JOURNAL OF RAMAN SPECTROSCOPY

J. Raman Spectrosc. 2003; 34: 845852

Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jrs.1056
Raman study of magnetite (Fe
3
O
4
): laser-induced
thermal effects and oxidation
Olga N. Shebanova

and Peter Lazor

Department of Earth Sciences, MineralogyPetrology, Uppsala University Villav agen 16, SE-752 36 Uppsala, Sweden
Received 19 February 2003; Accepted 1 June 2003
Natural magnetite (Fe
3
O
4
/ inthe formof single crystal andpowder was studiedbylaser Ramanspectroscopy
at various laser powers. The correlations between the power of the excitation laser, the temperature of the
sampled spot and the degree of oxidation of magnetite were accurately established. In the course of the
oxidation of the single crystal of magnetite, the rst characteristic features of hematite appear at about 300
and 410 cm
1
, at a temperature close to 240

C. This may explain the erroneous assignment of these modes

to the intrinsic Raman modes of magnetite in some studies. For the nely powdered magnetite, which
is much more easily prone to oxidation, the reaction mechanism proceeds via a metastable maghemite
(g-Fe
2
O
3
/ before the nal product hematite is formed. Three independent methods based on the quasi-
harmonic approximation and on the ratio of the Stokes to anti-Stokes intensities were used to calculate
the local temperature of the laser-heated spot. Temperature-induced shifts of phonon bands were also
evaluated. The phonons shift at the following rates: A
1g
0.023(1) cm
1
K
1
, T
2g
.2/ 0.030(2) cm
1
K
1
,
E
g
0.019(5) cm
1
K
1
and T
2g
.1/ 0.00.1/ cm
1
K
1
. Copyright 2003 John Wiley & Sons, Ltd.
KEYWORDS: Raman spectroscopy; magnetite; oxidation; laser heating
INTRODUCTION
Raman spectroscopy is a powerful experimental technique
for probing the vibrational and structural properties of
materials. It is well known that the high density of power
from a laser excitation source often poses a problem in a
Raman experiment owing to its adverse effects on a sample.
1
This is particularly true for micro-Raman experiments where
laser beams are focused to a spot size with a diameter of only
a fewmicrometers. Owing to the absorption of radiation, the
local spot temperature may increase by hundreds of degrees.
This causes the wavenumber shift of Ramanmodes or, worse,
the alteration of a sample as the result of effects such
as oxidation, recrystallization, orderdisorder transitions
(cation redistribution), phase transition or decomposition.
Iron oxides, being good absorbers in the range of
wavelengths of excitation lasers, belong to materials where
care has to be taken when conducting a Raman experiment.
This applies especiallytoRamanstudies onoxides containing
divalent iron, e.g. w ustite and magnetite, which are easily

Correspondence to: Olga N. Shebanova, Department of Earth

Sciences, MineralogyPetrology, Uppsala University, Villav agen
16, SE-752 36 Uppsala, Sweden. E-mail: olga.shebanova@geo.uu.se
Contract/grant sponsor: Swedish Research Council
(Vetenskapsr adet).
oxidized at elevatedtemperatures (w ustite also decomposes)
when studied in open air containing moisture.
The effects of the laser power and associated heating
have been studied in some detail on a number of iron
oxides and oxyhydroxides by de Faria et al.
1
We have
recently conducted a detailed polarized Raman study on
magnetite (O. N. Shebanova and P. Lazor, Journal of Solid
State Chemistry, 174, in press) aimed primarily at the
complete symmetry assignment of Raman bands. In order
to resolve some discrepancies in the reported number
of peaks and wavenumbers, we have also carried out a
study of the evolution of the magnetite spectrum as a
function of laser power. We report the results in this paper.
Generally, we nd agreement with the conclusions of the
two earlier studies, mainly about the qualitative evolution of
the spectrum of magnetite at various laser powers. The new
contribution in this work lies in its quantitative approach
for calculating the local temperature of the heated spot.
Three independent methods basedonthe Stokesanti-Stokes
ratio of intensities and on the quasi-harmonic change of
wavenumbers with a change of volume yield consistent
temperature determinations, which is in good agreement
with reported observations on the oxidation of magnetite.
We performed experiments on the single crystal and also
on powdered magnetite in order to examine the grain-size
effect.
Copyright 2003 John Wiley & Sons, Ltd.
846 O. N. Shebanova and P. Lazor
EXPERIMENTAL
Sample characterization
A sample of natural magnetite was obtained from the
metamorphosed iron formation at Gr angesberg, Sweden.
The chemical composition is presented in Table 1.
2
The unit-
cell constant determined by x-ray powder diffraction is a D
8.3945 (11)

