ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 308 (2007) 46–55

www.elsevier.com/locate/jmmm

Synthesis of iron oxide nanoparticles under oxidizing environment

and their stabilization in aqueous and non-aqueous media
D. Maity1, D.C. Agrawal
Materials Science Programme, Indian Institute of Technology Kanpur, Kanpur 208016, India
Received 4 October 2005; received in revised form 22 March 2006
Available online 2 June 2006

Abstract

Synthesis of magnetite (Fe3O4) nanoparticles under oxidizing environment by precipitation from aqueous media is not straightforward
because Fe2+ gets oxidized to Fe3+ and thus the ratio of Fe3+:Fe2+ ¼ 2:1 is not maintained during the precipitation. A molar ratio of
Fe3+:Fe2+ smaller than 2:1 has been used by many to compensate for the oxidation of Fe2+ during the preparation. In this work, we have
prepared iron oxide nanoparticles in air environment by the precipitation technique using initial molar ratios Fe3+:Fe2+p2:1. The phases of
the resulting powders have been determined by several techniques. It is found that the particles consist mainly of maghemite with little or no
magnetite phase. The particles have been suspended in non-aqueous and aqueous media by coating the particles with a single layer and a
bilayer of oleic acid, respectively. The particle sizes, morphology and the magnetic properties of the particles and the ferrofulids prepared
from these particles are reported. The average particle sizes obtained from the TEM micrographs are 14, 10 and 9 nm for the water, kerosene
and dodecane-based ferrofluids, respectively, indicating a better dispersion in the non-aqueous media. The specific saturation magnetization
(ss) value of the oleic-acid-coated particles (
53 emu/g) is found to be lower than that for the uncoated particles (
63 emu/g). Magnetization
ss of the dodecane-based ferrofluid is found to be 10.1 emu/g for a volume fraction of particles j ¼ 0.019. Zero coercivity and zero
remanance on the magnetization curves indicate that the particles are superparamagnetic (SPM) in nature.
r 2006 Elsevier B.V. All rights reserved.

PACS: 75.50 Mm; 75.50 Dd; 75.50 Kj

Keywords: Magnetite; Maghemite; Nanoparticles; Iron oxide; Ferrofluids

1. Introduction mostly used as magnetic particles in ferrofluids due to

Ferrofluids or magnetic fluids are stable colloidal homo-
geneous suspensions of magnetic nanoparticles (around
10 nm in diameter) in an appropriate carrier (aqueous or
non-aqueous) liquid [1–4]. They are said to be super-
paramagnetic (SPM), meaning that they are attracted by a
magnetic field but retain no residual magnetism after the
field is removed [1–4]. Due to their small size and SPM
behavior, ferrofluids have been extensively used in several
technological and biomedical applications [4–7]. Iron oxide
(usually magnetite and maghemite) nanoparticles are
Corresponding author. Tel.: +91 512 2597892; fax: +91 512 2597664.
E-mail address: agrwald@iitk.ac.in (D.C. Agrawal).
1
Now at the Department of Metallurgical Engineering and Materials
Science, Indian Institute of Technology Bombay, Mumbai, India
their high saturation magnetization and high magnetic
susceptibility [8–10]; the magnetite (Fe3O4) particles are
preferred because of their greater saturation magnetization
[11–25]. The nanoparticles need to be stabilized in the
carrier liquid because they tend to agglomerate due to Van
der Waals forces. In addition, the magnetite nanoparticles
are very much susceptible to air oxidation [9,10]. In order
to prevent the possible air oxidation as well as agglomera-
tion, the Fe3O4 nanoparticles are coated with a surfactant
(e.g. fatty acids) [11–20] or a polymer (e.g. dextran)
[10,23–25]. Also once the dispersing agent is adsorbed on
the iron oxide particles, the number of accessible sites for
further crystal growth is reduced to keep the particle size
small [23].
Chemical co-precipitation has been widely used to
produce magnetite nanoparticles due to its ease and large

