Paper No.

09563

2009

CO2 CORROSION INHIBITION AND OIL WETTING OF

CARBON STEEL WITH FERRIC CORROSION PRODUCTS
Martin Foss and Egil Gulbrandsen
Institute for Energy Technology
Materials and Corrosion Technology Department
NO-2027 Kjeller, Norway
Johan Sjblom
Department of Chemical Engineering
Norwegian University of Science and Technology
NO-7051 Trondheim, Norway

ABSTRACT
Wettability of carbon steel and carbon steel with corrosion product films (iron carbonate
(FeCO3) and FeCO3 with oxidized surface) was investigated through contact angle and
inhibitor performance tests. Two corrosion inhibitors, an oleic imidazoline compound (OI)
and a phosphate ester compound (PE) were used. The inhibitor performance was studied in
CO2 corrosion tests at 60 C, 1 bar CO2, 3 Wt-% NaCl and 20 vol-% oil, where the samples
were alternately exposed to oil and aqueous phase. A refined, low aromatic, oil was used in
the tests.
Addition of both surfactants lead to significant changes in the wettability of oxidized FeCO3
surfaces. The contact angle tests showed that a transition from a preferential water-wet
state to a preferentially oil-wet state was achieved for both inhibitors.
Electrochemical measurements revealed that addition of OI enabled the oxidized FeCO3
surface to retain an oil film after exposure to oil. The retained oil film caused a significant
drop in corrosion rate in the presence of oxygen. The effect was also seen on a rusting
carbon steel surface without any surface deposits. No similar effect was seen for PE.
Keywords: Corrosion inhibitor, wetting, hydrophobic, iron carbonate, rust, FeCO3.

Copyright
Government work published by NACE International with permission of the author(s). The material presented and the views expressed in this paper are
solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.

INTRODUCTION
Carbon steel used in pipelines for oil and gas transport, is subject to corrosion caused by
the presence of water and acidic gases such as carbon dioxide (CO2), hydrogen sulfide
(H2S) and/or acetic acid (CH3COOH). Several mitigation methods have been developed to
reduce the corrosion rate in such pipelines to acceptable levels. Injection of corrosion
inhibitors, or stimulating the growth of protective corrosion film such as iron carbonate
1,2
(FeCO3) are two possible ways of lowering the corrosion rate.
The present work is a part of an effort to investigate how oil wetting of the pipe walls could
be used to protect against corrosion. In particular the effect of corrosion inhibitors, which
usually are surface active, on the wettability has been studied. The effect of oil on the
performance of corrosion inhibitors on bare steel and FeCO3 covered steel surface was
3,4
investigated in two previous papers. The main finding was that the inhibitor performance
increased in the presence of oil. No evidence of the formation of a stable macroscopic oil
film on the surface was found, and the increased performance was attributed to a change in
the protective properties of the inhibitor film. The investigation did, however, reveal that the
inhibitors increased the ability of an oil wetted surface to repel water droplets. The present
work focuses on the effect of CO2 corrosion inhibitors on the wettability of bare steel and
FeCO3 surfaces that has been exposed to oxygen in order to form ferric (i.e. Fe(III)) oxides
at the surface. While the corrosive environment in oil and gas pipelines is normally
anaerobic and ferrous containing corrosion products predominate (FeCO3, or iron sulfide,
FeS), ferric compounds may be present from several reasons:
i) Mill scale present from the pipe production
ii) Rust from hydrostatic testing with seawater
iii) Oxidation of ferrous compounds caused by air ingress into the pipelines
The samples were prepared using the same initial procedures as in reference [3] and [4]
before they were exposed to oxygen. The effect of oxidation of the surfaces can thus be
investigated and evaluated in light of previous results. Two CO2 corrosion inhibitors were
used in this study. They were chosen based on the previous results obtained with the same
3,4
The two inhibitors were; a phosphate ester (PE) and an oleic imidazoline salt
chemicals.
(OI) (Table 1).
Contact angle measurements have previously been used to investigate the characteristics
of liquid-solid interaction in liquids containing surface-active molecules, such as crude
oil.6,7,8 In surface chemistry the term wetting refers to the extent of contact established
between a liquid and a solid surface when the two are brought together. The wetting
properties of a surface/liquid system are determined by the balance of forces at the line of
9
contact between the liquids and the solid. The wetting of an FeCO3 surface in an oil/water
system is thus a function of the interfacial tension forces between oil and water (ow), water
9
and FeCO3 (sw) and oil and FeCO3 (so). The contact angle () and the surface energies
of the phases involved are related by Youngs equation (1):

so = sw + ow cos

(1)

