higher temperature. In this Letter we
ically, the synthesis of magnetic iron oxides has been attempted
demonstrate the efficacy of this improvement of the micro-
* Corresponding author. Fax: +34 81 520676. E-mail: fajmirap@usc.es.
emulsion method, obtaining crystallized magnetic iron oxide
X Abstract published in AdVance ACS Abstracts, September 15, 1997. nanoparticles.

S1089-5647(97)02046-4 CCC: $14.00 © 1997 American Chemical Society

8046 J. Phys. Chem. B, Vol. 101, No. 41, 1997 Letters

Figure 1. X-ray diffraction patterns of the as-obtained nanoparticles.

TABLE 1: Splitting Temperature between FC and ZFC dc

Magnetizations (TS), Interplanar Spacing (d), and Average
Particle Size, Obtained from X-ray Diffractograms (RX) and
Fits to the Langevin Law (mag.)
sample TS (K) d (Å) size (RX) (Å) size (mag.) (Å)a
A 210 2.511 73 7 (0.44)
B 140 2.512 56 63 (0.47)
C 75 2.511 36 41 (0.53)
D 60 2.527 24 30 (0.42)
E 45 2.542 19 24 (0.09)
a The standard deviation of a log-normal volume distribution is given

in parentheses.

2. Synthesis Procedure
In this microemulsion route inverse micelles are used, i.e.,
water nanodroplets are formed in an organic compound and used
as nanoreactors in order to control particle size. These
nanodroplets are surrounded by a surfactant coat that limits their
size and separates them from the organic compound. A nonionic
surfactant (Brij-97) and cyclohexane as organic phase have been
used here. The ternary system cyclohexane/Brij-97/water forms
microemulsions at low water concentrations for a wide range
of Brij-97 concentrations.9 Figure 2. TEM micrographs of some samples: (a, top) sample A, (b,
The synthesis procedure involves the mixture of two micro- middle) sample C, and (c, bottom) sample E.
emulsions M(I) and M(II) at 65 ° C. The microemulsion M(I)
3. Results and Discussion
is of cyclohexane/Brij-97/aqueous solution of iron salts in the
(93 - x)/7/x volume ratio (1 < x < 3). The molarities of the X-ray diffraction patterns of the samples were taken from
salts in the aqueous solution are 1 M in FeSO4‚7H2O, 0.5 M in 10 to 80° (2θ) using Cu KR radiation. Diffractograms are
FeCl3‚6H2O, and 0.1 M in HCl. Acidic medium is used in order presented in Figure 1 showing a progressive broadening of the
to avoid oxidation of Fe2+. The microemulsion M(II) is similar peaks when going from sample A to E, indicating a decrease
to M(I), but without salts in the aqueous solution and with a in particle size. The obtained patterns can be identified with
20% greater volume of cyclohexylamine. Cyclohexylamine is γ-Fe2O3. From these data we obtained the interplanar space,
used in order to produce an alkaline medium, necessary to d, and the mean particle diameter using the Debye-Scherrer
precipitate the iron salts. All chemicals were supplied by formula11 for the most intense peak, corresponding to the (311)
Aldrich Chemicals and used without further purification. reflection in maghemite (Table 1). d values increase slightly
M(I) (200 mL) and M(II) (25 mL) were heated separately in from sample A to E and are similar to the characteristic value
a water bath until 65 °C was reached. At this temperature one of maghemite (d ) 2.52 Å).12
single transparent phase of every microemulsion was formed. TEM micrographs were taken with a 200 KV-JEOL micro-
The M(I) was added to the M(II) under mechanical stirring. scope. For this purpose the samples were dispersed in ethanol
After 15 min of aging, the mixture was cooled to room and deposited onto a copper grid. Aggregates of particles with
temperature. The obtained precipitate was decanted with the a clear decrease in particle size from sample A to E are observed,
aid of a magnet and washed several times with large amounts in agreement with data from X-ray fits (Figure 2).
of acetone and water and finally dried at room temperature in Zero-field-cooled (ZFC) and field-cooled (FC) data were
a desiccator. Five samples, labeled A, B, C, D, and E, were recorded at 5 Oe between 4 and 300 K with a Quantum Design
obtained from microemulsions with x ) 3, 2.5, 2, 1.5, and 1. SQUID. They are presented in Figure 3, showing that moving
Given the high concentration of reagents employed and that from sample E to sample A the temperature at which FC and
the same amount of surfactant is present for each microemulsion, ZFC split, TS, and the temperature of the maximum of the ZFC
the smaller x, the smaller the size of the nanoreactors, and susceptibility are largely modified. Also the curves become
therefore smaller particles should be obtained.10 broader and broader. These changes, which reflect an increase
Letters J. Phys. Chem. B, Vol. 101, No. 41, 1997 8047

Figure 4. Magnetization versus field at room temperature for the

samples.

control, due to the known dependence of the magnetic particle

volume with the blocking temperature of a superparamagnetic
system.14 Above the temperature of splitting between ZFC and
FC curves, all the particles are in the superparamagnetic state;
actually the splitting temperature corresponds to the highest TB.
A DMS-1660 Vibrating Sample Magnetometer was used to
obtain magnetization versus field curves from 77 to 300 K in
fields up to 10 kOe. In Figure 4 we show the results at room
temperature. The maximum magnetization values decreased
from A to E, as well as the curvature of the M/H lines.
Providing that these data are taken at the superparamagnetic
state, a simple estimate of the average size can be deduced from
a fit to the Langevin law with a log-normal size distribution,15
yielding a reduction in the magnetic particle volumes (Table
1), in agreement with data from TEM and X-ray fits.
In summary, we demonstrate that the use of stable micro-
emulsions above room temperature represents an advance in
the synthesis of iron oxide magnetic nanoparticles, compared
to the classical use of microemulsions at room temperature. We
show also that with easy modifications in the synthesis procedure
the final particle size can be controlled.

References and Notes

(1) Matijevic, E. MRS Bull. 1989, XIV, 19. Ozaki, M. Ibid. 35.
(2) López-Quintela, M. A.; Rivas, J. Curr. Opin. Colloid Interface Sci.
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(3) López-Quintela, M. A.; Rivas, J. J. Colloid Interface Sci. 1993,
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(4) Physics of amphiphilic micelles, Vesicles and microemulsions;
Degiorgio, V., Corti, M., Eds.; North-Holland: Amsterdam, 1985.
(5) Micelles, solutions and microemulsions; structure, dynamics and
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(6) Lee, K. M.; Sorensen, C. M.; Klaubunde, K. J.; Hadjipanayis, G.
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(7) Ayyub, P.; Multari, M.; Barma, M.; Palkar, V. R.; Vijayaraghavan,
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(9) Klyachko, N. L.; Levashov, V.; Pshezhetsky, A. V.; Bogdanova,
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(10) Tojo, C.; Blanco, M. C.; López-Quintela, M. A. Langmuir, in press.
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(12) Inorganic crystallographic data base plus 40. Philips based on PDF-
Figure 3. Magnetization versus temperature (ZFC and FC) for the 2, 1990.
samples, taken with an applied field of 5 Oe.
(13) Dormann, J. L.; Fiorani, D. Magnetic Properties of fine particles;
North-Holland: Amsterdam, 1992.
of the average blocking temperature 〈TB〉 and a broadening of (14) Rado, G. T.; Suhl, H. Magnetism; Academic: New York, 1963.
the size distribution with increasing the particle size,13 can be (15) Chantrell, R. W.; Poplewell, J.; Charles, S. W. IEEE Trans. Magn.
considered as another probe of the trend in the particle size 1978, 14, 975.