A, which is in good agreement with a published
value
3
for natural Fe
3
O
4
, a D 8.3941(7)

A. The freshly
preparedne-grainedmagnetite powder (approximate grain
size 0.31 m) was compacted to a tablet prior to the
experiments.
Methods
Light-scattering experiments were conducted using a single-
stage imaging spectrograph (Oriel) equipped with a thermo-
electrically cooled (60

C) charge-coupled device (CCD)

detector (Andor, DV420 OE). The Raman spectra were
excitedby 514.5 nmradiationfromanargonionlaser (Coher-
ent, Innova) and collected in a backscattering geometry
withspectral resolution6 cm
1
. Two holographic supernotch
lters (Kaiser) were used to reject the Raleigh line. No polar-
izers were used. The laser beam was focused on the sample
by a 20 lens to a spot size of ca 510 m. The reported
Raman wavenumbers have uncertainties of 1.5 cm
1
. The
laser power reaching the sample surface was varied in the
range 760 mW. The typical acquisition time was 60 s. All
values of the laser power specied in this paper correspond
to estimates of power reaching the sample surface after
accounting for reection losses at the optical surfaces in the
system. Direct measurement of laser power at the sample
was not possible owing to the insufcient sensitivity of the
power meter.
RESULTS AND DISCUSSION
Experiment on single crystal of magnetite
Figure 1 shows the Raman spectrum of magnetite collected
from the polished octahedral face f111g. The symmetry
assignment of Raman bands is according to the results of
our recent study (see page 1). The evolution of the spectra
with stepwise increase in laser power is shown in Fig. 2.
New features in the spectra begin to appear when the power
Table 1. The content of trace elements in the studied sample
of natural magnetite
Element Concentration/ppm Element Concentration/ppm
Zn 59 Ti <425
Pb 9 V 1920
Cu 11 Cr 17
Co 41 Mo 4
Ni 92 Cd 1.0
Mn 365
-800 -600 -400 -200 0 200 400 600 800
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
Rayleigh line
514.53 nm
A
1g
A
1g
T
2g
(2)
T
2g
(2)
T
2g
(1)
T
2g
(1)
Eg
Eg
Wavenumber (cm
-1
)
Figure 1. Raman spectrum collected from the octahedral face
f111g of a single crystal of magnetite. The symmetry
assignment follows results of O. N. Shebanova and P. Lazor
(see page 1).
200
60
55
60
50
45
40
35
30
50
40
30
20
10
300
800
1000
1200
1400
W
a
ve
n
u
m
b
e
r (c
m
-1
)
400
500
W
a
v
e
n
u
m
b
e
r (c
m
-1
)
L
a
s
e
r

