1-1998
Corrosion of Duplex
Stainless Steels in Seawater
by
Bengt Wallén,
Avesta Sheffield AB, Research & Development, SE-774 80 Avesta, Sweden
Introduction
Duplex stainless steels were devel-
oped 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 con-
tained 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 composi-
tions of these steels were 25Cr, 5Ni
with 0 and 1.5% molybdenum re-
spectively, 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 applica-
tion 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 an-
nealed condition and the high ferrite
content resulted in rather bad me-
chanical and corrosion properties in
the heat affected zone after welding.
When it was discovered, in the begin-
ning of the fifties, that duplex steels
have a good resistance to stress
corrosion cracking (3, 4) the devel-
opment of steels with a better weld-
ability started.
acom
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). How-
ever, none of the duplex steels
existing in the early seventies were
resistant enough for a general sea-
water 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 super-
duplex 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 intro-
duced 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 AVESTA SHEFFIELD
types of corrosion occurring in sea- CORROSION MANAGEMENT
water applications is given. With just AND APPLICATION
a few exceptions, only tests using real ENGINEERING
seawater have been taken into con-
sideration. 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 No. 1-98

Table 1.
Superduplex stainless steels. Seawater as a
Steel grade Typical composition, % corrosive medium
UNS Trade name Cr Ni Mo Cu N W Ref.
S31260 DP 3 1 25 7 3.0 0.5 >0.10 0.4 5 Natural seawater
S32550 Ferralium 255 2 25 6 3.0 2.5 >0.10 6 In the mid-seventies Mollica, et al,
Alloy 381 3 25 7 3.9 0.15 7
noticed that stainless steels, indepen-
dent of their composition, have sur-
S31200 UR 47N 4 25 7 3.0 0.18 8 prisingly noble potentials in natural
S32550 UR 52N 4 25 7 3.0 1.5 0.18 8 seawater (19). Mollica attributed this
S32760 Zeron 100 5 25 7 3.5 0.7 0.25 0.7 9 observation to a microbial slime layer,
S32750 SAF 2507 6 25 7 4.0 0.30 10 the biofilm, which is quickly formed
Fermanel 2 27 8.5 3.1 1.0 0.23 11 on an inert surface. He showed that
Atlas 958 7 25 7 4.5 0.18 12
the biofilm has a catalytic effect on
the cathodic reaction in the corrosion
DPS 28 1 27 7.5 3.8 0.3 0.30 13
process, i.e. the oxygen reduction.
S32520 UR 52N+ 4 25 6.5 3.4 1.5 0.24 14 After this discovery a very large num-
(1.4469) Märker G-4469 8 26 7.5 4.7 0.27 15 ber of investigations have been
S39274 DP 3W 1 25 7 3.0 0.30 2.0 16 carried out to study the nature and
S39277 DTS 25.7 NWCu 9 25 7.5 3.9 1.7 0.28 1.0 17 effects of the biofilm.
(1.4501) A911 10 25 7 4.0 0.6 0.23 0.7 18 The noble corrosion potentials,
normally in the 300 to 350 mV SCE
Steel 1 Sumitomo Metal 6 Sandvik Steel
producers: 2 Langley Alloys 7 Atlas Foundry range, mean that the risk for initiation
3 Climax Molybdenum 8 Schmidt & Clemens of localized corrosion such as crevice
4 Creusot Loire 9 CSM and pitting corrosion is greater in
5 Weir Materials 10 Böhler Edelstahl natural, living seawater than in sterile
solutions like artificial seawater or
Table 2.
sodium chloride solutions, where the
Superaustenitic stainless steels used as reference material.
potentials are at least a couple of
Steel grade Typical composition, % hundred mV lower. Also due to the
UNS Trade name Cr Ni Mo Cu N biofilm the rate of the oxygen re-
S31254 254 SMO 1 20 18 6.1 0.7 0.20 duction is higher in the natural water.
S32654 654 SMO 1 24 22 7.3 0.5 0.50 At a potential corresponding to that
S34565 Alloy 24 2 24 18 4.5 1.0 0.40 of a stainless steel specimen attacked
N08926 1925 hMo 2 20 24 6.2 0.9 0.20 by crevice corrosion (≤ 0 mV SCE), the
N08031 Alloy 31 2 27 31 6.5 1.5 0.20
reduction current is about two orders
of magnitude greater than in a sterile
N08926 UR B26 3 20 24 6.2 0.9 0.20
chloride solution (20). This means that
N08932 UR SB8 3 25 25 4.7 1.5 0.20
also the propagation rate of any
N08926 25-6Mo 4 20 24 6.2 0.9 0.20
localized corrosion is higher in the
N08367 AL 6XN 5 20 24 6.2 0.2 0.20
natural water.
- K-C 32 6 26 37 5.2 1.0 0.20 Even if an active biofilm seems to
Steel 1 Avesta Sheffield 4 Inco Alloys exist in all seawaters, independent of
producers: 2 KruppVDM 5 Allegheny Ludlum the temperature, heating of the water
3 Creusot Loire 6 Schmidt & Clemens will kill the biofilm and stop its cata-
lytic ability. In northern Atlantic this
happens when the water is heated to
around 30°C (21), while in the Medi-
terranean the activity is not com-
pletely lost until at 40°C (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 25-
30°C in the northern Atlantic.

