5

Formation of Protective Corrosion Films During

CO 2 Corrosion of Carbon Steel

A. DUGSTAD
Institute for Energy Technology, (IFE)Norway

ABSTRACT
For many oil and gas pipelines the use of carbon steel is limited by C O 2 corrosion. The
parameters affecting formation of protective corrosion films have been studied in a large
number of flow loop experiments performed with 2 bar CO 2 partial pressure and pH
5.8 at 40-120°C and flow rates 0.1-7 ms -1. The importance of dissolved corrosion
products, temperature, pH and flow rate has been studied in detail. The risk for local
attack during operation is also dependent upon the previous history of the steel surface.
Periods of shutdown or oil wetting may facilitate formation of protective films because
corrosion products accumulate at the steel surface. The presence of mill scale or rust
from tube manufacturing and storage may also enhance the protectiveness of the
corrosion film and reduce the risk for local attack. Periods with stagnant conditions
during the loop experiments were shown to increase the protectiveness. The influence
of the history of the steel surface can be one explanation for the tendency to lower
corrosion in the field compared to laboratory experiments.

1. I n t r o d u c t i o n

The successful application of carbon steel in oil and gas pipelines and production
tubulars depends to a large degree on either the formation of protective corrosion
product films or the use of corrosion inhibitors. Protective iron carbonate films can
form in wet CO 2 systems at all temperatures provided that the p H and the dissolved
iron carbonate concentration in the bulk is sufficiently high. The growth of iron
carbonate is a slow temperature-dependent process. A high supersaturation of Fe 2+
a n d CO32- is therefore necessary in order to form a protective film. Once the film is
formed, however, it will remain protective at a much lower supersaturation.
Protective film formation is accelerated by all measures that restrict the transport
of reaction products from the surface and which can anchor the corrosion product.
Freshly ground and continuously exposed specimens are therefore m u c h more
susceptible to high corrosion rates than real pipelines, where the surface is covered
by oxide layers grown during rolling and storage and carbonate layers formed during
stagnant periods and periods with low water wetting w h e n the surface is water wet
but the water is replenished at a low rate.
The initiation, growth and stability of corrosion product films has been studied
extensively at The Institute for Energy Technology (IFE) during the three multi-client
projects Kjeller Sweet Corrosion III, IV and V [1,2] and the ESI project [3]. Some of
 Formation of Protective CorrosionFilms During CO2 Corrosionof Carbon Steel 71

the results obtained in the KSC-III project carried out in the period 1990 to 1993 are
presented and discussed in this paper. The project is particularly focused on how
operational parameters like stagnant periods and periods with low water-wetting
affect the protective properties of the corrosion product film.

2. E x p e r i m e n t a l

The flow loop experiments were carried out in an 80 m m i.d. high pressure one-
phase water flow loop made of duplex stainless steel (IR10). The steel specimens
were tested as flat 50 x 60 x 2.5 m m coupons mounted along the diameter of the flow
channel and separated by PTFE spacers. Three to four specimen racks with different
flow rates were used, and up to twelve specimens could be mounted in each specimen
rack. This enabled testing of a large n u m b e r of different steels at different flow rates
from 0.1 to 7 ms -1 in one loop experiment. The specimens were electrically insulated
from each other and from the loop, and some of the specimens had electrical
connections enabling electrochemical measurements to be made. Corrosion rates were
measured for all specimens by weight loss and by measurement of the depth of
mesa attack or pits. The corrosion rates of some of the specimens were followed during
the experiment by linear polarisation resistance m e a s u r e m e n t s (LPR) and by a
radioactive technique where some of the steel specimens were neutron activated and
the decrease in activity resulting from metal loss was measured with a scintillation
counter [4].
Experiments were performed at 40, 60, 80 and 120°C. The CO 2 partial pressure varied
from 1.8 to 2.6 bar and pH values between 5.5 and 6.0. The desired pH value was obtained
by addition of sodium bicarbonate. Distilled water was used in all the experiments.
Some experiments were done with 0.1% NaC1 in the water and some without salt. Only
the radioactive corrosion monitoring technique was used in the experiments without
salt. The loop pressure was kept constant at 8-12 bar by using a pressuriser half filled
with water and kept at a higher temperature than the loop. Corrosion products were
precipitated out in the pressuriser due to the lower iron carbonate solubility at higher
temperature. The level of ferrous ions was kept at the desired level by adjusting the
flow of loop water through the pressuriser. The Fe 2+ content was usually 5-40 p p m in
experiments above 80°C and 50-300 p p m at lower temperatures. The duration of the
experiments was two to three weeks. A large number of carbon steels have been studied
and the chemical composition of those discussed in this paper are shown in Table 1.
Under field conditions the pipe wall can be exposed periodically to the water and