0304-8853/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jmmm.2006.05.001
 ARTICLE IN PRESS
D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55
volume capability [26,27]. The method involves co-pre-
cipitation from Fe2+ and Fe3+ aqueous salt solutions by
addition of a base. The chemical reaction may be written
[28,29] as follows:
Fe2þ þ 2Fe3þ þ 8OH ! Fe3 O4 þ 4H2 O (1)
According to this reaction an initial molar ratio of
Fe3+:Fe2+ ¼ 2:1 is needed for the production of Fe3O4.
But when the preparation is carried out in air, Fe2+ gets
oxidized to Fe3+ (Fe2++O2 - Fe3+). It is known that the
formation rate of Fe3+ by oxidation with air is nearly
independent of the ferrous ion concentration [30] and
hence oxidation reaction can go to nearly completion. It is
thus very difficult to maintain the Fe3+:Fe2+ ratio ¼ 2:1.
To overcome this problem, two approaches have been
used. In one the nitrogen (N2) gas is bubbled into the
reaction mixture [6,10,17–19]. This not only prevents the
oxidation of the magnetite but also reduces the particle size
[6,19]. Other workers have performed the synthesis of
magnetite nanoparticles under oxidizing environment
(air atmosphere) by lowering the initial molar ratio
(Fe3+:Fe2+o2:1) so that after the oxidation of Fe2+ to
Fe3+, the ratio approaches to 2:1 [15,22–25]. Initial molar
ratios ranging from Fe3+:Fe2+ ¼ 1:1 to 1.7:1 have been
used by various researchers [15,21,24,25]. However, the
particles thus obtained have not been adequately char-
acterized with respect to the phase(s) present—it is usually
assumed that the phase is magnetite. This problem is made
difficult because of the nearly similar X-ray diffraction
(XRD) patterns of magnetite and maghemite.
In the present work, we have prepared iron oxide
particles using various molar ratio of Fe3+:Fe2+ p 2:1 and
have characterized the resulting powders with respect to
the phase(s) obtained and other characteristics. It is found
that the particles consist mostly of maghemite with little
amount of the magnetite phase. We have also prepared and
characterized aqueous and non-aqueous-based ferrofluids
from one batch of these powders. It is shown that the phase
obtained in the powders is predominantly maghemite
despite the use of lower Fe3+: Fe2+ ratios.
2. Experimental
Analytical grade ferric chloride (FeCl3  6H2O), ferrous
chloride (FeCl2  4H2O), oleic acid (C18H34O2), ammonium
hydroxide (NH4OH) and dodecane (C12H26) are used;
kerosene used is of commercial grade.
Initial molar ratios of Fe3+:Fe2+ ¼ 2:1, 1.75:1, 1.5:1 are
used. Required amounts of FeCl3  6H2O and FeCl2  4H2O
are dissolved in 40 ml of deionized water. The solution is
heated at 80 1C for 1 h while being stirred. Then 5 ml of
NH4OH (30% w/w) are added rapidly to it. The resulting
suspension is vigorously stirred for another 1 h and then
cooled to room temperature. The precipitated particles are
washed five times with hot water and separated by
magnetic decantation. These are called uncoated particles.
47
The iron oxide nanoparticles prepared using
Fe3+:Fe2+ ¼ 1.5:1 are stabilized in oil (dodecane and
kerosene) and water media following a procedure reported
by Shen et al. [18], except that the oleic acid is used for both
single-layer and bilayer coating (Fig. 1) of the iron oxide
nanoparticles.
To prepare the single-layer oleic-acid-coated particles, a
solution of 0.1 ml oleic acid in 5 ml acetone is added to the
heated salt solution before the addition of NH4OH. A
black suspension is formed upon the addition of NH4OH.
Further additions of oleic acid are made in five 0.2 ml
(undiluted) volumes over 5 min intervals. The crystal
growth is allowed to proceed for 30 min at 80 1C with
constant stirring. The suspension is then cooled to room
temperature. The suspended particles are flocculated by
acetone and are washed five times with acetone and MeOH
mixture (equal volumes) to remove the excess oleic acid
and are recovered by magnetic decantation. This produces
the single-layer oleic-acid-coated iron oxide particles.
To prepare an oil-based ferrofluid, the single-layer oleic-
acid-coated iron oxide particles (
1 g) are mixed with
30–50 ml oil and 3–5 ml oleic acid (i.e.
10 vol% with
respect to carrier liquid) and the resulting mixture is
peptized by heating it at 80 1C for 30 min with vigorous
stirring. The coated particles are gradually transferred into
the oil medium. No phase separation is observed on
exposing the suspension to a strong magnet for 30 min
indicating that a stable oil-based ferrofuid is obtained.
For the preparation of a water-based ferrofluid, the
single-layer oleic-acid-coated iron oxide particles (
1 g) are
added to 20 ml deionized water and the slurry is heated to
60 1C under vigorous stirring. A solution of 10% (w/v)
ammonium salt of oleic acid (pH ¼ 10) is prepared
separately by mixing 30 ml water, 3 ml oleic acid and
30–40 drops of a solution of NH4OH (30% w/w). This
solution is added to the slurry dropwise under constant
Fig. 1. Schematic representation of bilayer surfactant-coated magnetic
nanoparticles.
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48 D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55

