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Part 4

Corrosion Resistant
Alloys

34
Localised Corrosion of some Selected Corrosion
Resistant Alloys in the Presence of Very High
Salinity

T. C H E L D I a n d L. S C O P P I O
Eni Agip Explorationand Production, Italy
Centro Sviluppo MaterialiS.p.A.,Italy

ABSTRACT
Oil well reservoir water can have very high salinity values of more than 200 gL -1 as
NaC1, and have w e a k l y ' s w e e t ' e n v i r o n m e n t s (pCO 2 = 0.2 MPa) and m e d i u m
temperatures (100-110C). Experimental work was carried out to investigate the
corrosion resistance of some CRAs (Corrosion Resistant Alloys) in these conditions
and to verify their suitability for tubing strings in wells. Autoclave exposures and
p o t e n t i o d y n a m i c tests were conducted in simulated environments to verify the
resistance to uniform and localised (pitting, crevice) corrosion. Results showed that
duplex and superduplex stainless steels present good resistance to pitting and crevice
corrosion. Supermartensitic steels are affected by rare pitting; potentiodynamic test
results revealed significant differences between the vaious tested supermartensitic
steels showing differing pitting resistances.

1. I n t r o d u c t i o n
In Africa, several oil fields h a v e similar e n v i r o n m e n t a l a g g r e s s i v e n e s s w h i c h is m a i n l y
c h a r a c t e r i s e d b y the v e r y h i g h salinity of the r e s e r v o i r water. Well c o n d i t i o n s of s o m e
s e l e c t e d oil fields are s u m m a r i s e d in Table 1.
Based on literature d a t a [1-3], the available m a t e r i a l selection expert s y s t e m s [4,5]

Table 1. Some selected field conditions characterised by very high salinity reservoir water
Geographical
Area

B.H.T.
(C)

B.EP.
(MPa)

B.H.P.
(MPa)

CO 2 in gas
phase at
BPP (%mol.)

Formation
water
salinity (gL-1)

in situ

Algeria (on-shore)

90

14

32

250-330

4.5

Congo (off-shore)

100-120

26-29

26-32

0.8-1

190

4.6

Congo (off-shore)

80-90

13-20

22

3-3.5

250-300

3.7-3.9 (1}

Libya (on-shore)

120

21

21

3.8

250

//(2)

pH

....

.....

B.H.T. = bottom hole temperature; B.P.P. = bubble point pressure; B.H.P. = bottom hole pressure.
(1)In situ pH values have been calculated on the basis of dissolved CO2, ignoring any buffering effects
from bicarbonate ions as no data were available on water chemical composition.
(2)No data were available on water chemical composition.

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Advances in Corrosion Control and Materials in Oil and Gas Production

and manufacturers engineering field diagrams and guidelines, it was concluded that
materials as noble as duplex stainless steel 22 or 25%Cr or higher, had to be selected
to avoid corrosion in such environments. Carbon steel use is considered a high risk
because of the potentially high corrosivity of the produced water; the consequent
high corrosion rates mainly depend on the water cut, water chemical composition
and on the oil filming efficiency. Other solutions to corrosion mitigation, such as
internally coated carbon steels have been considered to be unsafe for production
environments where damage to the coatings during wire line operations cannot be
excluded in advance [6].
Martensitic stainless steels are normally considered safe up to a medium value of
80-150 gL-1NaC1 depending on the temperature [4]. The following empirical formulae
are also used to provide limits for the applicability of martensitic and supermartensitic
stainless steels, in the absence of H2S, depending on salinity and temperature:

$ if
No
No
NaCI (gL-~) < 130-2/3 T(C) ~ NaCI (gL-1) < 200-8/15 T(C) ~ higher resistant steels

yes
martensitic S S 1 3 C r

yes
supermartensitic SS S13Cr or 15Cr

Nickel Development Institute (NIDI) guidelines [7] limits the use of martensitic
13%Cr to a maximum temperature of about 80C with 250 gL -1 NaC1 depending on
CO 2 content; the temperature limit decreases if the NaC1 content is increased.
The behaviour of the modified martensitic and duplex stainless steels at high
chloride contents (> 20 % NaC1) has not yet been studied in detail [8]. In 200 gL -1
NaC1, low H2S (0.005 MPa) conditions, pitting occurs in the range 70-130C on
martensitic steel and slight general corrosion and severe general corrosion are
observed in the range 130-180C and above 180C respectively [6].
Experimental work has been carried out to investigate the corrosion behaviour of
the most used CRAs (Corrosion Resistant Alloys) for well completions in slightly
sweet environments, i.e. as characterised by low CO 2 contents, medium temperatures
of up to 120C, very high salinity values > 200 gL -1, with the objective of selecting
the most cost'effective CRAs.