A sketch showing the direction of the forces in Equation 1 is seen in Figure 1. The reported
contact angles were measured in the aqueous phase. A contact angle in the aqueous

phase of 90 or greater generally characterizes a surface as hydrophobic, while an angle of

less than 90 means that the surface is hydrophilic.

EXPERIMENTAL
Chemicals and materials
A refined, low aromatic oil product was used as model oil in the tests. It has a density of
o
10
0.788 kg/L and boiling point range 193-245 C, corresponding to kerosene. The oleic
imidazoline salt was supplied as technical grade (67.5 Wt-% in a solvent), formed by
reaction of diethylenetriamine and a tall-oil fatty acid. The phosphate ester was also
supplied as a technical grade product; details of its composition are not known. The
reported concentrations are referred to the supplied product. An outline of the basic inhibitor
structures is given in Table 1. The test brine consisted of distilled water with 3 Wt%
technical grade NaCl added. The CO2 gas was grade 4.0 grade, with a maximum O2
content of 10 ppm (by volume). The water-air surface tensions versus concentration curves
11
for the two inhibitors have been published previously. No clear break points in the surface
tension versus concentration curves could be found for any of the inhibitors, and therefore
4
no critical micelle concentrations (cmc) could be established. Water-to-oil partitioning tests
3
showed that both inhibitors partition preferentially to water. The test specimens used in
both the contact angle measurements and the corrosion inhibition experiments were
machined from API X-65 ferritic-pearlitic low carbon pipeline steel (Element analysis (wt%):
C, 0.08; Mn, 1.54; Ni, 0.03; Si, 0.25; Cr, 0.04; P, 0.019; S, 0.001; V, 0.045; Mo, 0.01; Al,
0.038; Nb, 0.04; Sn, 0.001).
Contact angle experiments
The contact angles were measured with a commercially available drop tensiometer
instrument, using a liquid measuring chamber. Continuous CO2 gas purging of the
measurement chamber was done to avoid oxygen contamination before the intended
oxidation of the sample surface. The experiments were performed with an oil droplet
deposited on an inversed, horizontal sample surface immersed in brine.
The experiments were conducted at different inhibitor concentrations. A detailed description
of the FeCO3 sample preparation up to the point of oxygen exposure can be found in
reference [4]. Following the FeCO3 formation at 80 C the temperature was lowered to 50
C and the coupons were exposed to air saturated test brine at ambient pressure for 3 days
before inhibitor addition. The inhibitor concentrations were increased every 24 h and one
coupon removed before each increase. The samples removed were rapidly lifted through
the oil layer, and dried by blowing pressurized CO2 onto the surface of the steel to rid the
steel surface of the liquid film covering the surface. The dry sample was then immersed in
the contact angle cell, which was filled with brine sampled from the precorrosion cell. The
experiments were done with an inverted surface where the oil droplet was placed onto the
surface by means the droplet buoyancy. Some of the samples were examined by SEM after
termination of the tests. This was done to ensure that the iron carbonate films were
comparable for all the tests. Figure 2 shows a typical oxidized FeCO3 surface used in the
contact angle experiments. The surface has been exposed to oxygen for several days after
formation of the FeCO3 layer was terminated.

