Corrosion Science 50 (2008) 24932497

0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.06.034
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Corrosion Science
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1. Introduction
Formation and transformation of iron oxides is of interest to a
wide variety of industries including steel making, power generat-
ing, paint systems, pharmaceutical, and petrochemical, to name a
few. The thermal hydraulic performance and integrity of the steam
generators in nuclear power plants may be compromised due to
the presence of corrosion deposits. The amount of iron transported
in a steam generator is dependent on the composition of iron oxide
formed in the feed train. Deposits that contain well crystallized
magnetite and maghemite are more stable than deposits contain-
ing a combination of oxides and oxyhydroxides [1]. Therefore, it
is very important to quantitatively understand the composition of
the deposits.
Standard methods for identications and characterizations of
iron oxides have traditionally used either X-ray diffraction (XRD)
or Mssbauer spectroscopy (MS) [2]. XRD has been widely used
in characterizing corrosion products. Although these techniques
have served industry well in the past, they suffer from shortcom-
ings that could be replaced by Fourier transform infrared spectro-
photometry (FTIR). MS is a technique that utilizes a live radioactive
source, which makes the technique relatively unsafe from an oper-
ational point of view, since it poses a potential health risk to the
operator. The main limitations of MS technique include the level
of operator expertise requirements and the complexity of spectral
interpretation. Even though XRD is easier to operate and interpret,
its spectra is limited in its ability in differentiating magnetite and
maghemite.
On the other hand, FTIR instrumentation is simple and spectra
interpretation is relatively easy [3]. In the past, it has been estab-
lished that the FTIR technique can be routinely used to eciently
differentiate and quantify different iron oxides and oxyhydroxides.
To the best knowledge of the authors, no attempts have been made
in using FTIR for quantitative analysis of iron oxides formed in the
power plants. The main objective of this research is to quantify
iron oxide phases formed in the secondary side of the steam gener-
ator units at Comanche peak steam electric station (CPSES). Such
analysis will allow better interpretation and control of the corro-
sion process.
2. Literature review
Magnetite is a well-known form of iron oxide that forms at
room temperature in crevices between steel plates and at elevated
temperature inside boiler tubes, heat exchangers etc. The oxida-
tion product of Fe
3
O
4
is either c-Fe
2
O
3
or a-Fe
2
O
3
depending on
the oxidation temperature and/or possibly the crystallite size of
the starting magnetite [45].
Studies performed by Nasrazadani and Raman [4] have shown
that transformation of magnetite to hematite goes through the for-
mation of maghemite. The production of maghemite begins with
Quantitative analysis of iron oxides using Fourier transform infrared
spectrophotometry
H. Namduri, S. Nasrazadani
*
College of Engineering, University of North Texas, Denton, TX-76207, USA
a r t i c l e i n f o a b s t r a c t
Article history:
Received 14 August 2007
Accepted 17 June 2008
Available online 4 July 2008

In this study, a systematic approach based on the application of Fourier transform infrared spectropho-
tometry (FTIR) was taken, in order to quantitatively analyze the corrosion products formed in the sec-
ondary cycle of pressurized water reactors (PWR). Binary mixtures of iron oxides were prepared with
known compositions containing pure commercial magnetite (Fe
3
O
4
), maghemite (c-Fe
2
O
3
), and hematite
(a-Fe
2
O
3
) for calibration purposes. Calcium oxide (lime) was added to all samples as a standard reference
in obtaining the calibration curves. Using regression analysis, relationships were developed for intensity
versus concentration for absorption bands corresponding to each of the phases in their corresponding
FTIR spectrum. Correlation coecients, R
2
, of 0.82, 0.87, and 0.86 were obtained for maghemitemagne-
tite, hematitemagnetite, and hematitemaghemite systems, respectively. The calibration curves gener-
ated were used to quantify phases in multi-component unknown eld samples that were obtained from
different components (moisture separators, condensers, and high and low pressure heaters) of the two
units (units 1 and 2) of the secondary cycle of the Comanche Peak PWR.
