JOURNAL OF RAMAN SPECTROSCOPY, VOL.

28, 873878 (1997)

Raman Microspectroscopy of Some Iron Oxides

and Oxyhydroxides

D. L. A. de Faria,1* S. Vena ncio Silva2 and M. T. de Oliveira1

1 Laboratorio de Espectroscopia Molecular, Instituto de Qu mica, Universidade de Sa8 o Paulo, CP 26077, 05599-970 Sa8 o
Paulo, Brazil
2 Departamento de Engenharia Metalurgica e de Materiais, Escola Politecnica da Universidade de Sa8 o Paulo, 05599-970 Sa8 o
Paulo, Brazil

Hematite (a-Fe O ), magnetite (Fe O ), wu stite (FeO), maghemite (c-Fe O ), goethite (a-FeOOH), lepido-
2 3 3 4 2 3
crocite (c-FeOOH) and d-FeOOH were studied by Raman microscopy. Such compounds have already been studied
by Raman spectroscopy, but there are some disagreements in the reported data. Here, Raman microscopy was
employed to investigate the laser power dependence of the spectra of these oxides and oxyhydroxides. Low laser
power was used for the reference spectra in order to minimize the risks of spectral changes due to sample degrada-
tion. The results obtained show that increasing laser power causes the characteristic bands of hematite to show up
in the spectra of most of the compounds studied whereas the hematite spectrum undergoes band broadening and
band shifts. ( 1997 John Wiley & Sons, Ltd.
J. Raman Spectrosc. 28, 873878 (1997)
No. of Figures : 7. No. of Tables : 2. No. of References : 35.

al.,6 who reported the Raman spectra of FeO, Fe O ,

INTRODUCTION
The understanding of rusting mechanisms is of funda-
mental importance in corrosion control and therefore it
is very important from both the technological and eco-
nomic points of view.
Rust composition has been the subject of several
investigations, mainly because it can provide insights
into corrosion mechanisms.1,2 X-ray diraction, IR
absorption spectrometry and electrochemical methods
are the techniques most often employed in such studies.
Oxides and oxyhydroxides, the main metal corrosion
products,3 strongly absorb infrared radiation but they
are usually poor light scatterers. This is probably the
reason for the larger number of studies on rust com-
position using IR spectrometry compared with Raman
spectroscopy.
However, despite this drawback, Raman spectroscopy
presents at least two important advantages over IR
spectroscopy : there is no need for sample preparation
and the spectra of watermetal interfaces are easily and
quickly obtained.4 For example, some studies have
combined eletrochemistry and Raman spectroscopy to
investigate in situ lms formed on metal surfaces in
corrosive aqueous environments (see, for example, Ref.
5 and references cited therein).
The need for reference spectra for the most common
iron oxidation products inspired the work of Thibeau et
* Correspondence to : D. L. A. de Faria.
Contract grant sponsor : FAPESP.
Contract grant sponsor : CNPq.
CCC 03770486/97/11087306 $17.50
( 1997 John Wiley & Sons, Ltd.
3 4
a-Fe O , a-FeOOH and c-FeOOH. Hematite and mag-
2 3
netite were also studied by Hart et al.,7,8 who presented
a precise and complete assignment for the observed
Raman spectrum ; orientation eects of a-Fe O single
2 3
crystals were investigated by Beattie and Gibson.9
Raman spectroscopy was also employed by Boucherit
et al.,10 Thierry et al.,11 and Nauer et al.,12 who aimed
to characterize corrosion processes in ironwater inter-
faces. For the same purpose, Oblonsky and Devine13
used surface-enhanced Raman scattering (SERS) to
study the nature of the passive lms formed on iron,
nickel, chromium and stainless steel in a borate buer.
All of these studies reported Raman spectra for some of
the iron compounds investigated here. In these studies,
high laser power was employed (from 100 to 500 mW)
and this could lead to sample degradation. In fact,
Thibeau et al.6 found that the Raman spectrum of FeO
was very similar to that of Fe O and they interpreted
3 4under illumination.
this as due to FeO decomposition
With the remarkable developments in Raman instru-
mentation, it is now possible to obtain good quality
spectra even from very poor light scatterers using a few
hundred micro watts or even less.
Some disagreements in the reported spectra of iron
oxides and oxyhydroxides motivated the present work,
because reliable reference spectra are essential for the
correct use of the information obtained by Raman spec-
troscopy in iron corrosion studies.
In this paper, we report investigations of the Raman
spectra of hematite (a-Fe O ), magnetite (Fe O ),
wustite (FeO), maghemite2 (c-
3 Fe O ), goethite3 (a-
4
2 3
FeOOH), lepidocrocite (c-FeOOH) and d-FeOOH in
order to clarify the inuence of laser power on the
Received 20 February 1997
Accepted 4 July 1997
874 D. L. A. DE FARIA S. VENA NCIO SILVA AND M. T. DE OLIVEIRA

