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Transformation mechanism of magnetite nanoparticles

Article  in  MATERIALS SCIENCE-POLAND · July 2015


DOI: 10.1515/msp-2015-0037

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Materials Science-Poland, 33(2), 2015, pp. 278-285
http://www.materialsscience.pwr.wroc.pl/
DOI: 10.1515/msp-2015-0037

Transformation mechanism of magnetite nanoparticles


U MAR S AEED K HAN 1∗ , A MANULLAH 1 , A BDUL M ANAN 1 , NASRULLAH K HAN 2 ,
A MIR M AHMOOD 1 , A BDUR R AHIM 3

1 Department of Physics, University of Science and Technology Bannu, Pakistan


2 Department of Physics, Kohat University of Science and Technology, Kohat, Pakistan
3 Interdisciplinary Research Centre in Biomedical Materials (IRCBM), COMSATS Institute of Information Technology,
Lahore, Pakistan

A simple oxidation synthesis route was developed for producing magnetite nanoparticles with controlled size and mor-
phology. Investigation of oxidation process of the produced magnetite nanoparticles (NP) was performed after synthesis un-

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der different temperatures. The phase transformation of synthetic magnetite nanoparticles into maghemite and, henceforth, to
hematite nanoparticles at different temperatures under dry oxidation has been studied. The natural magnetite particles were

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directly transformed to hematite particles at comparatively lower temperature, thus, maghemite phase was bypassed. The phase
structures, morphologies and particle sizes of the produced magnetic nanoparticles have been investigated by X-ray diffraction
(XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectrometry (EDX) and BET surface area analysis.
Keywords: transformation; magnetite; maghemite; hematite; nanoparticles
© Wroclaw University of Technology.
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1. Introduction bulk magnetite in an aerobic atmosphere is very
slow, so no protection against oxidation is required.
Iron oxides (IO), such as magnetite, maghemite On the other hand, synthetic magnetites NP are ei-
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and hematite nanoparticles (NP), have attracted ther oxidized to other iron oxides during the syn-
great attention in the recent years, because of their thesis process or during storage in ambient atmo-
technological and industrial applications due to sphere [8]. Maghemite can be considered as an en-
their excellent and unique properties [1–7]. Iron tirely oxidized magnetite: the intermediate form of
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oxides are metal oxides used in such fields as hematite and magnetite. It is metastable with re-
high density magnetic recording media, gas sen- spect to hematite, which is a stable and common
sors, catalysts, pigments, nonlinear optics, anticor- phase of IO [11].
rosive agents, inorganic dyes, adsorbents, electron-
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ics, magnetic storage, biomedicine, ferrofluids and In this paper we present preparation of mag-
so on [8–10]. Iron oxides are common compounds netite nanoparticles by a modified oxidation
that exist as natural minerals and can also be pro- method and, henceforth, transformation of the
duced artificially. The IO polymorphic nature has prepared samples into maghemite and hematite
been known for a long time. Nowadays, IO and iron nanoparticles performed through dry oxidation
hydroxides exist in sixteen types. Some iron oxides process in ambient atmosphere. The transforma-
contain iron(II) and the others contain iron(III), but tion of bulk magnetite to maghemite and hematite
magnetite, having a unique nature, contains both through dry oxidation under atmospheric condi-
iron(II) and iron(III) in its structure [9, 10]. Ther- tions has been proven in [12, 13]. However, a com-
modynamically it is not stable in aerobic atmo- prehensive study of the possible transformations of
sphere. The oxidation rate of natural magnetite, i.e. the magnetite NP to other phases of IO with respect
to particle size, surface area and shape has not been
∗ E-mail: omar aps@yahoo.co.uk discussed in details so far.
Transformation mechanism of magnetite nanoparticles 279

2. Materials and methods


Magnetite NP were produced by modified oxi-
dation route. 20.00 g of FeCl2 ·4H2 O was dissolved
in 140 mL deoxygenated deionized water. 6.46 g
of KNO3 and 11.22 g of NaOH were dissolved in
60 mL deoxygenated water. The mixed solution of
KNO3 and NaOH was dropped into the iron solu-
tion at the rate of 1 mL/s until the temperature of
the iron solution achieved 40 or 80 °C, then the sys-
tem was stirred for 20 hours at that temperature.
The product obtained at 40 °C was divided into
three parts. Two parts of the product were heated
in the furnace at 350 and 600 °C. The product ob-

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tained at 80 °C was also divided into three parts.
Two parts were also heated in the furnace at 400

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and 800 °C. Detailed information about the pre-
pared samples has been included in Table 1.