Table 1. Chemical composition and microstructure of the tested steels. Descriptive names
of the steels have been given in the first column for easy identification in the text.

Material C Si Mn S P Cr Ni Cu Microstructure
St52 St-52 0.15 0.18 1.57 0.011 0.014 0.03 0.04 0.015 Ferritic-pearlitic
Cr0.87 16MnCr5 0.18 0.31 1.08 0.029 0.010 0.87 0.09 0.12 Ferritic-pearlitic
Cr0.53 API 5LX-X60 0.06 0.24 1.12 0.003 0.008 0.53 0.02 <0.01 Quenched and tempered
Ni 1.0 API 5LX-X60 0.05 0.25 1.32 0.003 0.013 0.02 1.00 0.01 Quenched and tempered
72 Advances in Corrosion Control and Materials in Oil and Gas Production
the oil (condensate) phase. W h e n the oil p h a s e replaces the w a t e r p h a s e , the steel
surface b e c o m e s either oil w e t or it c o n t i n u e s to be w e t t e d b y a thin w a t e r film
e m b e d d e d in the corrosion p r o d u c t layer. A similar w a t e r film will be p r e s e n t if the
p i p e is d r a i n e d . As long as the thin w a t e r films are p r e s e n t the corrosion attack will
continue, b u t at a m u c h l o w e r rate since the w a t e r is r e p l e n i s h e d at a v e r y l o w rate or
not at all. U n d e r these conditions, corrosion p r o d u c t s are forced to precipitate out o n
the surface, a n d this facilitates protective film f o r m a t i o n significantly. The d e s c r i b e d
scenario w a s s i m u l a t e d w i t h so-called ' d r y p e r i o d s ' d u r i n g the exposure. The flow
loop w a s d r a i n e d in these p e r i o d s a n d the steel surface w a s k e p t w e t b y e x p o s i n g
the s p e c i m e n s in a C O 2 a t m o s p h e r e w i t h h i g h humidity.

3. R e s u l t s

A s u r v e y of the corrosion rates o b t a i n e d in the v a r i o u s loop e x p e r i m e n t s is g i v e n in

Table 2. F o u r t y p e s of results can be d i s t i n g u i s h e d . The corrosion rates g i v e n in the
first c o l u m n of results are o b t a i n e d on fresh g r o u n d steel s p e c i m e n s w h i c h w e r e
c o n t i n u o u s l y e x p o s e d at low iron c a r b o n a t e s u p e r s a t u r a t i o n . Protective films d i d

Table 2. Survey of the results obtained from various experiments carried out at 1.8-2 bar
CO 2 partial pressure and pH 5.7-5.9. Corrosion rates are measured by weight loss (W),
LPR and radioactive techniques (Ra). The supersaturation S is indicated in the table