Raman spectra. This is of particular importance because

of recent interest in the photochemical behavior of goe-
thite.14 The spectra were obtained directly from pow-
dered samples with very low laser power (ca. 0.7 mW),
minimizing the problems caused by sample handling.

EXPERIMENTAL

The Raman equipment was a Renishaw Raman imaging

microscope15 (System 3000) consisting of a single
spectrograph (0.25 m focal length) containing a holo-
graphic grating (1800 grooves mm~1), an Olympus
metallurgical microscope and a Peltier-cooled CCD
detector (600 ] 400 pixels). The spectra were excited Figure 1. Raman spectra of (a) a-Fe O and (b) c-Fe O .
2 3 2 3
with 632.8 nm radiation from a 35 mW air-cooled
HeNe laser (Spectra Physics, Model 127) and the laser
beam was focused on the sample by a ]80 lens to give hematite, there is a consensus on the reported
a spot size of ca. 1 lm ; the resolution was better than 2 data.6,8,9,19
cm~1. The laser power was always kept below 0.7 mW Hematite belongs to the D6 crystal space group and
at the sample, to avoid sample degradation, except in 3d
seven phonon lines are expected in the Raman spec-
the laser power dependence experiments. After each trum,20 namely two A modes (225 and 498 cm~1) and
spectrum had been recorded, a careful visual inspection 1g 299, 412 and 613 cm~1). In
ve E modes (247, 293,
was performed using white light illumination on the g
previous work,8,9 the 293 and 299 cm~1 bands were
microscope stage in order to detect any change that
could have been caused by the laser.
All the samples were studied on a microscope slide as
prepared or received and their compositions were
checked by x-ray diraction. The diractograms were
obtained with a Philips Model PW 1710-based instru-
ment, tted with a Cu tube (40 kV and 40 mA).
The samples were obtained from the following
sources : a-Fe O , mineral (Minas Gerais, Brazil) and
commercial 2product
3
(Labormax) ; Fe O , mineral
3 4 from the
(Minas Gerais, Brazil) ; c-Fe O , donation
2 3
Institute of Physics, University of Sa8 o Paulo ; FeO, kind
gift from Cyro Tanabe (Escola Politecnica, USP) ; a-
FeOOH, mineral (Minas Gerais, Brazil) and prepared
according to the literature ;16 c-FeOOH, synthesized
according to the literature ;17 and d-FeOOH, synthe-
sized according to the literature.18
The eect of temperature on the Raman spectrum of
magnetite was investigated using a TS 1500 temperature Figure 2. Raman spectra of (a) a-FeOOH, (b) c-FeOOH and (c)
stage (Linkam Scientic Instruments), coupled to a d-FeOOH.
TMS92 temperature control unit (Linkam) and a PS
1500 power unit (Linkam).
The acquisition time ranged from 10 s in the most
favorable cases (hematite and goethite) to 5 min in the
worse cases (wustite and magnetite).
Data analysis was performed using the Grams386
package (Galactica) and, in all the curve ttings per-
formed, a Lorentzian lineshape was assumed.