2

Microbially induced corrosion (MIC)
other than that caused by the biofilm
has been much discussed but seems
not to be a problem with the super-
steels recommended for seawater
applications (23). One exception,
however, is the sulphate reducing
bacteria, the effect of which is dis-
cussed 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 chlorin-
ated water as long as the effective
cathodic area is not very large.
Since there is no temperature-sensi-
tive 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 chlo-
rine 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).
acom No. 1-98
Seawater tests
When stainless steels are used for
handling seawater the main corrosion
risks are crevice corrosion and some-
times pitting corrosion in weld areas.
Stress corrosion cracking seldom
occurs at the water temperatures nor-
mally encountered. One exception,
however, is when seawater evapor-
ates 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 evaluat-
ing the crevice and pitting corrosion
resistance of a material is to perform
tests with prototype systems com-
posed 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 corro-
sion" = 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 super-
duplex 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 water-
line. 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 tempera-
tures, 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 35°C but
only at 45°C. Welded specimens, not
equipped with crevices, were not
attacked at 45°C, however (33, 39).
The second generation superauste-
nitic steel UNS S32654 resisted both
crevice and pitting corrosion at 45°C
(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 (30°C) and 3
ppm of chlorine where only the super-
austenitic 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 corro-
sion results too positive. It is not likely
that the steels are resistant to crevice
corrosion at 70°C and 1.5 ppm of
chlorine.
 acom No. 1-98

Table 3.
Results of immersion tests in natural seawater.
Test conditions Results
Temp. Duration Type of Superduplex steels Superaust. Ref.
°C months specimens S31260 S39274 S31200 S32550 S32760 S32750 S39277 steels
Amb. 12 crevice o 5
Amb. 24 crevice o o S08932(o) 8, 27-30
Amb. 3 crevice o o o o S31254(o) 31
S08932 (o)
N08926 (o)
30 6 crevice o 32
35 3 crevice o S31254(o) 33
35 3 welded o
35 12 crevice o S31254 (cc) 13
30 3 crevice o/o S31254 (o/o)
40 3 crevice o/p S31254 (o/p) 34
70 3 crevice o/p S31254 (o/o)
35 6 crevice cc o S31254 (cc) 16
Amb. 1 crevice cc o S31254 (o) 35
40 6 crevice o o 17
60 6 crevice cc o
Amb. 3 crevice o (cc) S31254 (cc) 36
N08031 (cc)
o = no corrosion
p = pitting corrosion
cc = crevice corrosion