p
o
w
e
r

(
m
W
)
L
a
s
e
r

p
o
w
e
r

(
m
W
)
I
n
t
e
n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
600
700
800
Figure 2. Raman spectra taken from a single crystal of
magnetite with a stepwise increase in laser power. The inset
shows spectra in the high-wavenumber range.
is increased above 20 mW. The rst and the most apparent
sign of the onset of a change is the growth of new peaks
at 410 and 300 cm
1
. In the early stages of this change the
Copyright 2003 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2003; 34: 845852
Raman study of magnetite 847
detection of the inconspicuous peak at 300 cm
1
may be dif-
cult because of its overlap with the much more intense E
g
mode at 306 cm
1
. However, the onset of its growth may be
seen by plotting the A
1g
/E
g
and T
2g
2/E
g
ratios of the inte-
grated intensities of Raman bands (Fig. 3). The decrease in
the ratios at laser power higher than 15 mW reveals the exis-
tence of a new contribution to the intensity of the E
g
mode.
This is clearly conrmed with a further increase in the laser
power: the appearance of several new strong bands, includ-
ing the band at 300 cm
1
, signies a dramatic change in the
nature of the sample (Fig. 2). Concurrently, the intensities of
the Raman bands of magnetite gradually vanish. Analysis
of the spectrum of the nal reaction product shows that
magnetite, subjected to increased laser power in the course
of the Raman experiment conducted in air, was oxidized to
the trivalent iron oxide hematite (-Fe
2
O
3
. The presence of
the two bands at around 300 and 410 cm
1
in the early stages
of the oxidation of magnetite may lead to their incorrect
assignment as intrinsic Raman modes of this spinel, in cases
when a minor surface oxidation is left unnoticed. Such an
oxidation may be brought about either by the laser beam
during the Raman experiment or by a prolonged exposure
to the environmental conditions prior to the experiment. For
example, a thin hematite lm may cover an unpolished sur-
face of a crystal of natural magnetite. Indeed, several studies
have reported Raman bands of magnetite close to 300 cm
1
(Refs 46) and/or 410 cm
1
(Refs 48).
Laser Raman spectroscopy represents a powerful tool
for the in situ investigation of processes of oxidation. A
large number of oxidation studies using this technique
10 15 20 25 30
I
n
t
e
n
s
i
t
y

r
a
t
i
o
2
4
6
8
10
12
90 135 180 225
Temperature (C)
270
A
1g
/ E
g
T
2g
(2)/E
g
Laser power (mW)
Figure 3. Dependence of the intensity ratios of bands of
magnetite on the laser power: (

) A
1g
/E
g
; () T
2g
(1)/E
g
.
have been conducted on a wide range of materials (for
a review see, e.g., Ref. 9). It has been recognized that
reaction mechanisms, product morphologies and even the
nal products depend sensitively on the type of oxidation
process.
10
A laser-induced oxidation usually differs from
an isothermal oxidation or from a simple high-temperature
annealing in the presence of oxygen. The differences arise
primarily from the photolytic and pyrolytic inuence of
laser light. From a purely thermal point of view, the
large temperature gradient present in a spot heated by
the focused laser will result in thermal stresses, gradient
of lattice constant, enhanced diffusion of species, modied
nucleation rate (kinetics), etc. The photolytic effects of laser
light originate from the photonelectron interactions at the
irradiated surface. Although the phenomenon of electron-
transfer oxidation is well known,
11
its role in the case of
magnetite has yet to be established. The semiconducting
nature of magnetite is explained by the fast electron hopping
between iron cations on the octahedral sites. It is not unlikely
that the laser-assisted electron transfer, along with the
thermal effects, may play a major role in the oxidation of this
inverse spinel. Moreover, a realistic view of the oxidation
of magnetite has to consider also a possible catalytic effect
of hydroxyl (OH) groups adsorbed on the surface. Their
inevitable occurrence results from the dissociation of water
molecules interacting with the surface of magnetite.
12,13
It was not a purpose of this work to provide a detailed
picture of the mechanism of the laser-induced oxidation
process of magnetite. We rather aimed at establishing the
connections between the laser power, evolution of Raman
spectra due to the oxidation, the temperature of the laser-
illuminated spot and the grain-size effect.
The thermal effect of a laser beam results from its
absorption by a sample. Optical studies on the iron oxides
magnetite and hematite report a strong absorption of light
withabsorptivity8595%inthe range of wavelengths typical
for lasers used in Raman experiments.
1416
Apart from
changes resulting from the oxidation, the high-temperature
Ramanspectra exhibit redshifts of bands andalso anincrease
in bandlinewidths. At laser power higher thanabout 80 mW,
the heating effect is directly documented by the CCDcamera
image of thermal glow from the laser-heated spot, and by
the detection of a strong thermal background (blackbody
radiation) in the spectra.
We applied three independent methods for the temper-
ature calculation from Raman spectra using the observed
temperature-induced shifts of phonon wavenumbers. The
calculated temperatures represent the local temperature of
a heated spot and should be more representative than the
bulk sample temperatures obtained from thermocouples in
experiments using a heating stage.
Stokesanti-Stokes method
High-quality Raman spectra showing Stokes and anti-Stokes
bands (Fig. 4) provided peak positions and intensities for
Copyright 2003 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2003; 34: 845852
848 O. N. Shebanova and P. Lazor
-500 0 500 1000 1500
I
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s
i
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(
a
r
b
.