RESULTS AND DISCUSSION

The Raman spectra of iron oxides and oxyhydroxides

are shown in Figs 13. As mentioned before, the laser
power was set to avoid degradation of the sample,
which was checked through successive scans.
Among the iron compounds cited here, the most Figure 3. Raman spectra of (a) Fe O and (b) FeO (asterisk indi-
3 4
studied are hematite and magnetite. In the case of cates artifacts).

( 1997 John Wiley & Sons, Ltd. J. Raman Spectrosc., Vol. 28, 873878 (1997)
 RAMAN MICROSPECTROSCOPY OF SOME IRON OXIDES AND OXYHYDROXIDES 875

only resolved at 100 K or less. However, Fig. 1(a)
reports the Raman spectrum of hematite in the 100
1800 cm~1 range at room temperature and the 299
cm~1 band can be observed as a shoulder of the much
stronger 293 cm~1 peak.
Several samples from dierent sources (natural and
synthetic hematite) were studied and gave similar results
except for changes in relative intensities that occurred
when natural samples were studied. This can be
explained by considering that such samples are much
more crystalline than the synthetic one (available as a
ne powder) and consequently much more sensitive to
sample orientation, owing to the band polarization
behavior.9
Hematite is an antiferromagnetic material21 and the
collective spin movement can be excited in what is
called a magnon. The intense feature at 1320 cm~1 is
assigned to a two-magnon scattering which arises from
the interaction of two magnons created on antiparallel
close spin sites.8
Raising the laser power to 7 mW (at the sample)
causes the bands to broaden and to undergo a small
shift to lower wavenumbers, as shown in Table 1. Peak
positions and widths were obtained from curve tting
using Lorentzian band shapes.
The large increase in bandwidth shown in Table 1
probably arises from local heating due to the relatively
high laser power, which enhances anharmonic inter-
actions. Actually, at low temperatures (77 K) the a-
Fe O bandwidths decreases and the band positions
2 slightly
3 3 4 is transformed into hematite when powdered in
shift to higher wavenumbers, as rst noticed by
Beattie and Gibson.9 This behavior seems to be fully
reversible, as turning down the laser power causes the
bandwidth to decrease.
Magnetite has a spinel structure (O 7) above 119 K,22
h T , one E and
giving rise to ve Raman bands : three
one A . Table 2 summarizes the peaks2g reported
g for
1g
Fe O by several workers and, in contrast to hematite,
3 4are some disagreements.
there
Some of the Fe O peak positions that have been
3 4
reported7,23,24 are suspiciously close to the values
expected for hematite. Thibeau et al.6 reported the
Raman spectrum of a mixture of 90% Fe O and 10%
a-Fe O by weight and the coincidence of 3this4 spectrum
2 3
with that reported by Dunnwald and Otto24 is evident.
Furthermore, the peak at 1322 cm~1, assigned to a
hematite two-magnon scattering, is not a feature
expected in a magnetite spectrum, reinforcing the
assumption that hematite is present as a contaminant in
the above-mentioned studies.
Figure 3(a) depicts the Raman spectra of a freshly
fractured Fe O crystal face at room temperature. As
3 4
mentioned before, only the bands at 300, 532 and 661
cm~1 are observed despite the very reasonable signal-
to-noise ratio. However, as shown in Fig. 4, the laser
power has a clear eect on the sample. The spectrum
recorded with 0.7 mW shows the behavior discussed
above, but when the laser power is raised to 7 mW new
bands show up. Comparison with Fig. 1 leads to the
conclusion that hematite is being formed at higher laser
power. Moreover, the spectral changes are irreversible,
as shown in Fig. 4(c), and clearly dependent on the
surface morphology. If a at portion of the crystal with
no apparent defects is irradiated, the changes are not
observed (Fig. 5).
Transformation of magnetite into hematite is a very
common phenomenon in nature and is called martitiza-
tion.25 The dependence of hematite formation on the
Fe O morphology is also observed for maghemite
which
preparation for x-ray studies.26