stirring at 60 1C until the slurry changes into a stable
suspension. The stability is checked by exposing the
suspension to a permanent magnet for 30 min. A stable
water-based ferrofluid is obtained after the addition of
30 ml of oleic acid.
The particles are characterized by XRD, transmission
electron microscope (TEM), Fourier transform infrared
spectroscopy (FTIR) and Mössbauer spectroscopy. Che-
mical analysis of the particles is performed to estimate the
ferrous and ferric iron content by a titration method [31].
Magnetic properties of the particles and magnetic fluids are
measured by a vibrating sample magnetometer (VSM)
operated in air at room temperature.
3. Results and Discussion
3.1. Morphology and size of the particles
Fig. 2 shows the TEM images of bilayer and single-layer
oleic-acid-coated iron oxide particles stabilized in aqueous
(Fig. 2a) and non-aqueous (Fig. 2b, kerosene; Fig. 2c,
dodecane) media. In the non-aqueous media, the particles

Fig. 2. TEM image of iron oxide nanoparticles: (a) bilayer coated particles dispersed in water, (b) single-layer coated particles dispersed in kerosene, (c)
single-layer coated particles dispersed in dodecane.
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D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55
are well dispersed but in aqueous medium they are
somewhat agglomerated. The average particle sizes from
the TEM micrographs were determined to be 14, 10 and
9 nm for the water-, kerosene- and dodecane-based
ferrofluids, respectively. Thus the single-layer coated
particles can be dispersed in oil (kerosene and dodecane)
medium effectively while the dispersion of the bilayer-
coated particles in water is not so effective.
Particle sizes of the uncoated powders and of the
particles in the ferrofluids were also measured by dynamic
light scattering using a particle size instrument (Malvern
HPPS). The results for the aqueous and dodecane
ferrofluids are shown in Fig. 3. The average particle sizes
obtained were (a) uncoated particles: 119 nm, (b) aqueous
ferrofluid: 107 nm, (c) kerosene ferrofluid 41 nm and (d)
dodecane ferrofluid: 29 nm. The average particle sizes
obtained by this technique are much larger than those by
TEM. This is because even in the absence of any external
magnetic field, the magnetostatic (magnetic dipole–dipole)
interactions between the particles can cause their agglom-
eration. It has been determined, experimentally [32] as well
Fig. 3. Size distribution for: (a) water-based ferrofluid, (b) dodecane-
based ferrofluid.
49
as by Monte Carlo simulations that the particles form
closed rings and long open loops with no particular spatial
orientation due to magnetostatic interaction in the absence
of any external magnetic field and form long chains parallel
to the applied field in the presence of an external field. The
chains or loops have a lower diffusion coefficient than the
single particle and the equivalent sphere diameter measured
by light scattering is higher than the elementary particle
size as revealed by other techniques (such as XRD and
TEM). The agglomerated ring and loop structures are not
seen in TEM, possibly because they are disturbed due to
the drying forces present during the sample preparation for
TEM.
3.2. Structural characterization of the particles
3.2.1. X-ray diffraction
Fig. 4 shows the XRD patterns of the iron oxide particles
prepared using the different initial molar ratios of
Fe3+:Fe2+ ¼ 2:1, 1.75:1, 1.5:1. The 2y values of the peaks
are compared with the standard data for Fe3O4 and g-
Fe2O3 in Table 1 [9]. It can be seen that the experimental
data can be assigned either to Fe3O4 or to g-Fe2O3 because
their peaks are very close to each other. However, it does
appear that our data is somewhat closer to g-Fe2O3 than to
Fe3O4. Nevertheless, additional verification is required to
confirm the correct phase. An extra peak at 2y E 32.81 is
present in the samples with the higher Fe3+:Fe2+ ratios.
This can be due to the presence of e-Fe2O3 in the samples.
Fig. 5 shows the comparison of XRD patterns of
uncoated and coated particles. The peaks for the coated
particles are broader than those for uncoated particles. The
crystallite sizes for the uncoated and coated particles
obtained from the analysis of the peak widths [33] are
found to be 10.8–13.2 and 5.2–7.3 nm, respectively.
Additional peaks, indicated by arrows in Fig. 3a, are
found to be present in the diffraction from the coated
powders. These can be assigned to the e-Fe2O3 phase. The
presence of this additional phase may be a size effect.
3.2.2. Chemical analysis
Iron oxide particles are analyzed chemically using 0.9997
(N/20) K2Cr2O7. Total amount of iron (Fe3++Fe2+) and
the amount of ferrous iron (Fe2+) thus determined are
shown in Tables 2 and 3, respectively. The experimental
results are compared with the calculated values obtained by
assuming the product to be pure magnetite (Fe3O4) and
pure maghemite (g-Fe2O3) phases. The amount of Fe2+
determined experimentally is smaller by a factor of 5–10
from that expected if the phase were pure Fe3O4. Also the
amount of total iron is closer what would be expected if the
powder were pure Fe2O3. It thus appears that the powders
obtained consist mostly of g-Fe2O3 with some Fe3O4 and e-
Fe2O3 (as determined from X-ray).
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50 D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55