u
n
i
t
s
)
22.5 mW
31.5 mW
34.5 mW
40.5 mW
49.5 mW
Wavenumber (cm
-1
)
Figure 4. Selected Raman spectra collected from a single
crystal of magnetite with a stepwise increase in laser power.
The ratios of the Stokes to anti-Stokes peak intensities of the
A
1g
mode below a laser power of 30 mW were used for the
temperature calculations.
the temperature evaluation using the following expression
based on the Boltzmann distribution of modes between the
energy levels:
I
anti-Stokes
I
Stokes
D

0
C
R

4
e

E
f
E
i
kT
where
0
and
R
are wavenumbers of the Rayleigh line
and the Raman mode, respectively, I
Stokes
and I
anti-Stokes
are
the intensities of peaks on the Stokes and anti-Stokes sides,
respectively, E
i
E
f
D hc
R
represents the change of energy
in the scattering process, k is the Boltzmann constant, c is
speed of light, h is Plancks constant and T is the absolute
temperature. Wavenumbers and intensities of the A
1g
mode
of magnetite were used as input parameters. The intensities
were correctedfor the spectral responses of the optical system
and the CCD detector (quantum efciency).
Quasi-harmonic approximation for the shifts of
wavenumbers
Inthis approximation, the entire effect of the observedchange
of wavenumbers is attributed to the volume change only.
The intrinsic anharmonicity due to the phononphonon
interaction is neglected. Recently, Gupta et al.
8
arrived at the
conclusion that the anharmonic contributions in magnetite
are very small. Using the denitions of isothermal
T
and isobaric
P
Gr uneisen parameters, the quasi-harmonic
approximation is expressed as

T
D
P
where

T
D
dln
vib
dlnV
m
D
K
T

vib
d
vib
dP
and
P
D
1

vib
d
vib
dT
K
T
is the isothermal bulk modulus, P is pressure, V
m
is
molar volume and is the coefcient of volume thermal
expansion. Inthis model, the observeddecrease of vibrational
wavenumbers originates entirelyfromthe thermal expansion
of magnetite. The equality of
T
and
P
further implies that
the volume change resulting fromthis thermal expansioncan
be presumed to originate from a pressure change instead.
This allows us to use our recent results on the high-
pressure dependence of Raman modes (O. N. Shebanova
and P. Lazor, Journal of Chemical Physics, 2003, 119, N12,
in press) for temperature calculations in this study. In
particular, we use Gr uneisen parameter
T
D 1.31 for the
A
1g
mode. The unknown temperatures T are obtained as
solutions of the following equation:
V
m
T V
m
P
T
D V
m0
e

T
T
0
tdt
where the pressure P
T
is so-called equivalent pressure,
causing the same volume change as the temperature T and
V
m0
is the molar volume of magnetite at ambient temperature
T
0
and at pressure 100 kPa. P
T
was determined from the
high-pressure equation of state for magnetite reported by
Nakagiri et al.
17
The thermal expansion coefcient T
was taken from Okudera et al.
18
in the form T D
2.137 10
5
K
1
C7.3 10
8
K
2
[T (K) 298 K].
Calculation of temperature from the thermodynamic
Gr uneisen parameter
The third possible way to estimate the temperature is based
on the following denition of the thermodynamic Gr uneisen
parameter :
T
therm
D
TK
T
TV
m
T
C
V
T
where C
V
represents the heat capacity at a constant volume.
Its temperature dependence has been studied by Grnvold
and Sveen.
19
For the bulk modulus K
T
we consider a linear
decrease with temperature at the rate 0.026 GPa K
1
taken
from the thermodynamic assessment on magnetite carried
out by Saxena et al.
20
By setting
therm
D
T
, we derive the following relation-
ship between the wavenumber and the molar volume:

vib
T D
0vib

V
m0
V
m
T

T
therm
Copyright 2003 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2003; 34: 845852
Raman study of magnetite 849
where
0vib
is wavenumber under ambient conditions. Using
the experimentally observed wavenumber values
vib
for the
A
1g
mode we solved the last equation for the corresponding
temperatures T.
Figure 5 shows the calculated correlations between
the laser power and sample temperature from all the
three methods. At the initial laser power of 7.5 mW,
temperatures determined from the quasi-harmonic method
and Gr uneisen parameter method were normalized to the
temperature calculated fromthe Stokes/anti-Stokes method.
The estimated accuracy for the Stokes/anti-Stokes method
is about 25 K, whereas for the methods based on the
quasi-harmonic approximation and Gr uneisen parameter
method the accuracy is about 40 K. The agreement
between the different methods of calculation is reasonably
good, particularly between the Stokes/anti-Stokes method
and the Gr uneisen parameter method. The more or less
linear relationship may seem surprising. Apparently, the
laser power densities remain sufciently low and do
not cause non-linear runaway effects. Strictly, from the
thermodynamics formalism point of view, the second and
third methods are not independent because they can be
relatedby the thermodynamic arguments. However, theyare
independent from the input parameters point of view. We
use different input experimental parameters that originate
from independent sources.
The temperature dependence of Raman mode wavenum-
bers up to 350

C is shown in Fig. 6. Temperatures

obtained from the Gr uneisen parameter method were
used in the plot. With temperature increase the mode
wavenumbers decrease linearly at the following rates:
A
1g
0.023(1) cm
1
K
1
, T
2g
2 0.030(2) cm
1
K
1
, E
g

0.019(5) cm
1
K
1
and T
2g
1 0.001 cm
1
K
1
. The num-
bers in parentheses represent standard deviations [e.g.
0.023(1) corresponds to 0.023 0.001].
10 20 30 40
T
e
m
p
e
r
a
t
u
r
e

(

C
)
100
200
300
400
500
the first sign
of oxidation
Laser power (mW)
Figure 5. Correlations of the laser power with a local
temperature of the sample evaluated by three methods. ()
Stokes/anti-Stokes method; () quasi-harmonic approximation
using the high-pressure phonon shift; ( thermodynamic
Gr uneisen parameter method. In all three methods only the
shift of the A
1g
mode was considered.
50 100 150 200 250 300 350
W
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
180
190
200
280
290
300
310
525
530
535
540
655
660
665
670
A
1g
T
2g
(2)
E
g
T
2g
(1)
11 23 34
Laser power (mW)
Temperature (C)
Figure 6. Wavenumbers of the Raman bands of magnetite as
a function of temperature/laser power.
Up to 240

C the spectra exhibit a steady shift to

lower wavenumbers for all bands of magnetite. Also, the
temperature dependence of peak widths for the A
1g
and
T
2g
(2) modes [Fig. 7(a)] shows a typical behavior of the
gradual increase of the FWHM. Above 240

C this regular
dependence is broken and the rst changes in the Raman
pattern become apparent. One can observe a signicant
decrease in the intensity of the A
1g
and T
2g
(2) modes relative
to the E
g
mode, andthe emergence of a newbandat 400 cm
1
.
With further increase in laser power corresponding to a
temperature of about 280

C, additional new peaks appear

at 600, 220 and 1293 cm
1
(Figs 2 and 4). Such a set of bands
is characteristic of the spectrum of hematite.
2123
The rst
two bands are assigned as E
g
(5) and A
1g
symmetry modes,
respectively, and the peak near 1300 cm
1
is identied as a
two-magnon scattering by Hart et al.
24
and Martin et al.
25
or
as a second-order phononphonon interaction by McCarty
26
and Massey et al.
22
.
The decrease of the peak width for the E
g
mode of
magnetite above 240

C [Fig. 7(b)] requires some comments.