Table 1. Wavenumbers (m8 ) and full widths at half maximum

(FWHM) for hematite as a function of laser power
0.7 mW 7 mW

l8/cm1 FWHM/cm1 l8/cm1 FWHM/cm1

226.7 4.8 219.6 10.2
245.7 6.0 236.5 22.0
292.5 7.1 282.7 20.0
299.3 8.5 295.2 17.3
410.9 11.6 395.9 29.3
497.1 21.2 492.3 51.9 Figure 4. Raman spectrum of magnetite : effect of laser power.
611.9 14.4 596.0 38.9 (a) 0.7 mW ; (b) 7 mW ; (c) same spot as in (b) but with 0.7 mW ;
(d) 0.7 mW after exposure to a flame.

Table 2. Wavenumbers (m8 ) for magnetite according to dierent workers

l8/cm1 l8/cm1 l8/cm1 l8/cm1 l8/cm1 l8/cm1 l8/cm1
(Ref. 6) (Ref. 10) (Ref. 7) (Ref. 23) (Ref. 24) (Ref. 19) (Ref. 11) l8 (this work)

298 300 (77 K) 298 301.6

320 320 (77 K) 319
420 420 (77 K) 418
513.0
550 550 560 (77 K) 550 540 550 533.6
616
663 670 676 680 (77 K) 676 665 670 662.7
1322

