by

Bengt Walln,
Avesta Sheffield AB, Research & Development, SE-774 80 Avesta, Sweden

Introduction
Duplex stainless steels were developed in the early thirties in Sweden
and in France. The driving force to
the development was the sensitivity
to intergranular corrosion of existing
austenitic steels which often contained 0.08-0.10% carbon. The
duplex steels had the same carbon
content but proved much less sensitive
to this type of corrosion.
Already before the end of 1930
Avesta Jernverk, now part of Avesta
Sheffield, had developed the grades
453 and 453S and in 1932 these
steels constituted 6.5% of the total
production (1). The typical compositions of these steels were 25Cr, 5Ni
with 0 and 1.5% molybdenum respectively, i.e. the latter steel was a
forerunner of AISI 329. The steels
were first produced as cast products
but also as plate. The main application area was in the sulphite industry.
The French correspondence to 453S
was Uranus 50 containing 21Cr, 8Ni,
2.5Mo and 1.5Cu (2).
The first duplex steels had about
65% of ferrite in the solution annealed condition and the high ferrite
content resulted in rather bad mechanical and corrosion properties in
the heat affected zone after welding.
When it was discovered, in the beginning of the fifties, that duplex steels
have a good resistance to stress
corrosion cracking (3, 4) the development of steels with a better weldability started.

One of the first new steels was

UNS 31500 (3RE60 = 17Cr, 4.5.Ni,
2.7Mo, 0.030 which was later
followed by UNS 31803 (2205 =
22Cr, 5.5Ni, 3Mo, 0.03C, N). However, none of the duplex steels
existing in the early seventies were
resistant enough for a general seawater use and not until the so-called
superduplex steels were introduced
did seawater resistant duplex steels
become available. These steels all
contain at least 25% chromium and
have increased levels of molybdenum
and nitrogen.
Table 1 summarizes various superduplex steels mentioned in the
approximate order they were
announced in the literature. The list
includes steels which are produced in
most product forms and have a great
use in seawater applications as well
as steels which seem to have been
used very little so far. Two of the first
superduplex steels were UNS 31260
and UNS 32550 which were introduced to the market already in the
seventies. In the eighties a number
of new superduplex steels were
introduced, all containing 25-27%
chromium, 3-4% molybdenum,
0.15-0.30% nitrogen and some with
copper and tungsten additions.
In the following a review over most
types of corrosion occurring in seawater applications is given. With just
a few exceptions, only tests using real
seawater have been taken into consideration. Whenever possible, the
behaviour of superduplex steels is
compared with that of superaustenitic
steels. The superaustenitic steels that
are included in any of the succeeding
tests are shown in Table 2.

acom

Corrosion of Duplex
Stainless Steels in Seawater

1-1998

AVESTA SHEFFIELD
CORROSION MANAGEMENT
AND APPLICATION
ENGINEERING

acom No. 1-98

Table 1.
Superduplex stainless steels.
Steel grade
UNS
Trade name

Typical composition, %
Cr
Ni
Mo

S31260
S32550

DP 3
Ferralium 255
Alloy 381

1
2
3

25
25
25

7
6
7

3.0
3.0
3.9

S31200
S32550
S32760

UR 47N
UR 52N
Zeron 100

4
4
5

25
25
25

7
7
7

3.0
3.0
3.5

S32750

SAF 2507
Fermanel
Atlas 958
DPS 28

6
2
7
1

25
27
25
27

7
8.5
7
7.5

4.0
3.1
4.5
3.8

4
8
1
9
10

25
26
25
25
25

6.5
7.5
7
7.5
7

3.4
4.7
3.0
3.9
4.0

S32520
(1.4469)
S39274
S39277
(1.4501)

UR 52N+
Mrker G-4469
DP 3W
DTS 25.7 NWCu
A911

Steel
producers:

1
2
3
4
5

Sumitomo Metal
Langley Alloys
Climax Molybdenum
Creusot Loire
Weir Materials

Seawater as a
corrosive medium
Cu

Ref.

0.5
2.5

>0.10
>0.10
0.15

0.4

5
6
7

1.5
0.7

1.0
0.3
1.5

1.7
0.6

0.18
0.18
0.25

8
8
9

0.7

0.30
0.23
0.18
0.30

10
11
12
13

0.24
0.27
0.30
0.28
0.23

14
15
16
17
18

2.0
1.0
0.7

6 Sandvik Steel
7 Atlas Foundry
8 Schmidt & Clemens
9 CSM
10 Bhler Edelstahl

Table 2.
Superaustenitic stainless steels used as reference material.
Steel grade
UNS

Trade name

S31254
S32654
S34565
N08926
N08031
N08926
N08932
N08926
N08367
-

254 SMO
654 SMO
Alloy 24
1925 hMo
Alloy 31
UR B26
UR SB8
25-6Mo
AL 6XN
K-C 32

Steel
producers:

1
1
2
2
2
3
3
4
5
6

1 Avesta Sheffield
2 KruppVDM
3 Creusot Loire

Typical composition, %
Cr
Ni
Mo

Cu

20
24
24
20
27
20
25
20
20
26

0.7
0.5
1.0
0.9
1.5
0.9
1.5
0.9
0.2
1.0

0.20
0.50
0.40
0.20
0.20
0.20
0.20
0.20
0.20
0.20

18
22
18
24
31
24
25
24
24
37

6.1
7.3
4.5
6.2
6.5
6.2
4.7
6.2
6.2
5.2

4 Inco Alloys
5 Allegheny Ludlum
6 Schmidt & Clemens

Natural seawater
In the mid-seventies Mollica, et al,
noticed that stainless steels, independent of their composition, have surprisingly noble potentials in natural
seawater (19). Mollica attributed this
observation to a microbial slime layer,
the biofilm, which is quickly formed
on an inert surface. He showed that
the biofilm has a catalytic effect on
the cathodic reaction in the corrosion
process, i.e. the oxygen reduction.
After this discovery a very large number of investigations have been
carried out to study the nature and
effects of the biofilm.
The noble corrosion potentials,
normally in the 300 to 350 mV SCE
range, mean that the risk for initiation
of localized corrosion such as crevice
and pitting corrosion is greater in
natural, living seawater than in sterile
solutions like artificial seawater or
sodium chloride solutions, where the
potentials are at least a couple of
hundred mV lower. Also due to the
biofilm the rate of the oxygen reduction is higher in the natural water.
At a potential corresponding to that
of a stainless steel specimen attacked
by crevice corrosion ( 0 mV SCE), the
reduction current is about two orders
of magnitude greater than in a sterile
chloride solution (20). This means that
also the propagation rate of any
localized corrosion is higher in the
natural water.
Even if an active biofilm seems to
exist in all seawaters, independent of
the temperature, heating of the water
will kill the biofilm and stop its catalytic ability. In northern Atlantic this
happens when the water is heated to
around 30C (21), while in the Mediterranean the activity is not completely lost until at 40C (22). This
means that natural seawater has its
highest corrosivity at temperatures
slightly below the temperature at
which the biofilm is killed, e.g. at 2530C in the northern Atlantic.

acom No. 1-98

Microbially induced corrosion (MIC)

other than that caused by the biofilm
has been much discussed but seems
not to be a problem with the supersteels recommended for seawater
applications (23). One exception,
however, is the sulphate reducing
bacteria, the effect of which is discussed in section "Sulphite polluted
water", page 7.

Chlorinated seawater
In most seawater applications the
stainless steels will handle water that
has been chlorinated in order to
avoid fouling problems. Chlorine/
hypochlorite is a strong oxidant which
displaces the corrosion potential of
stainless steels in the noble direction.
The high potentials, which are in the
order of 500 to 600 mV SCE, are
consequently more positive than
those measured in natural water and
make the risk for initiation of crevice
and pitting corrosion very great.
On the other hand, chlorine kills
the biofilm which then loses its ability
to catalyse the oxygen reduction.
Therefore the cathodic reaction, i.e.
reduction of oxygen plus chlorine, is
between two and three orders of
magnitude slower than in natural
seawater in the presence of a biofilm
(24). This means in practice that the
propagation rate of any localized
corrosion is much lower in a chlorinated water as long as the effective
cathodic area is not very large.
Since there is no temperature-sensitive biofilm in a chlorinated water a
higher water temperature will always
increase the corrosivity of the water,
and so will an increase in the chlorine
concentration. In practice, the chlorine additions are often higher than
necessary. It has been reported that a
residual chlorine level of 0.1-0.2 ppm
is sufficient to reduce the microbial
activity on a stainless steel surface to
close to zero (25, 26). If the chlorine
demand of most seawaters is added,
addition of less than 1 ppm at the
injection point is normally sufficient.
If intermittent chlorination is used, a
residual level of 1 ppm used during
30 minutes per day seems enough to
stop the microbial activity (26).

Seawater tests
When stainless steels are used for
handling seawater the main corrosion
risks are crevice corrosion and sometimes pitting corrosion in weld areas.
Stress corrosion cracking seldom
occurs at the water temperatures normally encountered. One exception,
however, is when seawater evaporates on a hot wall creating a very
concentrated chloride solution. This
type of corrosion will be treated in
section "External stress corrosion
cracking", page 8.
In this section just crevice and
pitting corrosion tests will be treated.
The most frequent way of testing the
crevice corrosion resistance is to
apply some kind of crevice formers
on the surface of the specimens and
then immerse them in the water.
Pitting corrosion may occur on the
creviced specimens but, since crevice
corrosion is normally the dominant
type, pitting is often studied on
welded specimens without using
intentional crevices. Tests of this kind
are valuable for the screening of
stainless steels in that they indicate
the probability of localized corrosion
initiation. However, the most reliable
(and most expensive) way of evaluating the crevice and pitting corrosion
resistance of a material is to perform
tests with prototype systems composed of real components. In the
following both types of tests will be
treated.