Temp. Flow Steel Corrosion rate mm/year

Fresh surfaces Fresh surfaces Dry period Pre-corroded
S=1-3 S = 10-100 2-5 days surfaces
2.5 St52B 2.5 W
120 6.8 St52B 2.1 Ra 0.05 Ra
Cr0.87 0.4 LPR
80 Nil.0 <<1 LPR
2.5 St52B 8** depth <0.3 Ra
Cr0.53 0.2 LPR
Cr0.87 1.8 LPR 0.11 LPR
60 Nil.0 1.0 LPR 0.1" LPR
2.5 St52B 7.5 Ra 4.3 LPR 0.3** depth
Cr0.53 1.1 LPR <0.1 LPR, Ra
Cr0.87 3.2 W <0.1" LPR 0.06 LPR
Nil.0 1.7 W <0.01 LPR <0.01" LPR
2.5 St52B 4.4 Ra 3.0 Ra 0.4 LPR <0.01 LPR
40 Cr0.53 2.0 Ra <0.1" LPR <0.1 LPR
Cr0.87 3.8 W 0.3* LPR <0.1 LPR
Nil.0 2.0 W 0.8 LPR <0.1" LPR
6.8 St52B 6.3 Ra 5.8 Ra 0.5 LPR <0.01 LPR
Cr0.53 2.1 Ra 0.4 LPR <0.1 LPR
* Small pits. **mesa atacked areas, corrosion rate calculated from depth measurement.
 Formation of Protective Corrosion Films During CO2 Corrosion of Carbon Steel 73

not form easily at 40 and 60°C under these conditions and the corrosion rates obtained
were therefore still high after a few weeks exposure.
When the temperature was increased to 80°C, however, protective films started to
form as the corrosion precipitation process accelerated. Only parts of the surface
obtained protection in the reported experiment and a mesa attack did therefore
develop. Mesa corrosion is characterised by a deep, more or less film free, attack
surrounded by a protected surface. Mesa attacked specimens are indicated with two
asterisks in the table. The film formed at 120°C gave protection, but less so than at
80°C, no localised attack was seen.
When supersaturation is increased iron carbonate films form more easily. Better
protection was therefore observed at all temperatures, as shown by the results in
column 2 in Table 2, where the supersaturation was higher. No mesa attack developed
at 80°C and 2.5 ms -1 flow velocity. At higher flow velocities (4.1 and 6.8 ms-l), however,
mesa attack was also observed in these experiments (not included in the table). At
lower temperatures, more film accumulated on the surface, but the film was very
porous and gave low protection. These films can be very thick as shown in Fig l(a).
The development of thick, non-protective porous films is not only a laboratory effect,
as similar films can be seen on steel exposed in the field (see Fig. l(b)). The films can
grow for months without giving protection unless the steel is exposed to stagnant or
'wet' conditions. After a stagnant or wet period of a few days, corrosion rates are
usually reduced 5-100 times, as shown by the results in column 3 in Table 1. This is
interesting as it can explain the large gap often seen between laboratory results and
corrosion rates measured in the field. Laboratory experiments have traditionally been
c o n d u c t e d w i t h c o n t i n u o u s l y exposed fresh g r o u n d steel samples and very
conservative worst case results have therefore been obtained. A corrosion survey
carried out by Elf showed that high corrosion rates were seldom experienced at pH
values higher than 5.6 [5]. This is also the case in the laboratory experiments when
simulation of operational parameters like shut d o w n and pre-formed oxide and
carbonate films are included in the test procedure.
When protective films are once formed they usually remain protective if the
supersaturation in the bulk is reasonable high. This is illustrated in column 4 in
Table 1, where pre-corroded steels have been exposed. Corrosion rates are generally
very low. Some small pits were seen now and then and it can be speculated whether
they were still active w h e n the experiments were stopped. Scanning electron
microscopy investigation showed that m a n y of them were filled with corrosion
products. It is therefore assumed that they would obtain protection with time.