( 1997 John Wiley & Sons, Ltd. J. Raman Spectrosc., Vol. 28, 873878 (1997)
876 D. L. A. DE FARIA S. VENA NCIO SILVA AND M. T. DE OLIVEIRA
Figure 5. Raman spectrum of magnetite : effect of laser power.
(a) Flat surface, 0.7 mW ; (b) flat surface, 7 mW.
A crystal of magnetite (natural sample) was heated in
a ame to compare the eects of irradiation and
heating ; the observed spectrum shown in Fig. 4(c) is
similar to that of hematite, indicating that the eects are
equivalent.
Using a temperature stage, it was possible to measure
the spectral changes in the magnetite spectrum when
the temperature was raised to 300 C, as shown in
Fig. 6.
Figure 6(c) (spectrum taken at 200 C) clearly shows
the maghemite bands [c-Fe O , Fig. 1(b)], while in Fig.
6(d) (spectrum obtained at 23003 C) characteristic hema-
tite peaks can be readily observed.
Magnetite is known to undergo the following phase
transitions with temperature increase :27
200 ]C 400 ]C
Fe O c [ Fe O aFe O present work.
3 4 2 3 2 3
The temperature in the ame is higher than 400 C but
this is probably not the case under laser irradiation
even with higher laser power or during grinding. This
reinforces the dependence of such structural changes on
the surface morphology.
Magnetite belongs to the D@ magnetic group, which
4h in this case the assign-
predicts a one-magnon band, but
ment is not as straightforward as in the hematite case,
mainly because one-magnon scattering is usually much
Figure 6. Raman spectrum of magnetite : temperature depen-
dence. (a) Room temperature ; (b) 150 C ; (c) 200 C ; (d) 300 C.
( 1997 John Wiley & Sons, Ltd.
weaker than the two-magnon process.28 Hart et al.7
found a very weak feature at 472 cm~1 and assigned it
to magnon scattering, in agreement with neutron data,
which predict the optical magnon at 468 ^ 8 cm~1.29
Wustite is a non-stoichiometric compound with an
approximate composition ranging from Fe O to
0.84
Fe O.30 Above 198 K its crystal structure is cubic
0.95
and below this temperature it is rhombohedral.
Thibeau et al.6 reported the Raman spectrum of
wustite from ca. 450 to 650 cm~1. They assigned the
observed peaks at 616 and 663 cm~1 to magnetite
which originated from sample decomposition owing to
the use of a relatively intense laser excitation. Figure 3
shows both the Fe O and FeO Raman spectra ; the
3 4
FeO spectrum was taken with 0.7 mW laser power but
the laser was defocused to decrease the possibility of
decomposition. It is clear that these spectra are not
equivalent as the bands at ca. 300 and ca. 535 cm~1
observed in the magnetite spectrum are not present in
the wustite spectrum. The peak at 663 cm~1 (magnetite)
shifts to ca. 652 cm~1 and appears signicantly
broadened, probably because of the contributions from
non-equivalent sites in the wustite structure.
Wustite is metastable below 570 C and its decompo-
sition leads to a-Fe and Fe O .31,32 Figure 7 shows the
3 wu
4 stite spectrum ; Fig. 7(a)
eects of laser power on the
clearly shows the characteristic peaks of hematite. It is
reasonable to assume that the Fe O formed during the
3 4 in to a-Fe O .
spectrum excitation was transformed
Maghemite (c-Fe O ) has an inverse spinel 2structure
3
2 3
and can be seen as an iron-decient form of magnetite,
with structural formula Fe3` K O2~, where K
21.33 2.67 32 sites.33 There
2.67
means 2.67 vacancies in octahedral spinel
are no signicant discrepancies between the Raman
band positions reported for maghemite10,19 and the
In contrast to hematite and magnetite, the maghemite
bands are not well dened and the resolution seems to
depend on sample preparation because it is directly
related to the degree of crystallinity of the material.
Nevertheless, the Raman spectrum of maghemite can be
characterized by three broad structures around 350, 500
and 700 cm~1, not present in any other spectrum of
iron oxide or oxyhydroxide reported here.
Despite the similar structural formulae of the oxyhy-
droxides a-FeOOH (goethite), c-FeOOH (lepidocrocite)
Figure 7. Raman spectra of wu stite : effect of laser power. (a) 7
mW (acquisition time 3 s) ; (b) 0.7 mW (acquisition time 5 min).
J. Raman Spectrosc., Vol. 28, 873878 (1997)
 RAMAN MICROSPECTROSCOPY OF SOME IRON OXIDES AND OXYHYDROXIDES
and d-FeOOH, their Raman spectra show substantially
distinct features, as has been reported extensively in the
literature.
Despite small dierences in peak positions (^5
cm~1), there is good agreement in the reported spectra
of goethite6,11,12,19 with bands at 243, 299, 385, 479,
550, 685 and 993 cm~1 (this work). Additional peaks at
1120 and 1255 cm~1 have also been reported24 but they
are not present in the spectrum shown here [Fig. 2(a)].
Comparison of the spectrum reported in Ref. 24 with
those in Ref. 12 and in Fig. 2(a) suggests that the former
may contain a contaminant species, probably lepido-
crocite ; the possibility of sample decomposition due to
intense laser excitation can be ruled out because hema-
tite bands (the product of goethite dehydration) are not
present in the spectrum.
The Raman spectrum of lepidocrocite (c-FeOOH) has
also been extensively investigated and there is a con-
sensus on the most important peaks :6,11,12,19,24 245,
373, 493 (shoulder), 522, 650 (shoulder), 719 and 1303
cm~1 (this work). The broad peak at 719 cm~1 has not
been reported before and it could arise from a small
amount of maghemite formed during the synthesis of
the compound. In contrast to goethite, lepidocrocite
dehydration leads to maghemite and because the
surface stability relative to the laser power depends on
its morphology, as discussed in the magnetite case, the
possibility of laser damage to the sample cannot be dis-
regarded, despite the low laser power employed here.
Finally, the Raman spectrum of d-FeOOH10,12,34
shows broad bands, due to the low degree of crys-
tallinity ; the peak positions are 400 and 680 cm~1 (this
work). Keiser et al.35 reported a weak band also at 296
cm~1, and this can be seen as a shoulder on the broad
main peak at 400 cm~1 in Fig. 2(c) ; two other broad
bands at 1160 and 1314 cm~1 (not reported before)
show up in the d-FeOOH spectrum.
Under high laser power, all the oxyhydroxides inves-
tigated here show the characteristic peaks of hematite,
the power threshold being dependent on the surface
morphology.
CONCLUSION
Rust composition studies using Raman spectroscopy
usually demand a high laser power for the excitation of
the spectra because some of the most common iron
oxides and oxyhydroxides are poor light scatters.
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