Corrosion experiments
Corrosion experiments were carried out on stationary cylinder (10 mm diameter, 10 mm
length and 3.14 cm2 exposed area) specimens in a 3-liters thermostatted glass cell at
ambient pressure. The steel specimens were ground with 1000 mesh SiC paper wetted with
isopropanol, cleaned with technical acetone in ultrasonic bath and flushed with ethanol.
The experiments were carried out at 60 C with 1 bar CO2 and 3 Wt% NaCl. 20 vol-% of
model oil was added to the test cells before the inhibitor was added. This was done to
saturate the water phase with the oil components (mainly aliphatic hydrocarbons). The pH
of the system was initially around pH 3.9. The pH increased to pH 5.7 at the end of the iron
carbonate formation stage due to the formation of HCO3 in the cathodic reaction. The
formation of the FeCO3 deposits on corroding steel surfaces have been described in detail
4
in ref. 4.
The corrosion experiment can be divided into two stages. The initial stage depends on the
type of surface that is to be tested. Two approaches were used; one to grow a FeCO3 layer
on the sample surface (A) and one to obtain a uniformly corroding bare steel surface (B).
(A) The FeCO3 layer was formed from the supersaturated solution created by corrosion
of the samples. A partly protective FeCO3 layer started to form after approximately 100 h.
The FeCO3 layer formation was stopped after about 200 h and air was bubbled through
the solution The corrosion had dropped to approximately 0.5 mm/y after the FeCO3
formation stage.
(B) The sample without surface deposits were corroded in a solution purged with CO2 at
20 oC for 24 h before air was bubbled through the cell.
The second stage was the inhibitor testing. It was performed at 20 oC for the bare steel
surface samples and at 60 oC for the FeCO3 samples, to facilitate comparison with other
results. The inhibitor was added from a 1 % stock solution. The glass cells used in the
experiments allowed the test specimen to be lifted vertically into the oil phase which formed
a layer above the water phase, and then be returned to the water phase. Such an oil
immersion step will be referred to as an oil exposure.
A three-electrode setup was used for the electrochemical measurements. An Ag/AgCl (3 M
KCl) electrode and a titanium ring surrounding the working electrode were used as
reference and auxiliary electrode, respectively. The Polarization Resistance technique (PR)
12
was used to monitor the corrosion rate. This technique is also commonly referred to as
the Linear Polarization Resistance Technique (LPR). The corrosion rate is reported as areaaveraged penetration rate in mm/y, and is obtained from the corrosion current using
2+
Faradays law calculation according to the anodic dissolution reaction Fe = Fe + 2 e , and
3
using 7.9 g/cm as the density of the steel. Measurements were done at 30 minutes
intervals throughout the test. A detailed description of the PR measurements can be found
in [3]. Electrochemical impedance spectra (EIS) were also recorded before and after each
oil immersion step throughout the experiment.

RESULTS
Contact angle oil-in-water
Based on the results in [3] and [4] only oil-in-water experiments were performed on the
oxidized FeCO3 surface. This was done to simulate the situation where the surface is
already water-wet before coming in contact with an oil phase.
Figure 3 shows the contact angles as a function of inhibitor concentration. The contact
angle in absence of inhibitor was below 20 degrees. The addition of PE did not have any
apparent effect at 10 and 35 ppm but a significant change in wetting behavior is seen at 95
ppm. The contact angle increases from below 20 degrees at 35 ppm to more than 100
degrees at 95 ppm. When OI was added the contact angle increased to 30 degrees after
addition of 10 ppm inhibitor. Increasing the concentration to 35 ppm caused the contact
angle to increase above the higher measurement limit for the drop tensiometer, 160
degrees is plotted to symbolize this result, the real contact angle might be higher than 160
degrees. This Contact angles in this range were also seen in the test with 85 ppm inhibitor.
Images showing the change in contact angle caused by addition of 35 ppm OI is shown in
Figure 4.
Corrosion experiments
The main objective of these tests were to investigate the impact of oxidation on the oil
wetting of carbon steel in the presence of two corrosion inhibitors. The tests were therefore
designed to detect the changes in corrosion rate caused by a direct exposure to oil in the
presence of corrosion inhibitor. The main focus is placed on the recorded corrosion rates
and the lasting effect of putting the surface in direct contact with oil.
Oxidized FeCO3 surface:
OI: A plot of corrosion rate as a function of time in a test with OI is seen in Figure 5.
Precipitation of FeCO3 was done by corroding the sample for more than 350 h at 80 C. The
average corrosion rate after this initial phase was 0.35 mm/y. The temperature was lowered
to 60 C after 380 hours of corrosion. The sample was exposed to aerated brine for 24 h
after 400 h of corrosion and 20 vol-% oil was added after 410 hours of corrosion. After this
initial exposure to aerated brine the system was purged with CO2 for 60 h before being
exposed to aerated brine again. The initial exposure to oil was done after 475 h but no
effect was seen. 10 ppm inhibitor was added after 480 h of corrosion and a drop in
corrosion rate from 0.4 mm/y to 0.2 mm/y was seen. At this concentration further exposure
to oil after 500 h had no impact on the corrosion rate. 35 ppm inhibitor was added after 505
h but no change in corrosion rate was observed. The sample was immersed in oil after 520
h and this had a significant impact on the corrosion rate, which decreased from 0.3 mm/y to
0.03 mm/y,. After this decrease in corrosion rate no further effect of oil exposure or inhibitor
addition was seen.
A SEM image of the surface after termination of the test of Figure 5 is seen in Figure 6. It is
apparent that an FeCO3/rust film is present on and in contact with the steel surface after
termination of the test. The structures furthest from the steel surface are porous and is
probably rust or oxidized FeCO3.

