4

Effect of C h r o m i u m on M e s a Corrosion of
Carbon Steel

R. NYBORG, A. DUGSTAD and P.-E. D R O N E N

Institute for Energy Technology, (IFE), Norway

ABSTRACT
The factors affecting local breakdown of protective corrosion films in C O 2 corrosion of
carbon steel have been studied in flow loop experiments at 40-80°C and pH 5.8. Above
60°C corrosion films with good protective properties can form under these conditions,
but mesa attack with very high local corrosion rates can occur especially at high flow
rates. The presence of 0.5% chromium in the steel was found to reduce significantly the
tendency for severe mesa attack in carbon steels during CO 2 corrosion.

1. Introduction

The 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. Above 60°C and at p H values higher than 5.5
iron carbonate corrosion films with good protective properties can form in wet CO 2
systems, but local b r e a k d o w n of the corrosion films m a y result in rapid local attack
or mesa corrosion attack, especially at high flow rates. In these mesa corrosion areas
the local corrosion rates can become very high.
Carbon dioxide corrosion of carbon steel is very d e p e n d e n t on water chemistry,
and it is important to differentiate between conditions leading to protective film
formation and the so-called 'worst case corrosion' where no protective films are
formed. The experiments presented here were performed at The Institute for Energy
Technology during the two multi-client projects Kjeller Sweet Corrosion III and IV,
which concentrated on conditions where protective corrosion films can form. Flow
loop experiments were performed at 40-80°C and p H 5.8. In this paper the focus is
on the factors affecting initiation of mesa corrosion and particularly the effect of
c h r o m i u m content of the steel. In the earlier projects Kjeller Sweet Corrosion I and II
experiments under conditions giving no or little corrosion films were performed
[1-3].

2. Experimental

Flow loop experiments were carried out in an 80 m m i.d. high pressure one-phase
water flow loop m a d e of duplex stainless steel. The steel specimens were tested as
flat 50 x 60 x 2.5 m m coupons m o u n t e d along the diameter of the flow channel and
64 Advances in Corrosion Control and Materials in Oil and Gas Production
separated by PTFE spacers. Three to four specimen racks with different flow rates
were used, and up to twelve specimens could be m o u n t e d 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 m e a s u r e m e n t to be conducted. Corrosion rates were
measured for all specimens by weight loss and by m e a s u r e m e n t 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 measurements (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].
Most experiments were conducted at 80°C, with some at 40°C and a few at 100-
150°C. All experiments were with 1.8 bar CO 2 partial pressure and p H values between
5.5 and 5.8. The desired p H value was obtained by addition of s o d i u m bicarbonate.
Distilled water was used in all the experiments. Some experiments were done with
3% NaC1 in the water and some 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 (Fe 2+)
was kept at the desired level by adjusting the flow of loop water t h r o u g h the
pressuriser. The content of ferrous ions was kept above the iron carbonate solubility,
thus enabling precipitation of iron carbonate films on the specimen. The Fe 2+ content
was usually 5-40 p p m in 80°C experiments and 100-300 p p m at 40°C. The duration
of the experiments was two to three weeks. Seven different steels were tested, three
carbon steels without addition of c h r o m i u m or nickel, two steels with 0.5-1% Cr and
two steels with 0.5-1% Ni. The chemical composition of the steels is shown in Table 1.

3. R e s u l t s

Several aspects of C O 2 corrosion of carbon steels were studied, including the

formation and b r e a k d o w n of protective corrosion films, effect of supersaturation of
iron carbonate, effect of small a m o u n t s of Cr and Ni in the steel, the influence of

Table I Chemical composition and microstructure of the tested steels

Material C Si Mn S P Cr Ni Cu Microstructure
St-52 batch I 0.18 0.34 1.50 0.017 0.023 0.08 0.03 0.010 Ferritic-pearlitic
St-62 batch 2 0.15 0.18 1.57 0.011 0.014 0.03 0.04 0.015 Ferritic-pearlitic
Low C steel 0.04 0.34 1.34 0.001 0.008 0.03 0.06 0.11 Ferritic
16Mn Cr5 0.18 0.31 1.08 0.029 0.010 0.87 0.09 0 . 1 2 Ferritic-pearlitic
API 5LX-X60 0.06 0.24 1.12 0.003 0.008 0.53 0.02 <0.01 Quenched and tempered
API 5LX-X65 0.20 0.32 1.6 0.009 0.003 0.02 0.75 Ferritic-pearlitic
API 5LX-X60 0.05 0.25 1.32 0.003 0.013 0.02 1.00 0.1 Quenchedand tempered
 Effect of Chromium on Mesa Corrosion of Carbon Steel 65