3. Analytical techniques
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The prepared samples were characterized for
phase composition and crystallinity with the help
of XRD (Rigaku RAD-B system) at a scan-
ning rate of 3°/min, employing CuKα radiation Fig. 1. XRD images of iron oxide NP produced under
(λ = 0.15405 nm). The morphology, particles size different conditions: (a1) 40 °C via oxidation of
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and their size distribution in the prepared samples Iron(II) ions (magnetite), (b1) 350 °C via dry
oxidation, 30 min (maghemite), (c1) 600 °C via
were studied by TEM (JEOL Model CM12), work-
dry oxidation, 60 min (hematite).
ing at 100 kV accelerating voltage. The BET (Nova
2000, Quantachrome Instruments, Boynton Beach,
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USA) method was used for measuring the surface The increasing of particle size was probably
area. The particle size ”d” of the prepared samples due to irregular diffusion of particles at a higher
was estimated using the relation d = 6/ρA, with temperature, which enhanced the growth kinetics
density “ρ” and surface area “A” of the sample. The
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of the particles and, consequently, larger sized par-


elemental composition of the sample was analyzed ticles were produced. Transformation of Fe(OH)2
by EDX (JSM-5910, JEOL). to magnetite and its conversion to maghemite and
hematite under different temperatures and medi-
4. Results and discussion ums are summarized in Table 1. The XRD re-
sults for samples b1 and e1 match well to ICDD
The X-ray diffractograms of samples a1 – f1 card 240081 (maghemite) and for samples c1 and
are shown in Fig. 1 and Fig. 2. The XRD results f1 correspond to ICDD card 330664 (hematite).
of samples a1 and d1 match well to ICDD card The lattice parameters of magnetite and maghemite
190629 (synthetic magnetite), revealing that on in- differ slightly from each other [14]. It is illus-
creasing the reaction temperature from 40 to 80 °C, trated in Table 2 that d-values of all the XRD
the sharpness of the XRD peaks increased, and as peaks of maghemite samples are somewhat shifted
a result, the particle size also increased from 9 to to higher 2θ values as compared to the mag-
15 nm. netite samples. The d-values of magnetite sample
280 U MAR S AEED K HAN et al.

Table 1. Transformation of Fe(OH)2 to magnetite and its conversion to maghemite and hematite under different
temperatures and mediums.

Sample Precursors Product Type of Preferred Temperature Matching


No. transformation medium ICDD Cards
a1 Fe(OH)2 Magnetite Oxidation N2 ; Solid solution 40 °C 190629
b1 Magnetite Maghemite Dry Oxidation Air 350 °C 240081
c1 Magnetite Hematite Dry Oxidation Air 600 °C 330664
d1 Fe(OH)2 Magnetite Oxidation N2 ; Solid solution 80 °C 190629
e1 Magnetite Maghemite Dry Oxidation Air 400 °C 240081
f1 Magnetite Hematite Dry Oxidation Air 800 °C 330664

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Fig. 3. XRD diffractograms of samples obtained with-


out N2 gas protection: (m) 80 °C via oxidation
of Iron(II) ions (magnetite), (k) 400 °C via dry
oxidation (maghemite), 30 min, (l) 800 °C via
dry oxidation (hematite), 60 min.
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absence of N2 . In this case, poorly crystalline mag-


netite particles were produced due to the mixing
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of different types of iron oxides with each others.


These magnetite NP converted to poorly crystalline
maghemite and hematite NP by heating magnetite
NP in the furnace at 400 and 800 °C under dry
Fig. 2. XRD images of iron oxide NP produced under
oxidation.
different conditions: (d1) 80 °C via oxidation of
Iron(II) ions (magnetite), (e1) 400 °C via dry ox- Electron diffraction patterns and results of EDX
idation (maghemite), 30 min., (f1) 800 °C via analysis of samples a1, b1 and c1 are shown in
dry oxidation (hematite), 60 min Fig. 4. The EDX analysis of these samples shows
that the prepared samples are composed of iron
and oxygen only. The EDX result of sample a1
are slightly larger as compared to the maghemite shown in Fig. 4 illustrates that the prepared sam-
samples. ple is made of iron and oxygen. The atomic ratios
Fig. 3 shows that X-ray diffractograms of in the samples shown in Fig. 4 are close to the the-
magnetic NP prepared by oxidation route in the oretical atomic stoichiometric ratios for magnetite,
Transformation mechanism of magnetite nanoparticles 281

Table 2. Comparison of d values and 2 theta angles of the prepared samples of magnetite and maghemite.