2. Experimental
2.1. Materials
All samples used in this investigation were taken from production tubing of oil
country tubular goods. For this study martensitic and some supermartensitic stainless
steels provided by different steel makers (indicated as 'A', 'B' and 'C' in Table 2),
were chosen. Supermartensitic stainless steels (SM) were characterised, from the
corrosion resistance point of view, by a slight difference in Mo and Ni contents.
Duplex 22%Cr (D22), 25%Cr (D25) and a superduplex stainless steel (SD) alloyed
with 0.7% Cu and 0.7% W were also tested. Carbon steel (CS) was selected as a
reference material. The chemical compositions of the tested materials are shown in
Table 2.

Localised Corrosionof some Selected CRAs in the Presenceof Very High Salinity

345

Table 2. Chemical composition of the tested steels (wt%) ( m nil or not tested)
Steel
CS
13Cr
15Cr 'B'
15Cr 'C'
SM 'A'
SM 'B'
D22
D25
SD

UNS
$42000
$42500
$42500
$41424
$41425
$31803
$31260
$32760

Mn

Cu

Ni

Cr

Mo

0.290
0.200
0.110
0.110
0.020
0.019

0.67
0.81
0.76
0.76
0.45
0.73

0.17
<0.05
<0.05
<0.05
0.08
0.09

0.10
0.19
1.55
1.55
5.50
4.75

1.07
13.70
14.87
14.59
13.50
13.29

0.53
0.02
1.55
0.50
2.06
1.62

0.01
<0.05
0.08
0.08
0.05
0.08

0.023
0.023
0.020

1.41
1.25
0.80

0.24
0.24
0.70

5.40
6.60
7.50

21.80
24.40
25.00

2.90
2.70
3.80

0.13
0.18
0.27

0.70

2.2. Corrosion Performance


The resistance to general and localised corrosion such as pitting and crevice was
investigated in two conditions simulating oilfield environments of increasing chloride
contents. Two m e t h o d s were utilised m n a m e l y autoclave long term exposure and
electrochemical p o t e n t i o d y n a m i c tests.

2.3. Autoclave Testing


Mass loss m e a s u r e m e n t s were obtained from flat coupon specimens taken from the
mid-thickness of the tubes. Specimens were ground with No. 800 emery paper, rinsed
with deionised water and then cleaned with acetone. The average corrosion rate in
m m / y e a r was calculated following the ASTM G-1 test procedure.
L o c a l i s e d c o r r o s i o n w a s i n v e s t i g a t e d u s i n g flat c o u p o n s a n d A n d e r s o n
multicrevice s p e c i m e n s a s s e m b l y according to ASTM G-78. After e x p o s u r e in
autoclaves the n u m b e r of c o r r o d e d sectors for each surface of the sample was
determined.
The chemical composition of the solutions and autoclave testing conditions used
to simulate the oilfield environments are s h o w n in Table 3. Tests were carried out at
a total pressure of 10 MPa obtained by a d d i n g nitrogen.

2.4. Electrochemical Potentiodynamic Tests

2.4.1. Pitting
Pitting corrosion behaviour was studied by means of the potentiodynamic technique
c o m p l e m e n t e d with optical microscopy.

Table 3. Environmental conditions chosen for the autoclave exposure tests


Environment
a
b

Ptot

NaC1 solution
(gLq)

Temperature
(C)

Exposure time
(h)

Pco2
(MPa)

(MPa)

330
315

115
115

720
720

0.2
0.2

10
10

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Advances in Corrosion Control and Materials in Oil and Gas Production

Critical current density (i c ), passivity potential (E p), passive current density (ip),
P
P
pitting potential (Ep), transpassivity (Et) and corrosion potential (Ec) were determined
for each test.
Specimens were polarised from a cathodic potential E c = -1.0 V in the anodic
direction until pitting occurred. Pitting potential values were taken as the last value
at which the current was as low as that of a completely passive specimen.
The environment for the pitting corrosion experiments was a deaerated NaC1 solution
(330 gL-1). Measurements were made at 90C with a conventional glass cell.
A scanning rate of 1 mVs -1 was chosen for all the tests. Tests were considered
completed when either the transpassivity E t or the pitting potential Ep value was reached.
2.4.2. Crevice

The potentiodynamic method developed by Crolet et al. [9] was used in order to
assess the crevice corrosion resistance of the selected materials. This is based on
determining a depassivation pH, that is, the pH at which the passive film no longer
offers protection against corrosion. Polarisation curves were a deaerated 330 gL -1
NaC1 solution at 90C at various pH values. The height of the active anodic peak
was plotted as a function of pH. The pH values at which the active peak reached a
nominal value of 0.1 Am -2 was taken as the depassivation pH [10].