Table 4.
Results of immersion tests in chlorinated seawater.
Test conditions Results
Cl2 Temp. Duration Type of Superduplex steels Superaustenitic steels
ppm °C months specimens S32750 S39274 S32760 S32550 Ref.
2 35 3 crevice o S31254 (o) 33
2 35 3 welded o 33
2 45 3 crevice cc S31254 (cc) 33
2 45 3 welded o 33
1 30 5 butt welded tubes o S31254 (o) 33
1 40 5 butt welded tubes o S31254 (o) 33
1 Amb. 1 crevice o cc S31254 (o) 35
10 45 3 crevice cc S31254 (cc), S32654 (o) 37
2 55 3 crevice cc S31254 (cc), S32654 (cc) 38
2 55 3 welded p S31254 (p), S32654 (o) 38
* 55 3 crevice cc S31254 (cc), S32654 (o) 38
* 55 3 welded p S31254 (p), S32654 (o) 38
1.5 30 3 crevice o/o S31254 (o/o) 34
1.5 40 3 crevice o/p S31254 (o/o) 34
1.5 70 3 crevice o/p S31254 (o/p) 34
3.0 30 3 crevice cc/p S31254 (o/o) 34
3.0 40 3 crevice cc/p S31254 (cc/p) 34
3.0 70 3 crevice cc/o S31254 (cc/p) 34
2 Amb. 1 crevice o 16

* 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

4
 acom No. 1-98

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

Test conditions Steels tested
Type of test Cl2 Temperature Duration Ref.
ppm °C months Superduplex Superaustenitic
Heat exchanger - ≤90 12-24 S31260 40,41
Heat exchanger - Amb. →35 12 S31260, S39274 16
Heat exchanger - 50→60 6 S31260, S39274 16
Piping system 0.5-0.8 Amb. 6-12 S32760, S32550 S31254 31
Heat exchanger 0.5-0.8 Amb.→≤50 3 S32550 S31254 31
Piping system 0.5 30 3 S32550, S32760, S31254, S08932,
S32750, (1.4469) N08367, N08926 15, 42, 43
Piping system 1.5 30 3 S32550, S32760, S31254, S08932,
S32750, (1.4469) N08367, N08926 15,42,43

Prototype tests Table 6.