Fig. 4. XRD patterns of the iron oxide particles prepared with ratios of Fe3+:Fe2+: (a) 2:1, (b) 1.75:1, (c) 1.5:1.

Table 1
XRD data (for 2y ¼ 20–80 1C) for Fe3O4, g-Fe2O3 from Ref. [9,31] and the experimental data from the uncoated particles prepared using different initial
molar ratios

From Refs. [9,31] Experimental data

Fe3O4 g-Fe2O3 Fe3+:Fe2+ ¼ 2:1 Fe3+:Fe2+ ¼ 1.75:1 Fe3+:Fe2+ ¼ 1.5:1

2y1 I 2y1 I 2y1 I 2y1 I 2y1 I

30.10 30 30.28 30 30.12 30 30.38 30 30.44 30

35.43 100 35.69 100 35.63 100 35.86 100 35.82 100
43.06 20 43.35 15 43.28 15 43.28 15 43.65 15
53.41 10 53.87 9 53.60 9 53.99 9 57.51 9
56.96 30 57.42 20 57.17 20 57.25 20 63.15 20
62.53 40 63.03 40 62.78 40 63.06 40 74.66 40
73.97 10 74.56 8 74.29 8 74.52 8 74.66 8

3.2.3. Infrared spectroscopy
Fig. 6 depicts the IR spectra of the uncoated, the single
layer and the bilayer of oleic-acid-coated iron oxide
nanoparticles prepared using the initial molar ratio of
Fe3+:Fe2+ ¼ 1.5:1. The corresponding adsorption fre-
quencies are given in Table 4 and are assigned to various
modes [9,34–40]. The IR bands at low wave numbers (p
700 cm1) come from vibrations of Fe–O bonds of iron
oxide. The experimental data for the Fe–O bonds of iron
oxide are compared with the standard IR data for iron
oxide particles in Table 5 [9]. It can be observed that IR
spectra of all the experimental particles consist of four
bands which are very close to those for maghemite. Little
shift of Fe–O bands from that of the standard maghemite
has occurred either due to the overlapping of two bands (to
give a band with average wave number) or due to the
particles being nanosized.
3.2.4. Mössbauer spectroscopy
Fig. 7 shows the Mössbauer spectrum for uncoated
particles prepared using the initial molar ratio of
Fe3+:Fe2+ ¼ 1.5:1. The corresponding Mössbauer para-
meters are given in Table 6. The experimental Mössbauer
spectrum actually consists of two sextets which are nearly
superimposed over each other. It is clearly different from
the spectrum observed from Fe3O4 which consists of two
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Fig. 5. Comparison of XRD patterns of (a) uncoated particles, (b) coated particles.