Only a qualitative and tentative evaluation of the EIS results will be presented at the present
stage. Figure 7 shows the modulus of the impedance versus frequency measured at
different times during the test in Figure 5. In principle, such a plot should show a plateau at
high frequency, which is the uncompensated resistance (Ru). Ru may in the present tests
contain contributions from electrolyte resistance, corrosion product layers, and oil layers. In
the low frequency limit, a plateau representing the sum of Ru and the polarization resistance
(Rp) should be observed. In practice these plateaus may not be observable within practical
limits of measurement frequencies. The modulus for the initial, uninhibited corrosion in
Figure 8 displays both plateaus (Ru = 1 ohm, Rp = 10 ohm). In the spectrum measured
after 498 h (10 ppm OI and oil exposure) the modulus still had a slightly decreasing trend
with increasing frequency at 5 kHz. It is, however, reasonable to conclude that Ru was not
substantially different from the initial value. Previous work indicated that Ru increased about
4
3 times due to the FeCO3 formation. The modulus was still increasing with decreasing
frequency at 10 mHz, but a Rp of 200 300 ohm could be estimated, in fair agreement with
the PR measurements. The spectra measured from 522 h onwards (with 35 ppm OI) had a
different appearance. The capacitive to faradic transition was no longer clearly observed,
and Ru could not be determined. The potentiostat failed to determine any impedance above
500 Hz. Similar results were observed in several comparable tests with the ferric corrosion
products in presence of oil, but not in the absence of oil. It may be noted that the low
frequency modulus values were in fair agreement with the values measured by the PR
14
measurements (which can be compared with EIS data at approximately 3 mHz. ) The
results may tentatively be explained by a great increase of Ru and/or a significant drop in
electrode capacitance, which would shift the capacitive to faradic transition to higher
frequencies. These changes are consistent with the formation of an oil layer at the surface,
possibly penetrating into the ferric corrosion product film that had been made hydrophobic
by the corrosion inhibitor. The EIS results obtained with FeCO3 covered electrodes that had
not been exposed to air, and thereby remained hydrophilic in presence of the inhibitor, did
not show similar dramatic changes in the high frequency behavior.4
OI was also tested on oxidized FeCO3 where the inhibitor had achieved maximum effect
before aeration of the brine. A plot of corrosion rate as a function of time for this test is
seen in Figure 8. The corrosion rate before aerating the brine (after ~430 h) was 0.03 mm/y.
The corrosion rate increased from 0.03 mm/y to 0.3 mm/y after the brine had been
saturated with air. The first exposure to oil in the presence of air was done after 455 h and it
had a significant effect on the corrosion rate which decreased from 0.3 mm/y to 0.02 mm/y.
After this exposure to oil the inhibitor concentration was increased to 60 ppm. Addition of
inhibitor itself had no impact on the corrosion rate but exposure to oil following the
increased inhibitor concentration leads to a decrease in corrosion rate from 0.02 mm/y to
0.005 mm/y. After this decrease the system was purged with CO2 but this had no significant
effect on the corrosion rate. The corrosion rate was stable at 0.003 mm/y at the end of the
test.
A SEM image of the surface after termination of the test of Figure 8 is seen in Figure 9. It is
apparent that an FeCO3/rust film is present on and in contact with the steel surface after
termination of the test. The film seems to be mainly dense and no signs of any porous
material attached to the film is seen.
PE: A plot of corrosion rate as a function of time in a test with PE is seen in Figure 10.
Precipitation of FeCO3 was done by corroding the sample for more than 270 h at 80 C. The
corrosion rate after this initial phase was 0.2 mm/y. The temperature was lowered to 60 C
after 290 hours of corrosion. 20 vol-% oil was added after 320 hours of corrosion. The steel