Immersion tests
natural seawater
A great number of immersion tests
have been reported in the literature
and in Table 3 a compilation of some
tests reported in recent years is shown.
The table includes the superduplex
and superaustenitic steels tested. The
results are presented as "no corrosion" = 0, "crevice corrosion" = cc or
as "pitting" = p. No attempt has been
made to classify the degree of attack.
Table 3 does not include lower
alloyed steels like S31803 or N08904.
However, when these steels have
been tested they have almost always
corroded. In most cases the superduplex and the superaustenitic steels
3

behave similarly and are mostly not

attacked at all. In the tests reported in
ref. 34 however, most specimens have
been attacked by pitting corrosion
beneath salt deposits which formed
on the test plates above the waterline. The crevice corrosion reported
in ref. 36 was very mild and only
occurred as end grain attack in the
holes through which the retaining bolt
was passing.

Immersion tests
chlorinated seawater
As can be seen in Table 4 most of
these tests have been performed at
elevated and controlled temperatures, and they involve only a few of
all superduplex steels available. The
superaustenitic steel UNS S31254 has
almost always been included as a
reference material. UNS S32750 and
S31254 seem to have practically the
same corrosion resistance. When the
water is chlorinated to 2 ppm, crevice
corrosion did not occur at 35C but
only at 45C. Welded specimens, not
equipped with crevices, were not
attacked at 45C, however (33, 39).
The second generation superaustenitic steel UNS S32654 resisted both
crevice and pitting corrosion at 45C
(38).
A comparison between UNS
S32760 and S31254 is reported in
ref. 34. As in the preceding tests the
superduplex and the superaustenitic
steels have about the same corrosion
resistance. The only exception is at
the lowest temperature (30C) and 3
ppm of chlorine where only the superaustenitic steel was resistant. It should
be observed that in these tests pitting
corrosion often occurred beneath
salt deposits above the water-line.
These attacks will probably lower
the potential of the specimens and
consequently make the crevice corrosion results too positive. It is not likely
that the steels are resistant to crevice
corrosion at 70C and 1.5 ppm of
chlorine.

acom No. 1-98

Table 3.
Results of immersion tests in natural seawater.
Test conditions
Temp. Duration
C
months

Type of
specimens

Results

Amb.
Amb.
Amb.

12
24
3

crevice
crevice
crevice

30
35
35
35
30
40
70
35
Amb.
40
60
Amb.

6
3
3
12
3
3
3
6
1
6
6
3

crevice
crevice
welded
crevice
crevice
crevice
crevice
crevice
crevice
crevice
crevice
crevice

S31260

Superduplex steels
S31200
S32550
S32760

S39274

S32750

S39277

Superaust.
steels

o
o

o
o

S08932(o)
S31254(o)
S08932 (o)
N08926 (o)

o
S31254(o)

o
o

S31254 (cc)
S31254 (o/o)
S31254 (o/p)
S31254 (o/o)
S31254 (cc)
S31254 (o)

o
o/o
o/p
o/p
cc

o
cc

o
o

o
o

cc

(cc)

S31254 (cc)
N08031 (cc)

Ref.
5
8, 27-30
31

32
33
13
34
16
35
17
36

o = no corrosion
p = pitting corrosion
cc = crevice corrosion

Table 4.
Results of immersion tests in chlorinated seawater.
Test conditions
Cl2
Temp.
ppm
C
2
2
2
2
1
1
1
10
2
2
*
*
1.5
1.5
1.5
3.0
3.0
3.0
2

Results
Duration
months

35
35
45
45
30
40
Amb.
45
55
55
55
55
30
40
70
30
40
70
Amb.

3
3
3
3
5
5
1
3
3
3
3
3
3
3
3
3
3
3
1

Type of
specimens
crevice
welded
crevice
welded
butt welded tubes
butt welded tubes
crevice
crevice
crevice
welded
crevice
welded
crevice
crevice
crevice
crevice
crevice
crevice
crevice

S32750

Superduplex steels
S39274
S32760

Superaustenitic steels
S32550

Ref.

o
o

S31254 (o)

cc

S31254 (cc)

o
o
o
o
cc
cc
p
cc
p
o/o
o/p
o/p
cc/p
cc/p
cc/o

cc

S31254 (o)
S31254 (o)
S31254 (o)
S31254 (cc), S32654 (o)
S31254 (cc), S32654 (cc)
S31254 (p), S32654 (o)
S31254 (cc), S32654 (o)
S31254 (p), S32654 (o)
S31254 (o/o)
S31254 (o/o)
S31254 (o/p)
S31254 (o/o)
S31254 (cc/p)
S31254 (cc/p)