It is well known
4,8,14
(also O. N. Shebanova and P. Lazor,
Journal of SolidState Chemistry, 174, inpress) that the Raman
modes of magnetite are unusually broad (typical FWHMs
around 4050 cm
1
. The origin of this phenomenon has
been attributed to the strong electronphonon interaction in
this compound.
8
On the other hand, the typical linewidths
of the Raman modes of hematite are only 1020 cm
1
. The
evolution of linewidths above 240

C shown in Fig. 7(b) can

be understood as the disappearance of the broad E
g
mode
of magnetite and gradual growth of the narrow E
g
(3) mode
Copyright 2003 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2003; 34: 845852
850 O. N. Shebanova and P. Lazor
100 200 300 400
P
e
a
k

w
i
d
t
h

(
c
m
-
1
)
P
e
a
k

w
i
d
t
h

(
c
m
-
1
)
20
30
40
50
60
70
50 100 150 200 250 300
40
50
60
70
80
90
A
1g
T
2g
E
g
(b)
(a)
Temperature (C)
Temperature (C)
Figure 7. Dependence of the peak widths (FWHM) of Raman
modes of magnetite on temperature. (a) (

) T
2g
(2) mode and
(

) A
1g
; (b) E
g
mode.
of hematite. The usual behavior for the FWHM is restored
above 300

C where the entire contribution to the linewidth

comes solely from the E
g
(3) mode of hematite.
All the observations clearly testify to the beginning
of a hematite nucleation on the magnetite crystal above
some critical value of the laser power. The transformation
temperature calculated from the Stokes/anti-Stokes method
and the Gr uneisen parameter method is around 240

C
(Fig. 5), which is in a very good agreement with literature
data on the oxidation of magnetite in air.
27
Afurther increase
in illumination power leads to a rapid growth of peaks of
hematite accompanied by a gradual deterioration of the
modes of magnetite. Figure 8 summarizes the evolution
of mode wavenumbers of magnetite and hematite during
the process of oxidation. The open circles symbolize peak
positions in the spectrum taken from the quenched sample
after having been subjected to the highest laser power
during experimental runs (60 mW). The corresponding
Raman pattern is that of pure hematite [Fig. 9(c)]. Changes
documented for the magnetite sample were irreversible.
Examination under a microscope showed that the surface of
the sample subjected to laser irradiation exhibited traces
of alteration with the distinctive brownred features of
hematite.
1300
Temperature (C)
0 100 200 300 400
W
a
v
e
n
u
m
b
e
r

(
c
m
-
1
)
200
300
400
500
600
700
A
1g
A
1g
(2)
T
2g
(2)
A
1g
(1)
T
2g
(1)
Eg
E
g
(5)
E
g
(4)
11 23 34 45
Laser power (mW)
E
g
(2)+E
g
(3)
2nd-order
scattering
Figure 8. Wavenumbers of the Raman bands of magnetite
and hematite as a function of temperature/laser power. (

)
Magnetite; () hematite; (

hematite corresponding to the last

spectrum taken at the end of experimental runs [Fig. 9(c)].
Assignment of modes of hematite follows Beattie and Gilson.
21
Experiment on powdered magnetite
Another series of experiments were conducted on a freshly
prepared ne-grained powder of magnetite (approximate
grain size 0.31 m) compacted to a tablet. The starting
laser power at about 23 mW had no affect on the sample.
Further stepwise increases in power caused changes in the
Raman spectra, which we attribute to oxidation. Broadening
and a deterioration of bands in the 400600 cm
1
region,
along with the development of a new peak at about
700 cm
1
, indicate the rst stage of the oxidationof magnetite
[Fig. 9(a)]. These features are characteristic of the iron oxide
maghemite (-Fe
2
O
3
, a cation-decient magnetite with a
defective cubic structure. The presence of hematite bands in
the spectrum, along with those of maghemite, is explained
by the metastability of maghemite with respect to hematite.
The Raman spectra collected at higher powers are consistent
with pure hematite [Fig. 9(b)].
The different oxidation pictures obtained for the single
crystal andthe powder illustrate the difference inphenomena
underlying the oxidation mechanism for large and small
Copyright 2003 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2003; 34: 845852
Raman study of magnetite 851
Wavenumber (cm
-1
)
200 400 600 800 1000 1200 1400 1600
I
n
t
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n
s
i
t
y