sample was exposed to aerated brine after ~320 h of corrosion. Following the saturation of
the brine with O2 an increase in corrosion rate from 0.2 mm/y to 0.8 mm/y was seen.
Addition of PE and exposure to oil had no positive impact on the corrosion rate of the
system. The concentration of PE was increased to 165 ppm after 430 h. The corrosion rate
increased to 1 mm/y following the inhibitor addition. After 480 h the system was purged with
CO2 to remove the oxygen. This lead to a significant drop in corrosion rate. The corrosion
rate dropped from 1 mm/y to 0.2 mm/y. This lack of any effect of the exposure to oil was
found in all the tests with PE on an oxidized FeCO3. The EIS data for the test with PE
revealed that the addition of inhibitor and the exposure to oil had no significant effect on the
measured Ru. EIS data is therefore not included for the test on PE.
Steel surface with rust:
The inhibitor performance data and for the test with PE on rusted steel is not included since
no significant effect of the immersion in oil was seen.
OI: Corrosion rate data for a test with OI on corroding steel in aerated brine is seen in
Figure 11. The sample was precorroded in brine purged with CO2 for 24 h before being
corroded in aerated brine. The corrosion rate is 1 mm/ y before inhibitor addition. Exposure
to oil after 138 h and 142 h and addition of 5 ppm OI after 140 h had no significant effect on
the corrosion rate. When the corrosion inhibitor concentration is increased to 15 ppm a
small decrease in corrosion rate from 1 mm/y to 0.9 mm/y is seen. A third exposure to oil,
after 160 h of corrosion, had a significant effect on the corrosion rate which decreases from
0.9 mm/y to 0.3 mm/y. Further additions of inhibitor and exposure to oil have no significant,
further effect on the corrosion rate. The system is purged with CO2 after 190 h of corrosion
the corrosion rate decreases to less than 0.1 mm/ y. EIS measurements after oil exposure
showed similar trends to the results described in Figure 6.
A SEM image of the surface after termination of the test of Figure 11 is seen in Figure 13. A
500 m thick porous film is seen on the steel surface. A thinner (100 m), more dense film,
is also seen close to the surface but a significant lack of contact with the steel substrate is
apparent.

DISCUSSION
Both the contact angle measurements and the inhibitor performance experiments
demonstrate that the tested corrosion inhibitors could induce oil-wetting steel and FeCO3
surfaces that had been exposed to air. The inhibitor performance test with OI revealed a
significant effect of oil exposure when a certain inhibitor concentration had been reached.
The effect of the exposure to oil in the inhibitor performance tests with OI will be the main
focus of the discussion.
Previous testing on FeCO3 covered and corroding carbon steel have demonstrated the
3,4
inability of OI and PE to incite a water-wet to oil-wet transition . The dispersion contact
angle tests were therefore performed to investigate the influence of oxidation of the surface
on the wettability of FeCO3. As seen in Figure 3 the addition of the two inhibitors had a
significant effect on the wetting properties of a surface exposed to oxygen. The contact
angle measurements showed that the OI started to affect the wetting properties of the
surface at a concentration of only 10 ppm, where an increase in contact angle of about 20