* Intermittent chlorination (2 ppm, 1h/dl during 1 month followed by continuous chlorination (2 ppm) during 2 months.
o = no corrosion
p = pitting corrosion
cc = crevice corrosion

33
33
33
33
33
33
35
37
38
38
38
38
34
34
34
34
34
34
16

acom No. 1-98

Table 5. Environments used in prototype tests in natural and chlorinated seawater.
Type of test

Test conditions
Cl2
Temperature
ppm
C

Steels tested
Duration
months

Heat exchanger
Heat exchanger
Heat exchanger
Piping system
Heat exchanger
Piping system

0.5-0.8
0.5-0.8
0.5

90
Amb. 35
5060
Amb.
Amb.50
30

12-24
12
6
6-12
3
3

Piping system

1.5

30

Prototype tests
A summary of tests performed with
real components is shown in Table 5.
Results from testing of heat exchangers and piping systems have been
reported.
Heat exchangers: In ref. 40 and 41,
tubes of the superduplex steel UNS
S31260 have been roller expanded
into a S31260 tube plate forming a
model heat exchanger that has been
tested at different temperatures. It is
concluded that S31260 tubes allow
a maximum process fluid temperature
of up to 100C with a minimum seawater flow rate of 0.5 m/s. This corresponds to a maximum skin temperature of 80C.
In the same type of heat exchanger
a comparison has been made between the superduplex steels S31260
and S39274 (16). In one test ambient
temperature seawater was heated by
steam (125C) to 35C at a flow rate
of 1 m/s. S31260 suffered crevice
corrosion in the tube-tube plate joint
while S39274 was resistant. In a
second test the water (2 m/s) was
heated from 50 to 60 by 125C
steam. None of the steels corroded.
However, since the tube plate was
made of 316, cathodic protection of
the tube plate was employed. This
might explain why S31260 did not
corrode in this case.
A similar test is described in ref. 31.
Chlorinated, ambient temperature
seawater was used to cool steam
having a temperature of 50-60C.
Since the water velocity was very low
(0.1 m/s) one might assume that the
outgoing water had a temperature
close to that of the steam. Using

Ref.
Superduplex
S31260
S31260, S39274
S31260, S39274
S32760, S32550
S32550
S32550, S32760,
S32750, (1.4469)
S32550, S32760,
S32750, (1.4469)

Superaustenitic
40,41
16
16
31
31

S31254
S31254
S31254, S08932,
N08367, N08926
S31254, S08932,
N08367, N08926

15, 42, 43
15,42,43

Table 6.
Results of comparative testing in parallel loops.
Chlorinated seawater, 30C, 85 days (15, 42, 43)
Steel grade

0.5 ppm Cl2

Attacked (out of 12)

1.5 ppm Cl2

Attacked (out of 12)

UNS

Type

Flanges

Welds

Flanges

Welds

S31254
N08367
S08932
N08926
N08926
K-C 32

Superaustenitic
Superaustenitic
Superaustenitic
Superaustenitic
Superaustenitic
Superaustenitic

0
1
3
8
0
5

0
0
0
0
0
0

3
2
1
8
3
7

0
0
0
0
0
0

S32550
(1.4469)
S32760
S32750
S31803

Superduplex
Superduplex
Superduplex
Superduplex
Duplex

3
0
0
0
7

6
0
2
1
0

2
0
3
4
6

7
0
0
1
0

S31254 tube plates, tubes made of

S32550, S31254, and titanium were
tested. Titanium and S31254 showed
no signs of corrosion and only one
pit was evident on the S32550 tubes.
Pitting corrosion under salt deposits
was detected, however, on the
S31254 tube plate just above the
waterline.
Piping systems: In a very extensive
programme different piping system
components were tested for 6-12
months in natural and chlorinated
(0.5-0.8 ppm) seawater of ambient
temperature (31). The programme
included several test loops containing
flanged pipes, valves, pipe branching
and deadlegs. Pumps were tested in
separate non-metallic systems.
In all tests, components made of
316L and S31803 were attacked by
severe crevice corrosion after a short
time. The highly alloyed steels
S32760 and S31254 performed in an

excellent way, and so did titanium

and S32550 which, however, were
only tested as pump and valve
respectively.
In another programme eleven 2 inch
pipe loops, composed of different
stainless steels, were tested in parallel
and thus being exposed to exactly
the same environment (15, 42, 43).
Each loop consisted of six 1 m long
pipes onto which flanges had been
welded. Two tests were performed,
one where the seawater was chlorinated to 0.5 ppm residual chlorine and
one where 1.5 ppm was used. Since
both tests were performed at 30C
the environments were considerably
more corrosive than in the preceding
test. The results of the tests are shown
in Table 6 where the number of
flanges attacked by crevice corrosion,
and the number of flange to pipe
welds attacked by pitting corrosion,
are given.

