Journal of Alloys and Compounds 449 (2008) 710

Particle size dependence in low temperature

nitridation reaction for Fe
16
N
2
Shinichi Kikkawa

, Kohei Kubota, Takashi Takeda

Graduate School of Engineering, Hokkaido University, N13W8, Sapporo 060-8628, Japan
Received 4 November 2005; received in revised form 14 December 2005; accepted 26 December 2005
Available online 21 December 2006
Abstract
Low temperature nitridation of -Fe powder was studied by reduction of -Fe
2
O
3
with three particle sizes using ow hydrogen. Most suitable
-Fe
2
O
3
powder had an average particle size of 60 nm. After hydrogen reduction, the -Fe showed average particle size of about 120 nm. The yield
of ferromagnetic Fe
16
N
2
obtained at 140

C for 100 h was the highest of its nitrided product among the products nitrided in a temperature range of
130170

C. Thermal decomposition of iron pentacarbonyl was also applied to obtain a narrow particle size distribution of monodispersed -Fe
spherical particles of 30 nm. It was performed in the presence of oleic acid stabilizer in octyl ether solvent.
2006 Elsevier B.V. All rights reserved.
Keywords: Iron nitride; Ferromagnetism; Fe
16
N
2
; Low temperature nitridation
1. Introduction
Fe
16
N
2
has attracted much attention due to its possible gigan-
tic magnetization [1]. Most of the investigations have been
performed on its thin lms prepared by applying various kinds of
deposition methods such as MBE and sputter deposition [24].
The values expected for the magnetic moments have been scat-
tered over a range between 2.4 and 3.9
B
.
Ferromagnetic Fe
16
N
2
ne powder was recently prepared by
low temperature nitridation of -Fe of about 20 nm crystallite
size obtained from -Fe
2
O
3
[5]. Its saturation magnetization
was 162 emu/g at room temperature. The value was too small
compared to the average magnetic moment of 2.52
B
estimated
from the hyperne elds in its M ossbauer spectrum. A satura-
tion magnetization value of 225 emu/g was recently observed
on the nitrided product at 130

C for 100 h from the -Fe ne

powder with about 100 nm particle size, which was obtained by
the reduction of -Fe
2
O
3
in hydrogen ow at 500

C for 8 h
[6]. An additional paramagnetic component was present in its
M ossbauer spectrum with an area ratio of 19%. A maximum
saturation magnetization of 278 emu/g could be expected for a
sample entirely formed of the ferromagnetic phase. This value
was about 30% larger than that of -Fe. There was a wide par-

Corresponding author. Tel.: +81 11 706 6739; fax: +81 11 706 6739.
E-mail address: kikkawa@eng.hokudai.ac.jp (S. Kikkawa).
ticle size distribution of -Fe
2
O
3
in the range of 5100 nm. Its
small size region might lead to a formation of either superpara-
magnetic Fe
16
N
2
or higher nitrides such as Fe
4
N with a smaller
magnetization.
The low temperature nitridation reaction should strongly
depend on the starting powder, especially on its particle size, size
distribution, surface morphology and the preparation method. In
the present study, particle size dependence of the low tempera-
ture nitridation was studied on -Fe ne powders prepared from
-Fe
2
O
3
with narrow particle size distribution.
2. Experimental
Three kinds of -Fe
2
O
3
ne powders with narrow particle size distributions
at 30 nm (A), 60 nm (B) and 200 nm (C) supplied by Sakai Chemicals Co. Ltd.
(FRO3, 6, 20) were used as starting materials. They were reduced to -Fe in
hydrogen stream at 500

C for 1 h. They were directly nitrided in ammonia ow

for 100 h at a temperature range between 130 and 170

C without air exposure.