4. D i s c u s s i o n

All the e x p e r i m e n t s discussed above were c o n d u c t e d u n d e r s u p e r s a t u r a t e d

conditions. That means that iron carbonate can precipitate and deposit on the surface
if it is not removed progressively by the flow. Whether it deposits or not depends
amongst other factors on how it is anchored to the surface. If a massive precipitation
takes place a dense iron carbonate film can form on most steel surfaces. At lower
precipitation rates, however, the formation of an iron carbonate film depends on the
presence of a skeletal substrate which can strengthen the film during the initial growth
74 Advances in Corrosion Control and Materials in Oil and Gas Production

process. This substrate can be iron carbide (steel St52) as shown in Fig. 1, chromium
oxides or carbides (steel Cr 0.87 and Cr 0.53) or other constituents accumulated on
the steel. Iron carbonate precipitation can then fill up the porous skeletal substrate.
Since small differences in the steel composition and the microstructure can affect the
anchoring properties, it is not surprising that large differences in the performance of
similar carbon steels has been seen in both field applications and laboratory work.
When iron carbonate precipitates on the steel surface it is the morphology and the
density of the corrosion film which controls the transport of different species through
the film. Both laboratory and field experiments have shown that thick, non-protective

Fig. 1 (a) Cross-section of a corrosion product film formed in a laboratory experiment carried out
at 60 °C, pH 5.8 and 5-10 times supersaturation. A carbide film partly filled with iron carbonate
can be seen (x450 magnification). (b) Cross-section of a corrosion product film formed on a
weight loss coupon exposed 3 months in a flow line in the North Sea. Temperature 60 °C and
1 bar CO 2 partial pressure. A carbidefilm partly filled with iron carbonate can be seen. The film
was more than i mm thick (x120 magnification).
 Formation of Protective Corrosion Films During CO2 Corrosionof Carbon Steel 75
films containing large amounts of iron carbonate can form. This is particularly the
case at low temperatures (20-60°C). The loop experiments have shown that such
films can be sealed by denser carbonate precipitates and the corrosion rate reduced
substantially by draining the system or by exposing the steel to stagnant conditions.
Once a reasonably dense corrosion product film has formed it can be speculated
whether it is the reduced transport through the iron carbonate film or the formation
of a passive film which reduces the corrosion rate [6]. Experiments carried out at IFE
in collaboration with Elf have shown that the steel shows passive-like behaviour at
high pH. High pH values can be obtained close to the steel when the transport of
reactants and corrosion products is restricted by the deposited corrosion products.

5. Conclusions

Protective iron carbonate films can form in wet CO 2 systems at all temperatures
provided the pH and the dissolved iron carbonate concentration in the bulk is
sufficiently high. The growth of iron carbonate is a slow temperature-dependent
process. A high supersaturation of Fe 2+ and CO32- is therefore necessary to form a
protective film, particularly at low temperatures. Once the film is formed, however,
it will remain protective at a much lower supersaturation.
Protective film formation is accelerated by all measures which restrict the transport
of reaction products from the surface. Freshly ground and continuously exposed
specimens are therefore much more susceptible to high corrosion rates than real
pipelines, where the surface is covered by oxide layers grown during rolling and
storage and carbonate layers formed during stagnant periods and periods with low
water wetting. Corrosion films can grow for months without giving protection unless
the steel is exposed at stagnant or 'wet' conditions. After a stagnant or wet period of
a few days, corrosion rates are usually reduced 5-100 times because corrosion
products are accumulated at the steel surface and protective corrosion films more
easily formed.
The introduction of pre-formed film and stagnant and dry periods in laboratory
experiments gives a better simulation of the conditions in the field. Laboratory
experiments have traditionally been conducted with continuously exposed fresh
ground steel samples and very conservative worst case result have therefore been
obtained. The influence of the history of the steel surface can be one explanation for
the tendency to lower corrosion rates in the field compared to laboratory experiments.

6. A c k n o w l e d g e m e n t s

The experiments described in this paper were carried out in the multi-client research
project Kjeller Sweet Corrosion III financed by Elf, BP, Shell, Total, Mobil, Phillips
Petroleum, Statoil, Norsk Hydro, Saga Petroleum and Kawasaki Steel. The author
wish to thank these companies for their technical and financial support.
76 Advances in Corrosion Control and Materials in Oil and Gas Production

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