acom No. 1-98

As expected, most of the duplex
S31803 flanges exhibit crevice corrosion. The superduplex steels behave
very differently. While S32550 is
attacked by crevice corrosion in both
tests, S32750 and S32760 only corrode at the higher chlorine level. The
very highly alloyed cast material
1.4469 was resistant in both tests.
Also the superaustenitic steels behave
differently and only S31254 and one
N08926 grade resist crevice corrosion at the lowest chlorination level.
The results are quite different when
considering the joint welds. The
superaustenitic steels were never
attacked by pitting corrosion but only
two of the duplex steels were resistant
even at the lowest chlorine concentration. The fact that S31803 was not
attacked is due to the crevice attacks,
which exist on all six pipes, and which
brings cathodic protection to the rest
of the pipes.
Samples from the same steel grades
as those tested in the loops were used
for determining CCT (plate) and CPT
(butt welded tube) in the laboratory
(44, 45). The results do not always
show a good relation with the results
of the loop tests and this is especially
true for the CCT ranking. This emphasizes the importance of qualifying
a material by testing real components
under realistic conditions.

Repassivation
In practice, stainless steels which are
used within proven application limits
may still be attacked during unforeseen temporary service upsets, e.g.
by temperature excursions. Once
initiated the attack may continue to
propagate even when normal service
conditions are re-established.
The conditions for repassivation of
crevice corrosion, initiated in seawater at 75C and 300 mV SCE, have
been investigated in some detail (46,
47). The stainless steels studied were
superduplex S32750 and superaustenitic S31254, both in the form of
plate, welded plate and cast material. The repassivation was studied at
three temperatures under conditions
simulating a chlorinated water. The
results are shown in Table 7.

Table 7.
Effect of repassivation conditions on maximum repassivation time and maximum
crevice corrosion depth (46)
Steel grade
UNS

Repassivation conditions
Potential
Temp.
mV SCE
C

Product

Results
Time
days

Attack depth
mm

S31254

rolled
welded
cast

40

49
35
36

0.046
0.035
0.042

S32750

rolled
welded
cast

40

59
59
>182

0.010
0.060
2.510

S31254

rolled
welded
cast

600

40

11
16
17

0.378
1.211
1.242

S32750

rolled
welded
cast

600

40

25
26
17

0.501
0.598
0.930

S31254

rolled
welded
cast

15

31
68
45

0.006
0.013
0.011

S32750

rolled
welded
cast

15

129
>131
>131

0.023
0.034
0.093

S31254

rolled
welded
cast

600

15

<1
22
<1

0
0.009
0

S32750

rolled
welded
cast

600

15

<1
<1
2

0
0
0.001

S31254
S32750

rolled
rolled

200

40

12
35

0.162
0.080

Due to the low cathodic reaction

rate in a chlorinated water (see section "Chlorinated seawater", page 3)
the area ratio between cathode and
anode surface is very important.
A small cathodic surface, or a small
pipeline diameter giving high ohmic
drops, results in low potentials during
the repassivation while a large cathodic surface results in high potentials.
As shown in Table 7 the longest repassivation times for the rolled superaustenitic and the superduplex steels
were 49 and 129 days respectively.
For welded and cast specimens the
repassivation time was generally
somewhat longer. If small attacks
(<0.2 mm) can be tolerated, and if
cast S32750 is excepted, only the
repassivation at 40C and 600 mV
SCE is unacceptable.
In the previous investigation the
difference between the superauste6

nitic and the superduplex steels was

rather small. In another repassivation
study, S32760 specimens, taken from
3/4" solution annealed bar, were
compared with S31254 specimens,
machined from NPS 6 Sch 80S seamless pipe produced via the powder
route. The experimental technique was
similar to that used in the preceding
study (48).
Contrary to the previous investigation this investigation concludes that
crevice corrosion is much easier to
repassivate in the superduplex than in
the superaustenitic steel. The lowest
repassivation temperature of S32760
was 42C which is above the normal
operating temperatures 130-40CI.
The report concludes that restoration
of the normal process conditions,
after a short process upset, will result
in repassivation within a few hours
even if crevice corrosion initiates.

acom No. 1-98

The reason why S32760 is much
easier to repassivate than S31254,
while S32750 is not, is believed to be
due to the tungsten (0.7%) and
copper (0.7%) content in S32760.
These additions are said to increase
the resistance to the hydrochloric
acid-containing solution formed
within the corroding crevice. According to data given in ref. 48, S32760
has surprisingly good resistance to
hydrochloric acid, at least on a level
with that of Alloy C-276 and C-22 in
fact.

