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Corrosion Science
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i n f o
Article history:
Received 14 August 2007
Accepted 17 June 2008
Available online 4 July 2008
Keywords:
A. Steel
B. IR spectroscopy
C. Rust
C. Oxidation
C. Passivity
a b s t r a c t
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 (Fe3O4), maghemite (c-Fe2O3), and hematite
(a-Fe2O3) 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 coefficients, R2, 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 field 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.
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 identifications 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
* Corresponding author. Tel.: +1 940 565 4052; fax: +1 940 565 2666.
E-mail address: nasr@unt.edu (S. Nasrazadani).
0010-938X/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.06.034
2494
Table 1
Infrared bands of different iron oxides [4,13]
Iron oxide/hydroxide
Magnetite (Fe3O4)
Maghemite (c-Fe2O3)
Hematite (a-Fe2O3)
Goethite (a-FeOOH)
Lepidocrocite (c-FeOOH)
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 efficiently 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 specific 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 2cm1 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/Io ratio was used. The
intensity of the iron oxide peak (magnetite 570cm1, hematite540cm1 and maghemite 630cm1) is represented by I and Io rep
resents, the intensity of the 3640cm1 peak of CaO.
This calibration curve was used to quantify the amount of iron
oxides present in the field 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
2495
2496
1.20
Table 2
FTIR intensities for different known concentrations of iron oxides used in calibra
tion curves (I=intensity of iron oxide mixture, and Io=intensity of 3640cm1 peak
of CaO)
Maghemite/Magnetite
Maghemite 630 cm-1
1.00
I/IO
0.80
0.60
y = 0.0032x + 0.6477
R2 = 0.8222
0.40
0.20
0.00
20
40
60
80
100
1.50
1.40
Hematite/Magnetite
Hematite 540 cm-1
1.30
I/IO
1.20
y = 0.0059x + 0.6335
2
R = 0.8708
1.10
1.00
0.90
0.80
0.70
0.60
10
20
30
40
50
60
70
80
90
100
1.50
1.40
1.30
I/IO
1.20
Magnetite (%)
Maghemite (%)
I/Io
100
1.30
1.13
80
60
40
20
80
60
40
20
20
40
60
80
20
40
60
80
100
20
40
60
80
80
60
40
20
1.02
1.01
0.98
0.82
0.81
1.13
1.02
0.91
0.95
0.86
0.81
0.75
0.76
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 2cm1. These calibration curves
were then used to quantify the iron oxide phases present in the
field 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 field 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 quantification
using FTIR was not done in this study and is planned for future
work.
5. Summary and conclusions
1.10
1.00
y = 0.0046x + 0.7849
2
R = 0.8584
0.90
0.80
0.70
Hematite (%)
100
10
20
30
40
50
60
70
80
90
100
2497
Table 3
Concentration of field 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
Io
Maghemite (I)
Hematite (I)
I/Io
Final concentrations
1
2
3
4
5
6
Moisture separator
Main feedwater heater
Main condenser, hotwell
Main condenser
High pressure feedwater heater
Low pressure feedwater heater
3.02
4.29
3.08
0.28
0.75
5.81
2.81
2.85
4.01
0.49
1.03
5.37
0.94
0.66
1.3
1.74
1.37
0.92
a
b
Acknowledgement
Authors would like to thank both Mr. Jim Stevens and Mr. Rob
ert Theimer for providing field samples.
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