A summary of tests performed with Results of comparative testing in parallel loops.
Chlorinated seawater, 30°C, 85 days (15, 42, 43)
real components is shown in Table 5.
Results from testing of heat exchang- Steel grade 0.5 ppm Cl2 1.5 ppm Cl2
ers and piping systems have been Attacked (out of 12) Attacked (out of 12)
reported. UNS Type Flanges Welds Flanges Welds
Heat exchangers: In ref. 40 and 41, S31254 Superaustenitic 0 0 3 0
tubes of the superduplex steel UNS N08367 Superaustenitic 1 0 2 0
S31260 have been roller expanded S08932 Superaustenitic 3 0 1 0
into a S31260 tube plate forming a N08926 Superaustenitic 8 0 8 0
model heat exchanger that has been N08926 Superaustenitic 0 0 3 0
tested at different temperatures. It is K-C 32 Superaustenitic 5 0 7 0
concluded that S31260 tubes allow
a maximum process fluid temperature S32550 Superduplex 3 6 2 7
of up to 100°C with a minimum sea- (1.4469) Superduplex 0 0 0 0
water flow rate of 0.5 m/s. This corre- S32760 Superduplex 0 2 3 0
sponds to a maximum skin tempera- S32750 Superduplex 0 1 4 1
ture of 80°C. S31803 Duplex 7 0 6 0
In the same type of heat exchanger
a comparison has been made be- S31254 tube plates, tubes made of excellent way, and so did titanium
tween the superduplex steels S31260 S32550, S31254, and titanium were and S32550 which, however, were
and S39274 (16). In one test ambient tested. Titanium and S31254 showed only tested as pump and valve
temperature seawater was heated by no signs of corrosion and only one respectively.
steam (125°C) to 35°C at a flow rate pit was evident on the S32550 tubes. In another programme eleven 2 inch
of 1 m/s. S31260 suffered crevice Pitting corrosion under salt deposits pipe loops, composed of different
corrosion in the tube-tube plate joint was detected, however, on the stainless steels, were tested in parallel
while S39274 was resistant. In a S31254 tube plate just above the and thus being exposed to exactly
second test the water (2 m/s) was waterline. the same environment (15, 42, 43).
heated from 50° to 60° by 125°C Piping systems: In a very extensive Each loop consisted of six 1 m long
steam. None of the steels corroded. programme different piping system pipes onto which flanges had been
However, since the tube plate was components were tested for 6-12 welded. Two tests were performed,
made of 316, cathodic protection of months in natural and chlorinated one where the seawater was chlorin-
the tube plate was employed. This (0.5-0.8 ppm) seawater of ambient ated to 0.5 ppm residual chlorine and
might explain why S31260 did not temperature (31). The programme one where 1.5 ppm was used. Since
corrode in this case. included several test loops containing both tests were performed at 30°C
A similar test is described in ref. 31. flanged pipes, valves, pipe branching the environments were considerably
Chlorinated, ambient temperature and deadlegs. Pumps were tested in more corrosive than in the preceding
seawater was used to cool steam separate non-metallic systems. test. The results of the tests are shown
having a temperature of 50-60°C. In all tests, components made of in Table 6 where the number of
Since the water velocity was very low 316L and S31803 were attacked by flanges attacked by crevice corrosion,
(0.1 m/s) one might assume that the severe crevice corrosion after a short and the number of flange to pipe
outgoing water had a temperature time. The highly alloyed steels welds attacked by pitting corrosion,
close to that of the steam. Using S32760 and S31254 performed in an are given.

5
 acom No. 1-98

As expected, most of the duplex Table 7.

S31803 flanges exhibit crevice corro- Effect of repassivation conditions on maximum repassivation time and maximum
sion. The superduplex steels behave crevice corrosion depth (46)
very differently. While S32550 is Steel grade Repassivation conditions Results
attacked by crevice corrosion in both UNS Product Potential Temp. Time Attack depth
tests, S32750 and S32760 only cor- mV SCE °C days mm
rode at the higher chlorine level. The
S31254 rolled 0 40 49 0.046
very highly alloyed cast material
welded 35 0.035
1.4469 was resistant in both tests.
cast 36 0.042
Also the superaustenitic steels behave
S32750 rolled 0 40 59 0.010
differently and only S31254 and one
welded 59 0.060
N08926 grade resist crevice corro-
sion at the lowest chlorination level. cast >182 2.510
The results are quite different when S31254 rolled 600 40 11 0.378
considering the joint welds. The welded 16 1.211
superaustenitic steels were never cast 17 1.242
attacked by pitting corrosion but only S32750 rolled 600 40 25 0.501
two of the duplex steels were resistant welded 26 0.598
even at the lowest chlorine concen- cast 17 0.930
tration. The fact that S31803 was not S31254 rolled 0 15 31 0.006
attacked is due to the crevice attacks, welded 68 0.013
which exist on all six pipes, and which cast 45 0.011
brings cathodic protection to the rest S32750 rolled 0 15 129 0.023
of the pipes. welded >131 0.034
Samples from the same steel grades cast >131 0.093
as those tested in the loops were used
S31254 rolled 600 15 <1 0
for determining CCT (plate) and CPT
welded 22 0.009
(butt welded tube) in the laboratory
cast <1 0
(44, 45). The results do not always
S32750 rolled 600 15 <1 0
show a good relation with the results
welded <1 0
of the loop tests and this is especially
true for the CCT ranking. This em- cast 2 0.001
phasizes the importance of qualifying S31254 rolled 200 40 12 0.162
a material by testing real components S32750 rolled 35 0.080
under realistic conditions.