Another preparation method was also applied to obtain monodispersed -Fe
ne particles smaller than 30 nm with a narrow size distribution. Iron pentacar-
bonyl (1 mmol) dissolved in octyl ether (20 ml) with either an equimolar mixture
of oleic acid and oleyl amine or oleic acid alone as stabilizer (1 mmol) was ther-
mally decomposed in argon atmosphere at 280

Cfor 30 min. Ethanol was added

as a occulant after cooling, centrifuged to remove supernatant iron oxide par-
ticles and then dispersed again in hexane. The purication process was repeated
twice.
An X-ray diffractometer (Philips Xpert-MPD) with monochromatized Cu
K radiation was used for phase identication. Magnetic hysteresis was studied
0925-8388/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2005.12.134
8 S. Kikkawa et al. / Journal of Alloys and Compounds 449 (2008) 710
Fig. 1. SEM images: (a) -Fe
2
O
3
ne powder (B) and (b) its reduced product.
in a eld of 15 kOe at roomtemperature using a vibrating sample magnetome-
ter (Riken Denshi BHV-50). A M ossbauer spectrometer (Topologic Systems
220) was employed to measure the magnetic properties at room temperature
using Co
57
as a -ray source. The spectrum was analyzed using the program of
M ossWinn 3.0.
3. Results and discussion
Morphology of the three kinds of -Fe
2
O
3
particles was
hexagonal plate-like with a narrow particle size distribution as
shown in Fig. 1. After their reduction at 500

C, the -Fe par-

ticles were slightly sintered together with each other at their
grain boundary forming porous mass. Primary particle sizes
of the -Fe powders were larger than those of the original -
Fe
2
O
3
particles. They were 60, 120 and 300 nm for A, B and C,
respectively.
Fe
16
N
2
was formed as a mixture with the unreacted -Fe after
the nitridation at 130

C of the starting powder (A) as shown in

Fig. 2. Weak ferromagnetic Fe
4
N appeared at 140

C. Control
of the nitrogen content to obtain Fe
16
N
2
was not easy in these
cases. Nitridation was very slow in the reaction of the powder
(C). Fe
16
N
2
was not formed at all even at 150

C, and only Fe
4
N
appeared above 160

C as summarized in Table 1. Too much

nitrogen was absorbed in the product during the nitridation. The
Fe
16
N
2
formation was the most controllable on the starting pow-
der (B). The amount of Fe
16
N
2
was the largest in the nitrided
product at 140

C in this case. The most suitable particle size of

-Fe may be around 100 nm for the formation of Fe
16
N
2
. Rela-
Fig. 2. XRD of the nitrided -Fe obtained from-Fe
2
O
3
. (A-1 and -2) Nitrided
-Fe (A) at 130 and 140

C; (B-1 and -2) nitrided -Fe (B) at 140 and 150

C;
(C-1 and -2) nitrided -Fe (C) at 150 and 170

C, respectively.
tive amount of Fe
16
N
2
was smaller than previous study carried
out by the present authors using -Fe
2
O
3
powder with similar
particle size as the starting material [6]. Powder morphology was
much more voluminous in the previous -Fe
2
O
3
than the present
iron oxide prepared from aqueous solution. The saturation mag-
netization value of the present nitrided product at 140

C was
207 emu/g, which is almost comparable to the value for -Fe.
Magnetic coercivity increased to 0.34 kOe from0.10 kOe for the
-Fe powder in the nitridation.
Crystallite size of the Fe
16
N
2
was estimated as 27 nm from
XRD line broadening. The size is larger than the critical size
for a single magnetic domain. Its M ossbauer spectrum could be
tted with four ferromagnetic components: Fe (1), Fe (2), Fe (3)
in Fe
16
N
2
, -Fe (36.4%) and a paramagnetic singlet (5.5%) as
summarized in Table 2. Observed area ratio of these magnetic
components in Fe
16
N
2
was 1.5:1.55:0.95. It should be 1:2:1 as
estimated fromits crystal structure. The deviation fromthe ideal
ratio suggests that there is a partial disordering of nitrogen in
the present Fe
16
N
2
crystal lattice. Some amount of the nitrogen
atoms are distributed in a random way similar to the crystal lat-
tice of

-nitrogen martensite and the saturation magnetization

is thus reduced.
Small FePt particles were expected to be suitable for future
ultrahigh-density magnetic recording media applications [7].
Its monodispersed nanoparticles were prepared by reduction
of platinum acetylacetonate and decomposition of iron penta-
cabonyl in the presence of oleic acid and oleyl amine stabilizer
[8,9]. Similar preparation method was applied to control the
particle size of -Fe ne powder in thermal decomposition of
iron pentacarbonyl in octyl ether solvent. Equimolar mixture of
oleic acid and oleyl amine stabilizer was added to the solvent to
change its amount against Fe(CO)
5
. The reaction rate of the ther-
S. Kikkawa et al. / Journal of Alloys and Compounds 449 (2008) 710 9
Table 1
Phases observed in the nitrided products
Nitridation temperatures (