2008 Elsevier Ltd. All rights reserved.
Keywords:
A. Steel
B. IR spectroscopy
C. Rust
C. Oxidation
C. Passivity
* Corresponding author. Tel.: +1 940 565 4052; fax: +1 940 565 2666.
E-mail address: nasr@unt.edu (S. Nasrazadani).
2494 H. Namduri, S. Nasrazadani / Corrosion Science 50 (2008) 24932497
nucleation and growth of goethite or lepidocrocite, followed by
dehydration to hematite, and then reduction to magnetite.
The deposition rate of hematite is an order of magnitude
greater than magnetite. As seen from the Pourbaix diagram of iron,
it is important that the reducing conditions be maintained in the
steam generators during operation, so as to facilitate formation of
magnetite. Turner and Klimas showed that lowering the concentra-
tion of hematite relatively to magnetite in the feedwater will signif-
icantly lower the rate of tube bindle fouling [6]. Theoretical studies
by Jobe showed that hematite has a very low solubility and a much
smaller dissolution rate than magnetite and lepidocrocite in the
presence of 5 ppb of dissolved oxygen. Formation of thin layer of
maghemite/magnetite is known to act as a very good passive lm
[7].
FTIR spectra of iron oxides are well established. It is been
observed that the absorption band at a high wavenumber region is
due to OH stretching, and at lower wavenumber as a result of Fe-O
lattice vibration. FTIR spectrum of magnetite exhibits two strong
infrared absorption bands at 570 cm
1
(t
1
) and 390 cm
1
(t
2
) [8].
According to Ishii et al, these bands can be assigned to the Fe-O
stretching mode of the tetrahedral and octahedral sites for the
t
1
band at 570 cm
1
and the Fe-O stretching mode of the octahe-
dral sites for the t
2
band at 390 cm
1
, provided that Fe
3+
ion dis-
placements at tetrahedral sites are negligible [8]. FTIR spectrum
of magnetite exhibits two other absorption bands at 268 cm
1
and
178 cm
1
which were beyond the detection limit of our instru-
ment. Maghemite, a defective form of magnetite, has absorption
bands at 630 cm
1
, 590 cm
1
, and 430 cm
1
. Table 1 summarizes
possible FTIR peaks for different iron oxides.
Legodi and his group performed quantitative analysis on cal-
cium carbonate present in different cement blends using FTIR [9].
Reig and group performed quantitative FTIR analysis on calcium
carbonate and silica (quartz) using the constant ratio method. The
group used potassium ferricynaide as standard and successfully
showed the accuracy of quantifying the concentration of silica and
quartz in geological samples using FTIR [10]. The same group also
successfully showed that FTIR can be used to quantify butyl acetate
and toluene in binary and ternary mixtures using constant method
ratio. They used valeronitrile as the standard and they also showed
that the above method is independent of optical path length [11].
The Xu group showed that FTIR can be eciently used for quan-
tifying minerals. They used a multifunctional analysis, which is
based on Beers law to quantify different minerals present in oil
wells. In this method, the absorbance at a specic wave number
is equal to the sum of the absorbance of all sample components at
that wavenumber [12].
3. Experimental procedure
Commercially available powders of magnetite (puratronic
99.999% purity), maghemite (99+% purity), and hematite (99.99%
purity) were obtained. Three binary sets of sample mixtures with
known concentrations of maghemite and magnetite, hematite and
magnetite, and hematite and maghemite were prepared. All the
samples were added to KBr powder and compressed into pellets
using hydraulic press. Magnitude of compression applied in KBr
pellet preparation needs to be kept constant to avoid variance in
absorbance intensity from one sample to the next. Nicolet Avatar
370 DTGS FTIR was used to quantify iron oxides. FTIR spectra collec-
tion was done for 32 scans with 2 cm
1
resolutions. Three equiva-
lent runs of each of the three sets of the samples were made on the
FTIR spectrometer. The average values of background subtracted
peak intensity results were used for obtaining calibration curve.