Table 2
Total amount of iron in the iron oxide powder

Initial molar ratio of Amount of powder Weight of total iron Calculated weight of total Calculated weight of total
Fe3+:Fe2+ used for taken (g) (Fe3++Fe2+) determined iron assuming the powder iron assuming the powder
powder (g) to be Fe3O4 (g) to be Fe2O3 (g)

2:1 0.2039 0.141770.0001 0.147 0.143

1.75:1 0.2005 0.145370.0001 0.145 0.140
1.5:1 0.2035 0.142170.0001 0.147 0.142

Table 3
Ferrous iron (Fe2+) in the iron oxide powder

Initial molar ratio of Amount of powder Weight of ferrous iron Calculated weight of Calculated weight of
Fe3+:Fe2+ used for taken (g) (Fe2+) determined (g) ferrous iron assuming the ferrous iron assuming the
powder powder to be Fe3O4 (g) powder to be Fe2O3 (g)

2:1 0.2011 0.008970.0001 0.048 0

1.75:1 0.2066 0.004270.0001 0.050 0
1.5:1 0.2068 0.009570.0001 0.048 0

clearly distinct sextets with the high-velocity peak being of
significantly higher strength than the low-velocity peaks [9].
The spectrum appears to be close to that from maghemite,
but the presence of two nearly overlapping sextets indicates
that more than one phase may be present. In case of
magnetite, the isomer shifts of the two sextets are 0.26 and
0.67 mm/s [9] which are different from the present data.
Further, the parameters extracted from the experimental
spectra (Table 6) are close to those from other oxides such
as g-Fe2O3 and e-Fe2O3 than from Fe3O4 [9]. Thus,
Mössbauer spectroscopy measurements show that the
particles are predominantly g-Fe2O3 with possible e-Fe2O3.
The experimental spectrum consists of quite broad peaks
indicating a fine particle size. This small particle size also
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52 D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55

Fig. 6. IR spectra of the iron oxide nanoparticles: (a) uncoated particles, (b) single-layer coated particles, (c) bilayer coated particles.

Table 4
IR absorption frequencies from uncoated, single-layer and bilayer-coated powders

Uncoated Single-layer coated Bilayer coated Assignment of adsorption bands [9,33-39] (u:
stretching vibration; d: deformation vibration)

3200–3600 3200–3600 3200–3600 u(O–H) for H2O (sample taking up water) or

u(O–H) for H-bonded OH groups (from oleic acid)
— 2852 and 2922 2855 and 2924 u(C–H) for (–CH2) of oleic acid
1708.26
1705 — u(C–O) for CO2 (from air)
— 1714.38 — u(C ¼ O) for COOH (free)
— 1727.59 u(C ¼ O) for ammonium oleate (physically
adsorbed)
1630.51
1630 — u(O–H) for H2O
— 1525-1595 1587.60 u(COO) for COOH (chemically adsorbed)
— 1438.35 u(NH4+) for ammonium oleate
1403.60
1408.75
1402 u(C–O) for CO2 (from air)
— — 1100–1250 The couple between u(C–O) and d(O–H) for
COOH (free)
628.57, 584.80 and 440.87 621.43, 578.54 and 435.71 632.14, 579.98 and 421.43 u(Fe–O) (stretching vibration in tetrahedral site)
o401 o402 o413. 81 u(Fe–O) (that in octahedral site)

seems to be responsible for the difference in the experi- Thus, XRD, chemical analysis, FTIR and Mössbauer
mental Mössbauer parameters and those from the bulk g- spectroscopy results show that the particles are predomi-
Fe2O3 or e-Fe2O3. nantly g-Fe2O3 with some e-Fe2O3 and possible traces of
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D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55 53

Fe3O4. Although we aimed to prepare magnetite particles 3.3. Magnetic Measurements

by lowering the initial Fe3+:Fe2+ ratio, but the g-Fe2O3
phase is mostly obtained due to the oxidation of Fe2+ to Because of the significant differences in the magnetic
Fe3+ during the coprecipitation reaction for all the initial properties of different phases of iron oxide, the measure-
Fe2+:Fe3+ ratios. ment of magnetic properties can be of help in determining
the phases in the particles. Fig. 8 shows the magnetization
curves for the uncoated iron oxide particles prepared using
Table 5 the initial molar ratios of Fe3+:Fe2+ ¼ 2:1, 1.75:1 and
Comparison of observed IR bands (p700 cm1) with the standard data 1.5:1 and the single layer coated particle prepared using
for magnetite and maghemite [9]
Fe3+:Fe2+ ¼ 1.5:1. The specific saturation magnetization
Specimen IR absorption frequencies (cm1) (ss) values for the uncoated particles are found to be 63.6,
62.9 and 64.3 emu/g, respectively. The nearly equal values
Magnetite [9] 580 and 400
of ss indicate that all the particles prepared using the
Maghemite [9] 700, 640–660, 620, 580, 560, 460, 390 and 305
Uncoated particles 628.57, 584.80, 440.87 and
401.44a different ratios of Fe3+:Fe2+ consist of same magnetic
Single-layer coated 621.43, 578.54, 435.71 and
402.94a phase. Further, the ss values are close to that of bulk
particles maghemite (ss ¼ 73:5 emu=g) rather than bulk magnetite
Bilayer-coated 632.14, 579.98, 421..43 and
413.81a (ss ¼ 92 emu=g) [8]. Thus, these results also agree with the
particles
previous phase-identification results. The decrease in ss
a
Spectra are collected between the wave number ranges of compared to bulk maghemite is due to the small size of the
4000–400 cm1. particles [41–43]. Zero coercivity and zero remanance on
the magnetization curves indicate that the particles are