C) -Fe powder (A) with

60 nm in particle size
-Fe powder (B) with
120 nm in particle size
-Fe powder (C) with
300 nm in particle size
130 -Fe >Fe
16
N
2
-Fe >Fe
16
N
2
-Fe
140 Fe
16
N
2
>-Fe >Fe
4
N Fe
16
N
2
>-Fe -Fe
150 Fe
16
N
2
>-Fe >Fe
4
N -Fe
160 Fe
4
N
170 Fe
4
N
Fig. 3. Monodispersed -Fe nanoparticles prepared by thermal decomposition of iron pentacarbonyl in the presence of oleic acid and oleyl amine stabilizer with
different molar ratios of the stabilizer/iron pentacarbonyl: (a) 0.2; (b) 0.5; (c) 2.
mal decomposition reduced with the amount of stabilizer. Size
and shape of the -Fe ne powder changed with the amount of
stabilizer as shown in Fig. 3.
-Fe nanopowder of about 30 nm was obtained in the case of
the stabilizer/Fe(CO)
5
=1/2 as shown in the middle of Fig. 3.
It was nitrided at 130

C for 100 h after the removal of the

excess stabilizer by heating in argon ow at 400

C for 1 h.
Its nitrided product was a mixture of Fe
16
N
2
with -Fe and its
magnetization was 184 emu/g at roomtemperature, almost com-
parable to the value of the present -Fe nanopowder. It was again
nitrided at 130

Cfor 150 h after grinding. Saturation magnetiza-

tion value decreased to 121 emu/g because weak ferromagnetic
Fe
4
N appeared together with Fe
16
N
2
. Its magnetic coercivity
was increased to 1.95 kOe from a small value of 0.5 kOe for
the -Fe nanopowder. The -Fe particles should be grown to
a diameter of around 100 nm in porous sphere to obtain pure
Fe
16
N
2
.
Ironparticles were assumedtobe boundtoOOCinoleic acid
[4]. Their round shape in a narrowsize distribution was observed
on the -Fe nanopowder prepared in presence of only oleic acid
as a stabilizer, as shown in Fig. 4. The particles grew with the
amount of oleic acid. The maximumsize was about 10 nmwhen
twice the amount of oleic acid as iron pentacarbonyl was added
to the solution.
Table 2
M ossbauer parameters in the nitrided product at 140

C
Fe (1) Fe (2) Fe (3) -Fe Singlet
Isomer shift (mms
1
) 0.127 0.256 0.244 0.13 0.277
Quadruple splitting
(mms
1
)
0.11 0.09 0.04
Hyperne eld (T) 29.1 31.4 40.2 33.2
Area ratio (%) 21.1 22.9 14.1 36.4 5.5
Fig. 4. Monodispersed -Fe nanoparticles prepared by thermal decomposition
of iron pentacarbonyl in the presence of oleic acid stabilizer with molar ratios
of the stabilizer/iron pentacarbonyl: (a) 0.5 and (b) 2.
4. Conclusion
In summary, particle size dependence of low temperature
nitridation to prepare Fe
16
N
2
with a gigantic magnetization was
studied starting from -Fe
2
O
3
powder with a narrow particle
size distribution. The -Fe powder with 120 nm in particle size
10 S. Kikkawa et al. / Journal of Alloys and Compounds 449 (2008) 710
obtained by hydrogen reduction of -Fe
2
O
3
powder with a par-
ticle size of 60 nm was the most suitable to prepare Fe
16
N
2
.
The nal product was a mixture with -Fe possessing a satu-
ration magnetization of 207 emu/g. Thermal decomposition of
iron pentacarbonyl was also studied in octyl ether solvent to
control the size and shape of -Fe powder product. Particle size
of -Fe nanopowder changed with the amount of stabilizer such
as oleic acid. The maximum size obtained was less than 30 nm.
It was too small to obtain Fe
16
N
2
with a large magnetization.
Acknowledgement
This research was partly supported by a Grant-in-Aid for
Exploratory Research from JSPS (#17655090).
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