prehistory, different steel surfaces and precorrosion, and the effect of Ca 2+ or acetic
acid in the water. Only some of the results are presented here, with emphasis on the
effect of Cr on the occurrence of mesa attack.
Loop experiments at 80°C, 1.8 bar CO 2 and pH 5.8 resulted in severe mesa corrosion
attack at a high flow rate of 7 ms -1. The mesa attacks were deep and flat-bottomed
and usually without any corrosion film in the bottom, as seen in Fig. 1. The local
corrosion rate in the mesa attacked areas was very high, typically 20-40 m m / y . The
areas which were not mesa attacked usually had a 50-100 ~tm thick corrosion film
consisting mostly of iron carbonate. In these areas the corrosion rate was in the range
0.2-2 m m / y . Mesa attack occurred in the carbon steels without addition of chromium
or nickel and in the steels with 0.5-1% Ni. Deep, film-free mesa attack did not occur
in the two steels containing 0.5-1% chromium. In some of the experiments a shallow,
flat-bottomed mesa-like attack occurred in some of the chromium containing steel
specimens. This attack was covered with corrosion film in the bottom, as seen in Fig. 1.
In situ corrosion rate measurements with LPR measurements showed that the
specimens without mesa attack usually had high corrosion rates at the start of the
exposure, while the corrosion rate decreased rapidly during the first day or two due
to precipitation of protective corrosion films. The corrosion rates remained very high
throughout the experiment for specimens with deep, film-free mesa attack. The LPR
measurements for the 0.5% Cr steel specimens with a shallow, film-covered local
attack as seen in Fig. 1 showed that the corrosion rate in these specimens decreased
gradually during a period of two weeks towards the same level as specimens without
any mesa attack, as a result of reformation of protective films in the bottom of the
local attack.
Measured corrosion rates in loop experiments at 80°C, 1.8 bar CO 2 and p H 5.8 are
shown as function of liquid flow rate in Fig. 2. The group of very high corrosion
rates above 10 m m / y represent specimens with deep, film-free mesa attack. The
corrosion rates for these specimens are calculated from the depth of the mesa attack.
For specimens without local attack weight loss data are used. The corrosion rate in
these specimens decreased during the experiment due to protective film formation,
and final corrosion rates are lower than the weight loss data shown. The purpose of
this figure is primarily to show w h e n mesa attack occurs.
Corrosion rates in experiments at 40°C, 1.8 bar CO 2 and pH 5.8 are shown in Fig. 3.
At this lower temperature the specimens suffered either uniform attack with little

Fig. 1 Mesa attack in carbon steel without chromium (left) and with 0.5% Cr (right) x20
magnification.
66 Advances in Corrosion Control and Materials in Oil and Gas Production

100
o Unalloyed steel
[] 0 . 5 - 1 % Ni
• 0 . 5 - 1 % Cr
m Shell 95 model
--- IFE model
DD
OoO
o
10-
E
E

L,_
C
O
:" [] [] DA
[]
O •D D oo A
i_ D°
O
o OOA ~ AAD
1-
.
o AA
© DO
~O&D AO A
[]
[]

0.1 I I I

0 2 4 6 8

Flow rate (ms -1)

Fig. 2 Corrosion rates in loop experiments at 80 °C, 1.8 bar CO 2 and pH 5.8.

film formation or mesa attack w i t h o u t corrosion film in the bottom. This was the
case also for the c h r o m i u m containing steels. The mesa attack was not so deep as in
the experiments at 80°C, and the corrosion rates in areas w i t h o u t mesa attack were
higher than at 80°C. The corrosion films formed at 40°C were m u c h more porous
and less protective t h a n the films f o r m e d at 80°C because the iron carbonate
precipitation rate is m u c h lower at 40°C than at 80°C.