Fig. 7. Experimental Mössbauer spectrum at 298 K from the uncoated powder.

Table 6
Experimental Mössbauer parameters at 298 K

Initial molar ratio Isomer shift d Quadrupole splitting Hyperfine field Bhf Width of line W Area (%)
(mm/s1) DEQ (mm/s1) (T) (mm/s1)

Fe3+:Fe2+ ¼ 1.5:1 0.37 0.01 47.78 0.56 44.14

0.43 0.05 43.01 1.09 55.86
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54 D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55

σ VsH

(b) 1.75:1

(c) 1.5:1

(a) 2:1
σ (emu/g) (arbitary units)

(d) 1.5:1 (coated)

σ s (a) = 62.9 emu/g

σ s (b) = 64.3 emu/g

σs (c) = 63.6 emu/g

σs (d) = 53.1 emu/g

−15 −10 −5 0 5 10 15
H (kOe)

Fig. 8. Magnetization curves for the uncoated particles prepared using the ratios of Fe3+:Fe2+: (a) 2:1, (b) 1.75:1, (c) 1.5:1 and (d) single-layer coated
particles (Fe3+:Fe2+ ¼ 1.5:1).

σ Vs H
10 (a)
φ = 0.0194

5
(b)
φ = 0.0035
σ (emu/g)

0
σ s (a) = 10.1 emu/g
σs (b) = 4.2 emu/g

-5

-10
-15 -10 -5 0 5 10 15
H (kOe)

Fig. 9. Magnetization curves for the dodecane-based ferrofluids containing different volume fractions (j) of particles: (a) j ¼ 0:0194 and (b) j ¼ 0:0031.
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D. Maity, D.C. Agrawal / Journal of Magnetism and Magnetic Materials 308 (2007) 46–55
SPM in nature [38,43]. The ss value (53.1 emu/g) of the
coated particles is lower than the ss value (63.6 emu/g) of
the uncoated particles; this lowering is due to the smaller
size of the coated particles and the presence of a non-
magnetic oleic acid coating on the surface of the particles.
Magnetization curves for dodecane-based ferrofluids
with two different volume fractions (j ¼ 0:019 and
j ¼ 0:0035) of particles are shown in Fig. 9. There is no
hysteresis which indicates that ferrofluids are also SPM.
Magnetization is increased from ss ¼ 4:2 to 10.1 emu/g)
with increase in volume fraction from j ¼ 0:0035 to 0.019.
4. Conclusions
The main purpose of using molar ratios smaller than 2:1
is to compensate for the oxidation of Fe2+ to Fe3+ during
the preparation to obtain the magnetite phase. A variety of
techniques including XRD, chemical analysis, IR spectro-
scopy, Mössbauer spectroscopy and magnetic measure-
ments are used to determine the phases in the powders. All
the results indicate that, contrary to the assumptions in
literature, the main phase in the powders is maghemite (g-
Fe2O3) with possibly a small amount of the e-Fe2O3 phase.
Thus it is concluded that the oxidation of Fe2+ to Fe3+ in
air is quite rapid and the preparation of the magnetite
phase is difficult.
The particle size of the powder is found to be much
reduced when a surfactant (oleic acid) is used during the
preparation. Particles coated with a single layer of
surfactant can be stabilized in kerosene and dodecane
while the bilayer coating is necessary to obtain the water-
based ferrofluids. The saturation magnetization of the
powder is about 63 emu/g.
Acknowledgments
Helpful discussions with Professor H.C. Verma are
thankfully acknowledged. Partial support for this work
was provided by the Department of Science and Technol-
ogy, Government of India, under grant SR/S5/NM-41/
2002.
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