(
a
r
b
.

u
n
i
t
s
)
E
g
(
5
)
A
1
g
(
2
)
E
g
(
4
)
E
g
(
2
)
+
E
g
(
3
)
A
1
g
(
1
)
E
g
(
1
)
(c)
(b)
(a)
2nd-order
scattering
Figure 9. Selected spectra collected from the starting sample
of magnetite with a stepwise increase in laser power.
(a) Powdered magnetite at laser power 18 mW; arrow indicates
the peak of maghemite; (b) powdered magnetite at 24 mW;
(c) single crystal of magnetite after having been subjected to a
power of 60 mW. The Raman bands are identied as peaks of
hematite. Assignment follows Beattie and Gilson.
21
particles pointed out by Feitknecht and Mannweiler.
28
Dependingonthe crystalline size, two paths for the oxidation
of magnetite were proposed by Feitknecht and Gallagher.
29
A rst-step formation of the intermediate solid solution
phase Fe
3x
O
4
is common both for small and for large
particles, and thereafter the kinetics takes a main role in
the process. For small particles (less than about 3000

A) the
reaction rate is sufciently high to complete the oxidation
even at low temperatures whereas higher temperatures
are required if particles are larger. The end products in
both cases are different. Fine crystalline material yields -
Fe
2
O
3
whereas large particles respond to the temperature
increase by a disproportionation to -Fe
2
O
3
and Fe
3
O
4
from Fe
3x
O
4
. Reduced in such a way, magnetite goes
directly to -Fe
2
O
3
with a continuous temperature increase.
The different behavior depending on the particle size was
explained by the lattice strain developing during oxidation.
This conclusion was based on the model proposed by
Gallagher et al.,
27
whopredictedthat duringoxidationa high
concentration gradient of cation holes would develop in the
monocrystalline particles, leading to a gradient in the lattice
constant; thus lattice strain would develop. Hence the lattice
strain was assumed to be the driving force for the nucleation
of -Fe
2
O
3
. The difference in the concentration gradient
on the surface and in the core of a particle is responsible
for the change in the lattice parameters promoting the strain
development, andtherefore the abilitytoaccommodate stress
is better for small particles than large grains.
The nucleationof hematite inthe nal stage of our heating
experiments conducted on the ne powder is in agreement
with the possibility of the transformation of a metastable
-Fe
2
O
3
to the thermodynamically more stable -form even
for small particles at temperatures above 250

C.
27
CONCLUSIONS
We have conducted Raman experiments on magnetite at a
various laser powers. Above some critical value of the power,
the Raman spectra started to show bands of hematite. The
rst recognizable features of hematite appeared at about 300
and 410 cm
1
. With further power increase the intensity of
the bands of hematite grew dramatically and dominated the
spectra whereas the modes of magnetite diminished to non-
existence. For a powderedmagnetite, the power thresholdfor
the oxidation was signicantly lowered. Moreover, the rst
step of the oxidation of a ne powder involved the formation
of the metastable iron oxide maghemite, which transformed
to the nal product hematite with further increase in laser
power. The recorded changes were irreversible.
We have also demonstrated several possible ways to
calculate the local temperature of a sample heated by an
excitation laser in the course of a Raman experiment, and
correlated the calculated temperatures with the laser power
andchanges observedinthe Ramanspectra. The results show
that in the micro-Raman experiment on iron oxides, the use
of a strongly focused laser causes a temperature increase of
several hundreds of degrees. We have also quantitatively
evaluated the temperature-induced softening of the phonon
wavenumbers of magnetite.
Acknowledgments
We thank Professor Hans Annersten for providing the sample of
natural magnetite. The SwedishResearch Council (Vetenskapsr adet)
is gratefully acknowledged for nancial support.
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