3. Results and D i s c u s s i o n
3.1 Autoclave Exposures
3.1.1. Mass loss
The average corrosion rates of the flat coupons exposed to the environmental (see Table
3) conditions in the autoclave are reported in Table 4. Higher mass loss values were
obtained in the simulated oilfield solution a where the chloride content was 330 gL -1.
Carbon steel coupons were affected by general corrosion and high values of the
mass loss were obtained: 450-459 m m / y e a r and 172-210 m m / y e a r for solution a
and b respectively.
As expected [11,12], the corrosion rate of supermartensitic and duplex stainless
steels was practically nil, i.e. lower than 4 m m / y e a r for all the coupons exposed in
both environments (Table 4).
3.1.2. Crevice corrosion

Carbon steel was not considered since it was affected by general corrosion.
Specimens of duplex and superduplex stainless steel exposed in the simulated
environment were only slightly affected by crevice corrosion. (Fig. 1).
Specimens of 13%Cr, 15%Cr and supermartensitic steels were prone to crevice
corrosion (4-6 out of 80 corroded sectors).
However, it is worthy of note, that in all the examined cases, the affected sectors
were only partially corroded.
3.1.3. Pitting corrosion

Table 5 summarises the visual inspection of the pitting corrosion specimens after the
test completion.

Localised Corrosion of some Selected CRAs in the Presence of Very High Salinity

347

Table 4. Results of the autoclave exposure tests: mass loss determination


Environment a

Multicrevice

Steel

CS
13Cr
15Cr 'B'
15Cr 'C'
SM 'A'
SM 'B'
D22
D25
SD

.~9

Environment b

Multicrevice

corrosion rate

Flat coupons
corrosion rate

corrosion rate

Flat coupons
corrosion rate

(Bm/y)

(Bin/y)

(~tm/y)

(~tm/y)

450
Not tested
Not tested
Not tested
1.3
0.5
Not tested
0.2
0.1

459
Not tested
Not tested
Not tested
1.4
0.7
Not tested
0
0

210
59
24.7
17.7
0
0
4.2
0
0

172
94
17.7
16.5
0
0.1
3.4
0
0

82

0
0

<

rn

,-

~-

03

09

04

04

Steel

Crevice susceptibility
Fig. 1 Crevice corrosion susceptibility as a function of the environment salinity. Number of
corroded sectors out of 80 (series I = 330 gL -1 NaCI (a), series 2 = 315 gL -1 NaCI (b)).

All the specimen surfaces were very shiny except for carbon steel and martensitic
stainless steel specimens.
Diffuse pitting was seen on 13%Cr steel.
Supermartensitic stainless steel specimens exposed to environment a were slightly
prone to pitting: both SM 'A' and SM 'B' s h o w e d very few pits on at least one of the
specimen surfaces.
Pit d e p t h was evaluated by m e a n s of the stereomicroscope in order to determine
the seriousness of the localised corrosion attack. Pits were mainly 5-10 ~tm deep and
as a consequence the pitting corrosion rate was estimated to be 60-120 t,t m / y .
Samples of duplex (D25) and s u p e r d u p l e x stainless steels (SD) s h o w e d good
resistance to pitting corrosion.

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Advances in CorrosionControland Materials in Oil and Gas Production

Table 5. Pitting corrosion susceptibility of the tested steels exposed in the autoclave

Steel
CS
13Cr
15Cr 'B'
15Cr 'C'
SM 'A'
SM 'B'
D22
D25
SD

Environment a
pitting (side 1)
pitting (side 2)

Environment b
pitting (side 1)
pitting (side 2)

General corrosion General corrosion Generalcorrosion Generalcorrosion


Not tested
Diffuse
Diffuse
Not tested
Not tested
Rare
Rare
Not tested
Not tested
Rare
Very rare
Not tested
Very rare
No
Very rare
No
Rare
No
Very rare
Very rare
Not tested
No
No
Not tested
No
No
No
No
No
No
No
No
,

,.