Once all of the spectra for the samples were obtained, three cal-
ibration curves were drawn for the three sets of samples. To set
the calibration curve for known amounts of iron oxide (magnetite,
maghemite and hematite) in each mixture, I/I
o
ratio was used. The
intensity of the iron oxide peak (magnetite 570 cm
1
, hematite-
540 cm
1
and maghemite 630 cm
1
) is represented by I and I
o
rep-
resents, the intensity of the 3640 cm
1
peak of CaO.
This calibration curve was used to quantify the amount of iron
oxides present in the eld samples collected from the secondary
side of CPSES. The most readily available samples of the secondary
system were obtained from the feedwater heaters (FW HTR-low
pressure and high pressure feedwater heaters), condenser, and
moisture separator-reheater (MSR), as these components are rou-
Table 1
Infrared bands of different iron oxides [4,13]
Iron oxide/hydroxide Wave numbers of bands (cm
1
)
Magnetite (Fe
3
O
4
) Broad bands at 570 and 400 cm
1
Maghemite (c-Fe
2
O
3
) 700, 630660, 620 range (Fe-O range)
Hematite (a-Fe
2
O
3
) 540, 470 and 352 cm
1
Goethite (a-FeOOH) 1124, 890 and 810 cm
1
for OH stretch
Lepidocrocite (c-FeOOH) 1018 cm
1
(in plane vibration) and
750 cm
1

(out of plane vibration)
Fig. 1. Simplied schematic of secondary system sample locations.
H. Namduri, S. Nasrazadani / Corrosion Science 50 (2008) 24932497 2495
tinely opened during outages and represent major temperature
locations of the system as illustrated by Fig. 1.
The CaO absorption band was used primarily as a reference
because it does not interfere with any of the iron oxide phases.
Even though an absorption band of 3640 cm
1
is close to the
OH band, it has a very distinct peak and can be easily discerned
(Fig. 2). CaCO
3
(894865 cm
1
peak) has been previously used as
a standard reference in quantifying the amount of limestone in
different cement blends [9]. A linear t was used to obtain the
calibration curve.
4. Results and conclusions
Fig. 3 shows FTIR spectra of single phases of hematite, mag-
netite, and maghemite. A sharp peak at 3640 cm
1
belonging to
calcium oxide is shown in all of the spectra of iron oxides. The
peak intensity of CaO was fairly constant in all the spectra. Cali-
bration curves were obtained for combinations of two phases
of iron oxides. Correlation factors of 0.822 (magnetite added to
maghemite, Fig. 4), 0.8584 (maghemite added to hematite, Fig. 5),
and 0.8708 (magnetite added to hematite, Fig. 6) were obtained.
Fig. 3. FTIR spectra of 100% hematite, maghemite and magnetite.
Fig. 2. FTIR spectra of 100% CaO showing 3640 cm
1
peak.
2496 H. Namduri, S. Nasrazadani / Corrosion Science 50 (2008) 24932497
A condence limit of 95% was used in the calculations. The aver-
age values of I/I
o
for three runs made with mixtures with different
concentrations of iron oxides are shown in the Table 2. Hematite
peak at 540 cm
1
intensity (the most intense peak for hematite)
was used for the I value for mixtures containing hematite and mag-
netite, and maghemite and hematite. The peak at 630 cm
1
(the
most intense peak of maghemite) was used for I values in the case
of mixtures containing magnetite and maghemite. No peak inter-
ferences of any phases were observed in all of the mixtures since
FTIR spectra of all iron oxides are well resolved and spectra resolu-
tion of most FTIR instruments is 2 cm
1
. These calibration curves
were then used to quantify the iron oxide phases present in the
eld samples collected from the secondary side of unit 1 and unit
2 of CPSES.
The percentage concentrations of the iron oxides present in
the selected eld samples is given in Table 3. The samples from
the moisture separator mainly show hematite and magnetite.
The main feedwater heater sample showed 96% magnetite and
about 4% maghemite. The high-pressure feedwater heater sam-
ple showed mostly hematite; whereas, low-pressure feedwater
heater sample showed hematite and magnetite. The presence of
magnetite and hematite is expected in feedwater systems due to
the transformation of hydroxides and other hydrated iron species,
which move through the feedwater system into stable iron oxides
(Schikorr reaction). The two samples form the main condenser
mainly consisted of hematite with traces of magnetite and maghe-
mite. Detection limits determination for iron oxides quantication
using FTIR was not done in this study and is planned for future
work.