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

Mesa attack is a localised attack which can occur w h e n a protective corrosion film is
broken d o w n locally. A prerequisite for mesa attack is therefore that a partially
protective corrosion film is formed. The precipitation rate of iron carbonate is slow,
and a high degree of supersaturation of iron carbonate in the water is necessary in
order to precipitate iron carbonate in the corrosion film. Protective films are easily
formed at 80°C w h e n the p H is above 5.
The experiments reported here have s h o w n that carbon steels w i t h o u t c h r o m i u m
addition suffer mesa corrosion easily at 80°C and p H 5.8 w h e n the flow rate is above
 Effect of Chromium on Mesa Corrosion of Carbon Steel 67

100
o Unalloyed steel
[] 0 . 5 - 1 % Ni
• 0 . 5 - 1 % Cr
- - Shell 95 model
--- IFE model
10- [] []
E or-I ..............................
E
oA

c- o oE]A
o Do
. _ _ AOD o~ A°
o oA o
o
0 1
3[3
0
D

0.1 I I I
0 2 4 6 8
Flow rate (ms -1)

Fig. 3 Corrosion rates in loop experiments at 40 °C, 1.8 bar CO 2 and pH 5.8.

2.5 ms -1. At lower flow rates localised attack can occur but protective corrosion films
are easily reformed, thereby lowering the corrosion rate in the locally corroded areas.
At 4-7 ms -1 flow rate the experiments have s h o w n that protective corrosion films
are not reformed in the areas with mesa attack as long as the flow is maintained,
resulting in deep mesa attack with local corrosion rates in the order of 20 m m / y . The
corrosion rate in the mesa attacked area can even be higher than in the 'worst-case'
situation without any corrosion films, possibly due to a galvanic cell between the
film-free metal in the bottom of the mesa attack and the film-covered metal outside
the mesa attack. This is illustrated by the lines in Fig. 2, representing the Shell model
[5] and the IFE model [1] for CO 2 corrosion without protective corrosion films. Both
these models have been fitted to the large n u m b e r of loop experiments in the Kjeller
Sweet Corrosion II project at IFE [1].
Deep, film-free mesa attack was not found in the steels with 0.5-1% chromium.
While localised attack can initiate also in these steels, protective corrosion films seem
to reform more easily. This ability to reform protective films makes localised attack
less dangerous in chromium-containing steels than in plain carbon steels. Addition
of 0.5-1% nickel did not seem to have any p r o n o u n c e d effect on the occurrence of
mesa attack in these experiments.
68 Advances in Corrosion Control and Materials in Oil and Gas Production

The corrosion rates in specimens without mesa attack at 80°C are well below the
predicted worst case corrosion rates given by the lines in Fig. 2, showing that the
corrosion films have a protective effect. The corrosion films formed at 40°C offer
little protection, as seen in Fig. 3.
C h r o m i u m is commonly used to improve the corrosion resistance in wet CO 2
environments, and several oil companies have started to use 0.5% Cr steel in pipelines.
Work at Sumitomo [6,7], Kawasaki [8], and IFE [2] shows a good effect of small
amounts of chromium in CO 2 saturated water at temperatures below 90°C. It is a
general view that chromium does not reduce the corrosion rate significantly on a
film-free steel surface and that the effect is attributed to better protective properties
of the corrosion film. It is suggested that Cr is enriched in the iron carbonate film
and makes it more dense and stable. Kimura has reported [8] that mesa attack did
not occur in carbon steels containing more than 0.25% Cr in rotary immersion tests
at 80°C and pH 6.0. This is in accordance with the experiments reported here. At
higher temperatures the effect of Cr seems to be more unclear. Current experiments
at IFE in the Kjeller Sweet Corrosion V project includes similar loop experiments at
100-150°C.

5. Conclusions

Carbon steel without chromium addition can suffer severe mesa corrosion attack at
80°C and p H around 5.8 when the flow rate is higher than 2.5 ms -1. At lower flow
rates protective corrosion films can reform in areas with localised attack. The corrosion
rate in the mesa attacked area can be higher than in a situation without any corrosion
films, possibly due to a galvanic cell between the film-free bottom of the mesa attack
and the film-covered metal on the outside.
Addition of 0.5-1% chromium prevents the occurrence of deep mesa attack at
80°C and p H 5.8. While localised attack can initiate also in these steels, protective
corrosion films seem to reform more easily in the chromium-containing steels. This
ability to reform protective films makes localised attack less dangerous in chromium-
containing steels than in plain carbon steels.

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 two multi-client
research projects Kjeller Sweet Corrosion III and IV financed by Elf, BP, Shell, Total,
Mobil, Phillips Petroleum, Statoil, Norsk Hydro, Saga Petroleum and Kawasaki Steel.
The authors wish to thank these companies for their technical and financial support.

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"94, Paper No. 14, NACE International, Houston, Tx,1994.
 Effect of Chromium on Mesa Corrosion of Carbon Steel 69

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