Sample a1 Sample b1 Sample d1 Sample e1


(hkl)
2 Theta d(Å) 2 Theta d(Å) 2 Theta d(Å) 2 Theta d(Å)
(220) 30.119 2.96469 30.256 2.95163 30.114 2.96516 30.156 2.96177
(311) 35.499 2.52674 35.627 2.51798 35.495 2.52701 35.546 2.51851
(400) 43.151 2.09474 43.379 2.08428 43.192 2.09288 43.207 2.09218
(511) 57.094 1.61190 57.319 1.60611 57.163 1.61012 57.195 1.60931
(440) 62.708 1.48041 62.843 1.47756 62.729 1.47912 62.862 1.47717

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Fig. 4. Diffraction patterns and EDX images of samples a1, b1 and c1.

which are 42.9 % and 57.1 % for iron and oxygen, and hematite possess the same atomic and weight
respectively. The weight ratio of the elements in ratios, however, differentiation between them can
sample a1, which is also shown in Fig. 4, is close to be easily made with the help of their colours. The
the theoretical weight stoichiometric ratio (72.41 % colour of sample b1 is dark brown, which is the
Fe and 27.59 % O), as well. The EDX analysis colour of maghemite. The colour of sample c1 is
shows that sample a1 consists of magnetite phase. red, which is the colour of hematite.
The EDX analysis of samples b1 and c1 shows The electron diffraction patterns of samples a1,
that the atomic and weight ratios of these samples, b1 and c1 are also shown in Fig. 4. The images il-
which are also shown in Fig. 4, are close to the re- lustrate that the samples a1 and b1 are crystalline
spective theoretical atomic and weight stoichiomet- and have cubic spinel structures. The sample c1
ric ratios of maghemite and hematite. Maghemite is also crystalline and has a hexagonal structure.
282 U MAR S AEED K HAN et al.

The electron diffraction patterns confirm XRD and NP compared to magnetite NP, and the increase
EDX results for these samples. in the size of hematite NP compared to magnetite
TEM images of the samples, showing the shape and maghemite NP, most likely involve the well-
and particle size of the produced particles, have known Ostwald ripening process [15]. Maghemite
been summarized in Table 3 and illustrated in and hematite NP are produced through dry oxida-
Fig. 5. The morphology of the majority of particles tion of magnetite by chain mechanism involving
contained in the samples is spherical. The particle recrystallization of smaller particles of the precur-
size in the prepared samples (a1 – f1) was also mea- sor. The NP size is the most significant feature,
sured by the XRD and BET techniques the results, which describes the nature of aerosols. The nature
of which are also given in Table 3. of aerosol particles is described by three types of
forces, i.e. (i) inertial, (ii) gravitational and (iii) dif-
The transformations of magnetite to the other
fusional. The microparticle system is governed by
phases of IO via dry oxidation are shown in Ta-
the inertial and gravitational forces. The NP system
ble 1. The samples a1 and d1 of magnetite NP
is governed by diffusional forces and the nature of

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(black in colour) transformed to maghemite, which
NP is more similar to a gas or a vapor, thus, it sat-
is reddish brown in colour, on heating in furnace
isfies the basic laws of gaseous diffusion [16].