5. Summary and conclusions
A quantitative determination of iron oxides can be quickly per-
formed relatively accurately using FTIR technique. The technique
involves taking mid infrared measurements with samples in the
form of KBr pellets. By using a standard reference like CaO, nor-
malization can be performed. The peak of 3450 cm
1
is free from
interference with any of the major iron oxide peaks considered in
this study. This method makes it a very suitable method in quickly
determining the concentrations of major iron oxides in the power
industry.
The FTIR technique was reconrmed to be a valuable tool to dif-
ferentiate between Fe
3
O
4
and c-Fe
2
O
3
. It is also been shown that
this technique can be used in quantifying iron oxides.
It has also been shown that the infrared active mode of calcium
oxide can be eciently used in the quantication process. The FTIR
quantication method performed in this study can be further ne-
tuned and extended to other major metallic oxides including: chro-
mium oxide, nickel oxide, lead oxide, and silicon dioxide. This will
prove valuable for studying corrosion deposits formed in nuclear
power plants.
y
= 0.0059x + 0.6335
R
2
= 0.8708
0.60
0.70
0.80
0.90
1.00
1.10
1.20
1.30
1.40
1.50
Hematite Conc. (%)
I
/
I
O
Hematite/Magnetite
Hematite 540 cm
-1
0 20 10 40 30 60 50 80 70 90 100
Fig. 5. FTIR calibration for mixture containing hematite and magnetite.
y
= 0.0032x + 0.6477
R
2
= 0.8222
0.00
0.20
0.40
0.60
0.80
1.00
1.20
0 20 40 60 80 100
Maghemite Conc. (%)
I
/
I
O
Maghemite/Magnetite
Maghemite 630 cm
-1
Fig. 4. FTIR calibration for mixture containing magnetite and maghemite.
Table 2
FTIR intensities for different known concentrations of iron oxides used in calibra-
tion curves (I = intensity of iron oxide mixture, and I
o
= intensity of 3640 cm
1
peak
of CaO)
Hematite (%) Magnetite (%) Maghemite (%) I/I
o
100 1.30
100 1.13
100 1.02
80 20 1.01
60 40 0.98
40 60 0.82
20 80 0.81
80 20 1.13
60 40 1.02
40 60 0.91
20 80 0.95
20 80 0.86
40 60 0.81
60 40 0.75
80 20 0.76
y = 0.0046x + 0.7849
R
2
= 0.8584
0.70
0.80
0.90
1.00
1.10
1.20
1.30
1.40
1.50
Hematite Conc. (%)
I
/
I
O
0 20 10 40 30 60 50 80 70 90 100
Fig. 6. FTIR calibration for mixture containing maghemite and hematite.
H. Namduri, S. Nasrazadani / Corrosion Science 50 (2008) 24932497 2497
Acknowledgement
Authors would like to thank both Mr. Jim Stevens and Mr. Rob-
ert Theimer for providing eld samples.
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Table 3
Concentration of eld sample collected from different components of secondary side of unit 1 and unit 2 steam generator system of CPSES
Field samples Sample description Oxides present I
o
Maghemite (I) Hematite (I) I/I
o
Final concentrations
1 Moisture separator Magnetite and hematite 3.02 2.85 0.94 52% Hematite and 48% magnetite
2 Main feedwater heater Magnetite and maghemite 4.29 2.81 0.66 96% magnetite and 4% maghemite
3 Main condenser, hotwell Magnetite and hematite 3.08 4.01 1.3 Mostly hematite
a
4 Main condenser Maghemite and hematite 0.28 0.49 1.74 Mostly hematite
b
5 High pressure feedwater heater Maghemite and hematite 0.75 1.03 1.37 Mostly hematite
b
6 Low pressure feedwater heater Magnetite and hematite 5.81 5.37 0.92 52% magnetite and 48% hematite
a
Amount of magnetite was below the detection limit.
b
Amount of maghemite was below the detection limit.