Sulphide polluted water

Under certain circumstances sulphate
reducing bacteria (SRB) may become
active and start producing hydrogen
sulphide. It is known that this substance stimulates the anodic reaction
in the corrosion process of stainless
steels and that their pitting potentials
decrease when the concentration
increases (49, 50). However, hydrogen sulphide is a strong reductant
which displaces the corrosion potential in the negative direction thus
decreasing the risk for localized
corrosion. To illustrate which effect is
dominant a 95-day test was carried
out in ambient temperature seawater
containing about 1000 ppm of total
2
sulphide (Stot- = H2S + HS- + S -), a
concentration which is higher than
what is normally found in SRB-containing waters (37). There was no
crevice or pitting corrosion on any
of the steels tested, 316L and S31803
included. It is therefore concluded
that the low corrosion potentials
( ~ -500 mV SCE) bring chemical
cathodic protection to the stainless
steels.
Furthermore, there was no sign of
uniform corrosion on the specimens
and the weight losses correspond to
corrosion rates less than 0.001 mm/y.
Mollica and Ventura determined
anodic polarization curves for a
range of steels in SRB-containing
seawater with a total sulphide content of 350-500 ppm (51). At the free
corrosion potentials, i.e. -450 to -500
mV SCE, all steels, including 316L and
S31803, were passive and the corrosion current densities were in the
2
2
order of 10- A/cm . This corre-

sponds to very low corrosion rates.

However, others have found that in
SRB-containing seawater (Stot - 190
ppm), even highly alloyed steels like
S32760 show some uniform corrosion
at the free corrosion potential which
was around -500 mV SCE (52).
As pointed out by Mollica, et al,
SRB may become active also in systems handling natural, air-saturated
seawater (53). This is especially the
case in areas where the oxygen
diffusion is sluggish, e.g. underneath
barnacles and gaskets. In such a
system the major part of the surface
will be covered by a normal, active
biofilm but at the small spots where
SRB are active the sulphide content
can be rather high. If the ratio between the "free" surface and the SRB
affected areas is large, the latter
areas will be strongly polarized in
the anodic direction.
By means of anodic polarization
curves Mollica and Ventura determined the critical crevice corrosion
potentials for a range of stainless
steels in a water containing 350-500
ppm of total sulphide (51). They
found that even in the case of 316L
and S31803, the crevice corrosion
potentials were more positive than
the free corrosion potentials (-450 to
-500 mV SCE) which excludes the
possibility of spontaneous crevice
corrosion initiation. However, there is
a high probability of crevice corrosion if 316L and S31803 are polarized to around 0 mV at 15 or 30C
while the superaustenitic steel S31254
needs to be polarized to 300-350 mV
SCE at 30C. Neville and Hodgekiss
also detected pitting and crevice
corrosion in highly alloyed steels like
S32760 and S31254 after polarization to very positive potentials (1000
mV SCE) in a water containing 190
ppm of total sulphide (52).

Environmental
cracking
Hydrogen embrittlement
In 1989, five incidents of cracking
occurred in cold worked superduplex
S32760 and duplex S31803 stainless
steel used as production tubulars in a
North Sea offshore field (54). The
failures, which occurred after removal
of the equipment from the well, were
attributed to hydrogen embrittlement.
The tubulars were exposed to hot
(120C), inhibited seawater and were
polarized in the cathodic direction
due to galvanic coupling to the outside carbon steel casing. A laboratory investigation showed that tubing
which did not crack contained less
than 10 wt ppm of hydrogen while
components that cracked contained
in excess of 15 ppm. The cracking did
not occur in service but was generally
induced by the occurrence of local
overload during handling.
Other investigations conclude that
appreciable hydrogen embrittlement
in S32760 exposed to seawater may
occur only if the steels are polarized
to -900 mV SCE or lower but only if
the material is cold worked to more
than 35HRC and if very high stresses
are present (55). Superduplex S31260
is also considered to be safe for hydrogen embrittlement if the cathodic
protection potential in seawater is
more positive than -900 mV SCE (56).
However, galvanic coupling to carbon steel should result in potentials
considerably more positive (57, 58).
The effect of hydrogen on bolting
materials for sub-sea use has been
studied using different techniques (59,
60). Slow strain rate tests and fatigue
crack growth tests at high stress ratios
were applied on a range of alloys
subject to cathodic protection (-1030
mV SCE) in artificial seawater. The
two methods gave similar ranking of
materials regarding the embrittling
effects of hydrogen and they show
a similar sensitivity to the effects of
hydrogen. As can be seen in Table 8
the superaustenitic stainless steels,
even in 30% cold worked condition
(Rp 0.2 > 1000 MPal has no or little
liability to hydrogen embrittlement,
while the superduplex steel shows
some hydrogen effect.

acom No. 1-98

Table 8.
6
Slow strain rate (3.6 10- 1/s) results and fatigue crack growth rates, at a
stress intensity of 15 MPa m in air and in seawater with cathodic protection
(-1030 mV SCE) for some stainless steels (59, 60).
Alloy

UNS
S31254
S34565
S34565
S32750

Mechanical data*

C.W. %
30
30

Elong.