Repassivation
In practice, stainless steels which are
used within proven application limits
may still be attacked during unfore-
seen 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 sea-
water at 75°C and 300 mV SCE, have
been investigated in some detail (46,
47). The stainless steels studied were
superduplex S32750 and superaus-
tenitic S31254, both in the form of
plate, welded plate and cast mater-
ial. The repassivation was studied at
three temperatures under conditions
simulating a chlorinated water. The
results are shown in Table 7.
Due to the low cathodic reaction
rate in a chlorinated water (see sec-
tion "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 cath-
odic surface results in high potentials.
As shown in Table 7 the longest re-
passivation times for the rolled super-
austenitic 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 40°C and 600 mV
SCE is unacceptable.
In the previous investigation the
difference between the superauste-
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 seam-
less pipe produced via the powder
route. The experimental technique was
similar to that used in the preceding
study (48).
Contrary to the previous investiga-
tion 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 42°C which is above the normal
operating temperatures 130-40°CI.
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.

6

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. Accord-
ing 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 sub-
stance stimulates the anodic reaction
in the corrosion process of stainless
steels and that their pitting potentials
decrease when the concentration
increases (49, 50). However, hydro-
gen sulphide is a strong reductant
which displaces the corrosion poten-
tial 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-con-
taining 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 con-
tent 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 corro-
sion current densities were in the
2 2
order of 10- µA/cm . This corre-
acom No. 1-98
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 sys-
tems 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 be-
tween 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 deter-
mined 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 corro-
sion if 316L and S31803 are polar-
ized to around 0 mV at 15 or 30°C
while the superaustenitic steel S31254
needs to be polarized to 300-350 mV
SCE at 30°C. Neville and Hodgekiss
also detected pitting and crevice
corrosion in highly alloyed steels like
S32760 and S31254 after polariza-
tion to very positive potentials (≥1000
mV SCE) in a water containing ≤190
ppm of total sulphide (52).
7
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
(120°C), inhibited seawater and were
polarized in the cathodic direction
due to galvanic coupling to the out-
side carbon steel casing. A labora-
tory 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 hy-
drogen embrittlement if the cathodic
protection potential in seawater is
more positive than -900 mV SCE (56).
However, galvanic coupling to car-
bon 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.