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at 300 to 400 °C for 30 min. The sample a1 and
The magnetite NP on heating at 350 to 400 °C
d1 on heating at 600 and 800 °C in furnace for
in air, transformed to maghemite NP via dry oxida-
60 min, transformed to hematite, which is dark
tion. This transformation mechanism agrees with
red in colour. The results of colour variation of
diffusion phenomenon for magnetite. The trans-
different phases of IO, confirmed by XRD, show
formation of magnetite to maghemite takes place
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that at 300 to 400 °C, magnetite transformed to
by the dry oxidation of ferrous ions. The fraction
maghemite, which is metastable, and the heating
transformation equation is given below [8]:
of magnetite NP at 600 to 800 °C, transformed it to
hematite NP, the most stable phase of IO, which is
Mt /M∞ = 6π −1/2 (Dt/a2 )1/2 − 3Dt/a2 (1)
the end product of this transformation process.
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It was observed that magnetite transformed to where Mt is an iron species to be oxidized af-
maghemite at lower temperature in comparison to ter time t and M∞ is the corresponding amount of
hematite because both magnetite and maghemite iron after infinite time. D is the diffusion constant,
have CCP anion arrangement. Hematite conversion which is the function of temperature and a is the
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involves a change from a CCP anion arrangement average radius of the particles. The diffusion is
to HCP, and since substantial rearrangement of thebased on the particle size.
ions is needed, a higher temperature is required for It was observed that magnetite NP smaller than
the transformation of magnetite to hematite. It was
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15 nm were readily oxidized to maghemite and


also observed that the morphology of the precursorhematite NP at 350 to 400 °C and 600 to 800 °C
(magnetite) was preserved throughout the transfor-just for 30 and 60 min duration, respectively. It
mation to maghemite and hematite, which is shown means that NP possess higher reaction rate due to
in Fig. 5. This type of transformation involves in-
the small diffusion pathways and, therefore, trans-
ternal atomic rearrangement within a single crystal
form more rapidly to the other phases compared
of an initial phase, which being transformed into a
to the microparticles. The diffusion rate is slow in
single crystal of another phase, undergoes so called
the larger crystal so the diffusion pathway is very
topotactic process, which occurs within the solid long. Therefore, complete transformation of bulk
phase. Solid state transformation in dry state needs
magnetite to the other phases of IO needs higher
certain atomic movements; it usually occurs only at
temperature for a long time. The diffusion constant
the higher temperature [8]. is inversely related to the size of NP as it is given
The sizes of the samples summarized in Table 3 in equation 1. It also depends on the diffusion rate
show that the increase in the size of maghemite during the diffusion process. The dispersion rate of
Transformation mechanism of magnetite nanoparticles 283

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Fig. 5. TEM images of iron oxide NP produced under the following conditions:
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(a1) 40 °C via oxidation of Iron(II) ions (magnetite), (b1) 350 °C via dry oxidation, 30 min (maghemite),
(c1) 600 °C via dry oxidation, 60 min (hematite), (d1) 80 °C via oxidation of Iron(II) ions (magnetite), (e1)
400 °C via dry oxidation, 30 min (maghemite), and (f1) 800 °C via dry oxidation, 60 min (hematite).

Table 3. Comparison of the size of prepared particles obtained by XRD, BET and TEM.

Samples SA(BET) BET XRD TEM


(m2 /g) d (nm) d (nm) d (nm)
a1 124.70 9.50±0.32 9.02±0.34 9.66±0.66
b1 103.50 11.70±0.44 9.43±0.42 11.38±0.71
c1 35.60 31.44±0.54 22.63±0.46 23.86±0.62
d1 55.30 20.21±0.41 14.63±0.39 15.11±0.57
e1 45.02 27.51±0.72 16.32±0.53 18.55±0.47
f1 34.10 32.15±0.81 22.46±0.67 24.50±0.55
284 U MAR S AEED K HAN et al.

NP is higher than the dispersion of the microparti- the beginning, thus, stopped the further transforma-
cles because NP have greater diffusion coefficient tion process at that temperature.
and mix quickly in the aerosol system. NP undergo
numerous collisions with each other leading to ag-
5. Conclusions
glomeration and growth; this mechanism is em-
ployed for the formation of NP. The mobility and Synthetic magnetite nanoparticles were easily
concentration are two important factors, which in- transformed into maghemite and hematite by dry
fluence the rate of agglomeration of NP [8]. oxidation process in air for 30 min and 60 min in
the temperature range of 350 to 400 °C and 600
to 800 °C, respectively. Natural magnetite parti-
cles larger than 200 nm were not transformed to
maghemite but directly transformed to hematite. In
dry state transformation, maghemite and hematite
were dependent on the initial material used and

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retained the morphology of their precursor (mag-
netite). It was observed that the transformed par-

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ticles had bigger size compared to magnetite
particles.

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