Rp 0.2

MPa
1067
361
1278
631

8.0
52.5
5.4
35.3

Slow strain rate

TTF
Area red
Rm rel. to air
rel. to air

MPa
1163
792
1303
952

%
99 2
97 3
96 3
89 4

Crack growth
rate x 10-8
m/cycle
Air
2.5
4.1
6.0
3.0

%
106 3
93 3
77 4
77 2

Sea water
2.5
4.9
7.0
6.0

* Determined by slow strain rate test in air

Fatigue tests of cathodically protected (-1030 mV SCE), threaded

bolts made of S31254 and carbon
steel were performed in seawater
(61). The results confirm the good
behaviour of the superaustenitic steel
even when cold deformed to 30%.
Both materials give fatigue life curves
well above design curves given in
different construction codes.

External stress
corrosion cracking
Duplex stainless steels are considered
to possess much better stress corrosion cracking (SCO resistance than
standard austenitic steels like 304
and 316 and e.g. S31803 is considered resistant to SCC in neutral,
oxygen bearing chloride solutions, of
the same strength as seawater, up to
around 150C (62). Some years ago,
however, a big high pressure separator, made of S31803, on a North Sea
platform cracked after only a few
years in service in spite of a temperature of max. 100C (63). The cracking
occurred under the thermal insulation
which had been soaked with seawater. The water evaporated on the
hot steel surface leaving a very concentrated chloride solution able to
cause the cracking.
A test method, designed to simulate
such evaporative conditions, was
developed in the seventies (64). In this
so-called drop evaporation test a
dilute sodium chloride solution slowly
drips onto an electrically heated
specimen. The dripping frequency
is so adjusted that the solution
evaporates completely before the
next drop arrives. In a similar test,

using artificial seawater as an electrolyte, the specimens consist of

electrically heated C-rings, having a
constant temperature (65). The two
tests give the same ranking order
between different steel grades, i.e.
S31254 > S32760 > S31803.
A third test, by means of which it is
possible to determine the approximate temperature limits for external
SCC, has recently been developed
(66). It is shown that when evaporation takes place at elevated temperatures, the solution mainly consists of
very concentrated magnesium chloride having a low pH. For instance,
evaporation at 132C results in a
brine containing 9.5M Cl at pH 1.52.5. In the new test method C-rings,
loaded to slightly above the yield
strength, are immersed in this electrolyte up to 4000 hours. The temperature is varied until the limit for SCC is
found. This method gives the same
ranking order as the two preceding
tests and the lowest temperatures at
which cracking was observed are
110C for the superaustenitic steel
S31254 and 100C for the duplex
steels S32750 and S31803.

Application limits
of super steels
Practical experience
Before the experience from real
applications was known, especially
in the offshore industry, many steel
producers were somewhat optimistic
regarding the conditions under which
their super steels could be used, and

it was then believed that quite high

temperatures could be used without
risking crevice corrosion (8, 9, 67, 68).
However, the offshore industry mostly
restricted the use of superduplex and
superaustenitic steels to 30-35C and
1 ppm of residual chlorine (69).
The first deliveries of super steels
to the seawater systems on offshore
platforms took place in the mideighties and some years later the first
corrosion failures were reported (70,
71). Since then corrosion has been
reported from superaustenitic as well
as superduplex systems (72). In almost
all cases the failures have been due
to crevice corrosion. Threaded
connections have been especially
vulnerable and a warning against
their use was given quite early (39).
Crevice corrosion has also been
observed on the sealing surfaces of
flanges. In most cases the attacks can
be explained by temperatures widely
exceeding the design temperature,
e.g. in connection with coolers or with
heat tracing used on outdoor piping
(71). In some cases, however, crevice
corrosion has occurred at temperatures appreciably lower than 30C.
Unfortunately it has not been possible
to quantify how many of the approximately 50 000 delivered S31254
flanges that have corroded in seawater systems where the design limits
have never been exceeded. However,
the corrosion cases reported have
resulted in the Norwegian offshore
standard (Norsok) stipulating max.
15C and max. 1.5 ppm chlorine for
superaustenitic and superduplex
steels if crevices are present (73).
In the following some ways of extending the application limits of the
super steels in seawater systems will
be discussed.

Use of more
resistant material
In almost all cases the failures observed in practice have been crevice
corrosion while pitting corrosion on
free surfaces or in welds seems to
occur very seldom and only at very
high temperatures. Therefore, one
way to solve the crevice corrosion
problems is to use a more resistant
material in the pipe components
exposed to crevices. It has been

acom No. 1-98

shown that a piping system consisting
of S31254 pipes and S32654 flanges
has resisted chlorinated (2 ppm)
seawater at a temperature of 45C.
So using superaustenitic 6Mo or
superduplex pipes and 7Mo flanges
is a possible way to overcome most
crevice corrosion problems. (71).
Another way is to weld overlay the
parts of a component forming the
crevice with a corrosion resistant
nickel-base alloy. However, different
laboratory tests (Table 9) show that
the critical crevice corrosion temperature of weld deposits made from Alloy
625 or Alloy C-276 fillers are lower
than that of parent metal of most
superaustenitic and superduplex
steels. To get a real improvement over
the resistance of the original flange
material, fillers containing very high
amounts of chromium and molybdenum have to be used (74, 75).
Table 9.
Critical crevice temperatures for
Ni-base overlays on S31254 plate
MTI-2 method (74).
Composition, %
Cr
Ni
Mo Other
21.7
20.9
17.1
15.5
20
21.3
23.3
22.4
24.8