degrees above the initial value is seen. To enable oil to displace water and preferentially
wet the surface a much higher contact angle is, however, necessary. For OI such high
contact angles is reached at a concentration of 35 ppm where the surface showed superhydrophobic properties. PE also showed similar performance but the extreme
hydrophobicity seen in the test with OI was not seen for the tested concentrations of PE.
This might mean that even higher concentrations (>95 ppm) of PE is needed to obtain a
water-wet to oil-wet transition. In surfactant systems the monomers are expected to adsorb
individually at low concentrations of inhibitor. At higher concentrations (CMC and above) the
development of a structured inhibitor layer able to affect the wetting properties significantly
might be expected. An ordered surfactant structure of this kind is likely for both OI and PE.
Previous publications support the formation of such structured formations of imidazoline
13
compounds. .
The corrosion tests were conducted to investigate the ability of OI and PE to enhance oil
wettability of corroding carbon steel in the presence of oxygen. When determining the
polarization resistance, and thus the corrosion rate for systems with a high degree of
corrosion inhibition, some considerations regarding the accuracy of the measurements
should be made. According to the procedure described Foss et al. the corrosion current
3
density is calculated based on the measured polarization resistance. The polarization
resistance (Rp) is determined by subtracting the uncompensated resistance (Ru) from the
measured total resistance of the system. In previous experiments this has not been a
problem due to a relatively stable Ru. In the experiment where the EIS data is plotted in
Figure 7 it is evident that Ru changes significantly in the experiment with OI. This means
that the corrosion rate might be underestimated in some of the experiments. In addition to
the effect of the change in Rp a comment on the scan rate used in the LPR measurements
must be made. If the scan rate is too fast the measured corrosion rate can be
14
overestimated due to the contribution of capacitive current. . The maximum scan rate that
can be used depends on the capacitance, uncompensated resistance and polarization
resistance of the system. An estimation of the maximum scan rate of the system based on
the break-point frequency can be found in ref. [3]. The break point frequency is the
frequency at which the resistance curve reaches a plateau in the low frequency end of a
Bode plot.
The influence of the inhibitor on the oil wettability of the steel was investigated by immersing
the samples in oil during corrosion testing. By measuring the change in corrosion rate,
polarization resistance and uncompensated resistance an assessment of the possibility of a
water-wet to oil-wet transition could be made. Ru may comprise the resistances of the
electrolyte, the FeCO3 film, and a possible oil layer at the surface or in the FeCO3 film
(imbibition). The electrical resistivity () for the oil used in the experiments at 20C is >1012
10
m. . The increase in uncompensated solution resistance due to an oil film of thickness L
2
can then be calculated as: R= (L/A), where A is the surface area (3.14cm ). The
thickness corresponding to 10 of resistance is only L< 3 nm, i.e. of the same thickness as
an inhibitor film. The retention of oil on the surface (oil wetting) should thus be easily
detected by measurements of Ru. The tests where FeCO3 was precipitated before exposure
to aerated brine showed that significant changes in wetting behavior was obtainable. For OI
both the test where inhibitor was added after the surface was exposed to oxygen (Figure 5)
and the test where significant amounts of inhibitor was present before exposure to oxygen
(Figure 9) revealed that OI increased the surface ability to retain an oil film in or at the
FeCO3 film after exposure to oil. Previously published data on the influence of OI on the
wettability of FeCO3 covered and corroding steel have not found any signs of significant
alteration in surface wettability. 3,4

The oil retained in or at the surface increased the measured Ru by more than one order of
magnitude in tests with oxidized FeCO3 and OI (Figure 5). As seen in Figure 7 the
exposure to oil leads to Ru and Rp values of approximately the same magnitude. This
supports the idea that the increased uncompensated resistance caused by the oil film is the
main factor causing the reduction in corrosion rate. Bilkova and Gulbrandsen found that the
CO2 corrosion inhibition consisted of two processes: first a rapid process (order of minutes)
connected to adsorption of the inhibitor, leading to inhibition of the anodic part reaction, and
a second slower process (order of hours) leading to a reduction in the corrosion rate
15
through inhibition of the cathodic part reaction(s). The instantaneous change in corrosion
rate accompanying the oil exposure supports the idea that an oil film is the reason for the
lowered corrosion rate. From the EIS data it is also clear that the oil retained in or at the
corrosion product film were stable.
The corrosion test with PE (Figure 10) revealed that PE was not able not induce the same
change in wetting behavior seen for OI.
The corrosion test on corroding steel exposed to air/oxygen revealed that reductions in
corrosion rate following oil exposure was also possible for oxidized steel surfaces without
FeCO3 present (Figure 11).