3.2. P o t e n t i o d y n a m i c Tests
Potentiodynamic tests were performed on some duplicate material (see Table 6).
Duplex stainless steel (D25) had the highest observed E value, namely 991 mV,
confirming an excellent resistance of the passive film to [ocalised breakdown by
pitting.
Superduplex stainless steel (SD), although characterised by a higher PREN, had
an E value (804 mV) lower than D25, possibly due to the presence of some inclusions
in thPe microstructure.
Both supermartensitic stainless steel SM 'A' and SM 'B' pitting potential values
lower than those of duplex stainless steels, the mean values being 30 and --47 mV,
respectively. A significant difference of around 100 mV was observed between the
two steels; SM 'A' showing the better pitting resistance. The anodic polarisation curves
of the tested steels are shown in Fig. 2.
Figure 3 shows the ranking of the tested steels based on the depassivation p H
value. The higher the p H at which the passive film breaks down, the less resistant is
the material to crevice corrosion.
Decidedly higher crevice corrosion resistance was shown by the stainless duplex
25%Cr steel (D25). Some difference was observed between the two supermartensitic
stainless steels in that SM 'A' was less susceptible to crevice than SM 'B' (Fig. 3).
The depassivation p H of 15%Cr steels was approximately one p H unit greater
than the values for supermartensitic steels.

Table 6. Potentiodynamic test potential values (Ecorr , Ep') and current density (Ipass)
Steel
SM 'A'
SM 'B'
D25
SD

Ecorr (mV)
-650
-563
-650
-617

-680
-720
-700
-630

Ep (mV)
10
50
991
804

Ipass (mAm -2)


50
-44
991
804

19
17
15
13

17
19
15
13

Localised Corrosion of some Selected CRAs in the Presence of Very High Salinity
1000-

600

. . . . . .

D25
SD

349

.............

.~...~ . . . . . .
~o

SMA
SMB

-'""

i!
i/

i.."

~11,

200
>

E
tu

-200

-600

iii1

u111~

........

.....~....,~...,~ . . . . .

..........' ~ ,," :,,Z...,,.....


' ~ ...
"--.o

-1000
I

-9

-8

-7

-6

-5

-4

-3

current density (Acm -2)


Fig. 2 Anodic polarisation curves of supermartensitic steels (SM 'A'and SM 'B'), duplex (D25)
and superduplex steels (SD).

Resistance to
crevice corrosion

D 25

SMA
SM B

15CrB
15CrC

Depassivation pH

Fig. 3 Critical depassivation pH of


the tested steels in 330 gL-1 NaCI,
90C.

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Advances in Corrosion Control and Materials in Oil and Gas Production


3.3. Discussion

All the stainless steel specimens examined after autoclave exposure in simulated oil
field environments showed no general corrosion.
Martensitic stainless steels showed a high susceptibility to localised corrosion in
these environments. The 15Cr steels showed some tendency to localised corrosion
with pitting and crevice corrosion being detected. Critical depassivation pH values
are in fact higher than those of supermartensitic stainless steels.
Supermartensitic stainless steels present a slight susceptibility to localised attack
and proneness to pitting and crevice corrosion should be taken into account.
Resistance to pitting attack of steel 'A' was slightly superior to that of supermartensitic
stainless steel 'B'.
In particular, the positive effect of a higher m o l y b d e n u m content of the
supermartensitic stainless steel 'A' is shown by potentiodynamic tests, highlighting
the different film self-repairing capacity of the steels.
Duplex 25%Cr and superduplex stainless steels tested at 115C and in high chloride
solutions (concentration up to 330 gL -1NaC1) gave good localised corrosion resistance.
No susceptibility to pitting corrosion was observed and passive film resistance to
pitting attack was satisfactory. As regards crevice corrosion resistance although a
few examples of attack were observed in autoclave tests an excellent critical
depassivation pH was found.

4. C o n c l u s i o n s
Experimental work has been carried out to investigate the corrosion behaviour of
the most used CRAs for well completions in environments characterised by low
CO 2 contents, m e d i u m temperatures up to 120C, very high salinity values of
> 200 gL -1, with the purpose of selecting the most cost-effective material. Based on
the results the following conclusions have been drawn:
13%Cr and 15%Cr steels are not to be considered safe and applicable in the
tested environments because of their proneness to localised corrosion.
supermartensitic stainless steels can be used up to a salinity value of about
300 gL -1 in a temperature range of 100-120C with a low content of CO 2.
However, in these environmental conditions supermartensitic stainless steels
are not completely immune to localised corrosion.

duplex and superduplex stainless steels have higher corrosion resistance.

It is worthy of note that these environmental conditions are the 'border line' and
consequently the chemical composition which characterises the various martensitic
steels will affect the corrosion resistance mainly towards localised corrosion.

Localised Corrosion of some Selected CRAs in the Presence of Very High Salinity

351

5. A c k n o w l e d g e m e n t s
The authors w o u l d like to thank ENI-Agip Division for the kind permission to publish
the results presented in this paper and steel makers for the supply of tubular materials
for testing.

References
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