61.8
63.9
64.3
58.2
18
56.3
59.6
60.6
57.8

8.9
8.6
15.5
16.0
6.1
13.7
15.3
15.4
14.8

Nb
Nb
W
Cu
Nb

Type of
filler

CCT
C

SMAW
PTA
SMAW
PTA
Plate
SMAW
SMAW
GTAW
SMAW

25
25
25
30
45
65
80
85
90

SMAW: Shielded metal arc

PTA: Plasma transferred arc
GTAW: Gas tungsten arc

Mild start-up period

It is well known from CCT determinations in 6% ferric chloride that the
critical temperatures will be higher if
the same specimen is used until the
critical temperature is reached than
if new specimens are used at each
temperature. The explanation to this
is that the specimens become passivated by the oxidizing solution at
lower temperatures where no localized corrosion occurs. The improved
passive layer thus obtained has a low
passive current which reduces the risk
for crevice corrosion initiation (76).

The same effect can be observed in

seawater too. Laboratory tests, simulating a chlorinated water, show that
a slow increase of the potential up
to the level of a chlorinated water
results in higher a CCT than if the
high potential is applied from the
start (76). Similarly, aged specimens,
having a reinforced passive layer,
have a CCT which is at least 10C
higher than that of freshly prepared
specimens (77).
The effect has also been confirmed
in field tests performed in chlorinated
seawater at 55C. The corrosion resistance of S32750, S31254 and S32654
was considerably improved if the exposure started with a period of intermittent chlorination (2 ppm, 1h/d)
instead of exposing the specimens to
the continuously chlorinated (2 ppm)
water from the start (38).
This means, in practice, that the
corrosion resistance of a seawater
piping system is dependent on the
way its first contact with the seawater
is managed. The best way is to start
with a low temperature and to use no
or intermittent chlorination during the
first weeks. The worst way is to expose the system to a hot, continuously
chlorinated water from the start.

Cathodic protection
The critical temperatures for crevice
and pitting corrosion in seawater are
strongly dependent on the potential.
In a chlorinated seawater (600 mV
SCE) the CCT is around 30C for
superduplex and 6Mo superaustenitic
steels. If the potential is kept low
the CCT is much higher, e.g. 80C at
0 mV SCE (78). If a normal type of
cathodic protection, i.e. with sacrificial anodes, is applied the potential
will be very low (~ -1000 mV SCE).
Since the cathodic current density is
determined by the limiting current
density for oxygen reduction the
anode consumption rate will be high
in natural as well as in chlorinated
water.
In a non-chlorinated seawater, the
activity of the biofilm results in high
2
reduction currents (10 A/cm ) even
at 0 mV SCE. However, in a chlorinated water, where no active biofilm is
present, the reduction current at 0 mV
is two to three orders of magnitude
9

lower resulting in a very low anode

consumption rate (24, 79). This knowledge is now used in practice in the
so-called RCP method where a
resistor limits the current from the
sacrificial anode. Very low anode
consumption rates are reported for
the protection of stainless steel piping
in chlorinated seawater even at high
temperatures (78).

Conclusions
Immersion tests in natural and
chlorinated seawater show that
superduplex and superaustenitic
6Mo steels have about the same
resistance to initiation of crevice
and pitting corrosion.
Prototype tests, with real components, confirm that the difference
between the best grades of the two
types of steel is small but that there
are variations between grades
belonging to the same group.
Superduplex and superaustenitic
6Mo steels seem to have about the
same ability to repassivate a propagating crevice attack but opinions differ here.
Sulphide containing seawater is
less corrosive than natural seawater
but mixed aerobic-anaerobic conditions may be more corrosive.
Superduplex steels are more sensitive to hydrogen embrittlement,
caused by cathodic protection,
than superaustenitic steels.
Superduplex steels seem somewhat
more sensitive to external stress
corrosion cracking than superaustenitic steels.
Experience from large scale offshore installations shows that
crevice corrosion has occurred in
both superaustenitic 6Mo and
superduplex seawater systems but
that many failures are due to
service conditions exceeding the
design limits.
For both types of steels the application limits can be extended by
different methods.

acom No. 1-98

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This article was first presented as a

plenary paper at "Duplex Stainless
Steel '97". Published with the kind
permission of the copy right holder,
"Stainless Steel World".

Although Avesta Sheffield has made every effort to ensure the accuracy of this publication, neither it nor any contributor can accept any legal
responsibility whatsoever for errors or omissions or information found to be misleading or any opinions or advice given.

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