CONCLUSIONS
The effect of carbon dioxide corrosion inhibitors on the wettability of corroding steel with
ferric deposits was investigated. Also investigated was the effect of oil on the performance
of these inhibitors. The following conclusions may be drawn:

Both OI and PE increased the oil wettability of surfaces with ferric corrosion
products. Contact angle experiments showed that the addition of OI (>35 ppm)
lead to a hydrophilic-hydrophobic transition at the surface of the steel.
The inhibitor performance experiments in the presence of O2 revealed that the
addition of significant amounts of OI (>35 ppm) enabled the retention of an oil
film after a direct exposure to oil. This effect was seen on both oxidized FeCO3
deposits and on oxidized (rust covered) steel surfaces when OI was used as an
inhibitor. EIS data indicate that the retained oil remains stable in/on the film even
when the sample is re-immersed in the aqueous phase.

ACKNOWLEDGEMENTS
The work is a part of a joint project between Institute for Energy Technology and the
Norwegian University of Science and Technology, sponsored by the Research Council of
Norway (Project no. 158913/I30).

REFERENCES
1.

A. Dugstad, CORROSION/98, Paper no. 31, (Houston, TX: NACE International,

1998).

2.

S. Ramachandran, B. Tsai, M. Blanco, H. Chen, Y. Tang and W. A. Goddard,

Langmuir 12 (1996), p 6419.

3.

M. Foss, E. Gulbrandsen, J. Sjblom, Effect of Corrosion Inhibitors and Oil on

Carbon Dioxide Corrosion and Wetting of Carbon Steel with Ferrous Carbonate
deposits, Corrosion (2009), in press

4.

M. Foss, E. Gulbrandsen, J. Sjblom, Effect of Corrosion Inhibitors and Oil on

Carbon Dioxide Corrosion and Wetting of Carbon Steel with Ferrous Carbonate
deposits, Corrosion (2009), in press

5.

R. I. Hughes, Corrosion Science, 9 (1969): p. 535.

6.

M. Nordsveen, S. Nesic, R. Nyborg, A. Stangeland, Corrosion 59 (2003): p. 443.

7.

S. Hoeiland, T. Barth,A. M. Blokhus and A. Skauge, Journal of Petroleum Science

and Engineering 30, 10 (2001).

8.

Horsthemke and J. J. Schroder, Chemical Engineering and Processing, 19 (1985),

Issue 5.

9.

P. Atkins, J. de Paula, Atkins Physical chemistry, 7th edition (Oxford University

Press, 2002), p. 154.

10.

www.shellchemicals.com, Data sheet: Shellsol D-70, Issued 27-may-2005

11.

M. Foss, E. Gulbrandsen, J. Sjblom, , Adsorption of Corrosion Inhibitors onto Iron

Carbonate (FeCO3) Studied by Zetapotential Measurements, Journal of Dispersion
Science and Technology 30 (2009), 10.

12.

J. R. Scully, Electrochemical tests, in: R. Baboian (Ed.), Corrosion Tests and

Standards, Philadelphia: American Society for Testing and Materials, 1995.

13.

R. Atkin, V. S. J. Craig, E. J. Wanless, S. Biggs, Advances in Colloid and Interface

Science 103 (2003), p. 219.

14.

R. G. Kelly, J. R. Scully, D. W. Shoensmith, R. G. Buchheit, Electrochemical

techniques in corrosion science and engineering, p. 140 (CRC, New York: Marcel
Dekker, 2002)

10

15.

K. Bilkova, E. Gulbrandsen, , Electrochimica Acta 53 (2008), p. 5423.

11

FIGURES AND TABLES

FIGURE 1. Sketch showing the direction of the forces acting on the line of contact between the liquids
and the solid and the contact angle () of the droplet.

Inhibitor
compound
The
phosphate
ester (PE)

TABLE 1. INHIBITOR COMPOUNDS.

Type
Structure

Anionic

O
O

O
n
The oleic
imidazoline
(OI)

Cationic

12

FIGURE 2. SEM image; cross section of a steel sample with a FeCO3 film that had been exposed to air.

180
OI

160

PE

Contact Angle (Deg)

140
120
100
80
60
40
20
0
0

10

20

30

40

50

60

70

80

90

100

Inhibitor concentration (ppm)

FIGURE 3. Contact angle; oil-in-water experiments on steel with oxidized FeCO3 layer. Experiment
done at ambient temperature and pressure.

FIGURE 4. Images showing oil droplets in the tests with OI. Concentration 0 ppm (left) and 35 ppm
o

(right). The image to the left was captured 50 seconds after deposition. Both images were rotated 180 .

13

140 ppm

60C

70 ppm

35 ppm

10 ppm

80C

Corrosion rate (mm/y)

1.00

PR C . R.

0.10

Areated brine
0.01
350

400

450

500

550

600

Time (h)

FIGURE 5. Corrosion rate versus time for a test with OI. The temperature was reduced to 60 C after
380 h, oil was added after 410h. The test specimens were periodically exposed to oil (grey vertical
lines). Experimental conditions: 60 C, 3 Wt% NaCl brine, 20 vol-% oil, 1 bar CO2/Areated brine, X-65
steel. Inhibitor concentrations are given in the legend.

FIGURE 6. SEM image of the surface in the test shown in Figure 5. The image is captures with a
magnification of x200.

14

100000
Zmod_initial
10000
Zmod_498h
_after

Zmod (ohm)

1000
Zmod_522h
_before
100
Zmod_522h
_after
10
Zmod_546h
_before
1
Zmod_546h
_after
0.1
0.001

0.01

0.1

10

100

1000

10000

Frequency (Hz)

FIGURE 7. Plot of modulus of the impedance (Zmod) versus frequency (Hz) at different stages of the

35 ppm

60 ppm

experiment in Figure 5.

Corrosion rate / (mm/y)

1.000

0.100

0.010

Areated brine

0.001
407

417

427

437

447

457

467

Time / h

FIGURE 8. Corrosion rate versus time for a test with OI. The temperature was reduced to 60 C after
308h, oil was added after 310h. The test specimens were periodically exposed to oil (grey vertical
lines). Experimental conditions: 60 C, 3 Wt% NaCl brine, 20 vol-% oil, 1 bar CO2/Areated brine, X-65
steel. The inhibitor concentrations are given in the legend.

15

FIGURE 9. SEM image of the surface of the steel in the test shown in Figure 8. OI used as inhibitor.

165 ppm

100 ppm

35 ppm

80C

10 ppm

The image is captures with a magnification of x400.

60C

C orrosion rate (mm/y)

10.00

PR C.R.

1.00

Areated brine
0.10
270

320

370

420

470

520

Time (h)

FIGURE 10 Corrosion rate versus time for a test with PE. The temperature was reduced to 60 C after
290h, oil was added after 310h. The test specimens were periodically exposed to oil (grey vertical
lines). Experimental conditions: 60 C, 3 Wt% NaCl brine, 20 vol-% oil, 1 bar CO2/Areated brine, X-65
steel. The inhibitor concentrations are given in the legend.

16

135 ppm

85ppm

35 ppm

15 ppm

5 ppm

Corrosion rate / (mm/y)

10.00

1.00

PR C. R.

0.10

Areated brine
0.01
120

140

160

180

200

220

240

Time / h

FIGURE 11. Corrosion rate versus time for a test with OI. Oil was added after 20 h. The test specimens
were periodically exposed to oil (grey vertical lines). Experimental conditions: 60 C, 3 Wt% NaCl
brine, 20 vol-% oil, 1 bar CO2/Areated brine, X-65 steel. The inhibitor concentrations are given in the
legend.

FIGURE 12. SEM image of the surface of the steel in the test in Figure 11 (x400).

17