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 Mechanical data*
Elong. Rp 0.2
UNS C.W. % % MPa
S31254 30 8.0 1067
S34565 52.5 361
S34565 30 5.4 1278
S32750 35.3 631
* Determined by slow strain rate test in air
Fatigue tests of cathodically pro-
tected (-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 corro-
sion cracking (SCO resistance than
standard austenitic steels like 304
and 316 and e.g. S31803 is consid-
ered resistant to SCC in neutral,
oxygen bearing chloride solutions, of
the same strength as seawater, up to
around 150°C (62). Some years ago,
however, a big high pressure separa-
tor, made of S31803, on a North Sea
platform cracked after only a few
years in service in spite of a tempera-
ture of max. 100°C (63). The cracking
occurred under the thermal insulation
which had been soaked with sea-
water. The water evaporated on the
hot steel surface leaving a very con-
centrated 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,
acom No. 1-98
Slow strain rate Crack growth
TTF Area red rate x 10-8
Rm rel. to air rel. to air m/cycle
MPa % % Air Sea water
1163 99 ± 2 106 ± 3 2.5 2.5
792 97 ± 3 93 ± 3 4.1 4.9
1303 96 ± 3 77 ± 4 6.0 7.0
952 89 ± 4 77 ± 2 3.0 6.0
using artificial seawater as an elec-
trolyte, 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 approxi-
mate temperature limits for external
SCC, has recently been developed
(66). It is shown that when evapora-
tion takes place at elevated tempera-
tures, the solution mainly consists of
very concentrated magnesium chlo-
ride having a low pH. For instance,
evaporation at 132°C results in a
-
brine containing 9.5M Cl at pH 1.5-
2.5. In the new test method C-rings,
loaded to slightly above the yield
strength, are immersed in this electro-
lyte up to 4000 hours. The tempera-
ture 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
110°C for the superaustenitic steel
S31254 and 100°C 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
8
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 30-35°C and
1 ppm of residual chlorine (69).
The first deliveries of super steels
to the seawater systems on offshore
platforms took place in the mid-
eighties 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 tempera-
tures appreciably lower than 30°C.
Unfortunately it has not been possible
to quantify how many of the approxi-
mately 50 000 delivered S31254
flanges that have corroded in sea-
water systems where the design limits
have never been exceeded. However,
the corrosion cases reported have
resulted in the Norwegian offshore
standard (Norsok) stipulating max.
15°C and max. 1.5 ppm chlorine for
superaustenitic and superduplex
steels if crevices are present (73).
In the following some ways of ex-
tending the application limits of the
super steels in seawater systems will
be discussed.
Use of more
resistant material
In almost all cases the failures ob-
served 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 The same effect can be observed in
of S31254 pipes and S32654 flanges seawater too. Laboratory tests, simu-
has resisted chlorinated (2 ppm) lating a chlorinated water, show that
seawater at a temperature of 45°C. a slow increase of the potential up
So using superaustenitic 6Mo or to the level of a chlorinated water
superduplex pipes and 7Mo flanges results in higher a CCT than if the
is a possible way to overcome most high potential is applied from the
crevice corrosion problems. (71). start (76). Similarly, aged specimens,
Another way is to weld overlay the having a reinforced passive layer,
parts of a component forming the have a CCT which is at least 10°C
crevice with a corrosion resistant higher than that of freshly prepared
nickel-base alloy. However, different specimens (77).
laboratory tests (Table 9) show that The effect has also been confirmed
the critical crevice corrosion tempera- in field tests performed in chlorinated
ture of weld deposits made from Alloy seawater at 55°C. The corrosion resis-
625 or Alloy C-276 fillers are lower tance of S32750, S31254 and S32654
than that of parent metal of most was considerably improved if the ex-
superaustenitic and superduplex posure started with a period of inter-
steels. To get a real improvement over
the resistance of the original flange
mittent chlorination (2 ppm, 1h/d)
instead of exposing the specimens to
material, fillers containing very high the continuously chlorinated (2 ppm)
amounts of chromium and molybde- water from the start (38).
num have to be used (74, 75). This means, in practice, that the
corrosion resistance of a seawater
Table 9.
piping system is dependent on the
Critical crevice temperatures for
way its first contact with the seawater
Ni-base overlays on S31254 plate
is managed. The best way is to start
MTI-2 method (74).
with a low temperature and to use no
Composition, % Type of CCT or intermittent chlorination during the
Cr Ni Mo Other filler °C first weeks. The worst way is to ex-
21.7 61.8 8.9 Nb SMAW 25
pose the system to a hot, continuously
chlorinated water from the start.
20.9 63.9 8.6 Nb PTA 25
17.1 64.3 15.5 SMAW 25
15.5 58.2 16.0 W PTA 30 Cathodic protection
20 18 6.1 Cu Plate 45 The critical temperatures for crevice
21.3 56.3 13.7 Nb SMAW 65 and pitting corrosion in seawater are
23.3 59.6 15.3 SMAW 80 strongly dependent on the potential.
22.4 60.6 15.4 GTAW 85 In a chlorinated seawater (∼600 mV
24.8 57.8 14.8 SMAW 90 SCE) the CCT is around 30°C for
superduplex and 6Mo superaustenitic
SMAW: Shielded metal arc
PTA: Plasma transferred arc steels. If the potential is kept low
GTAW: Gas tungsten arc the CCT is much higher, e.g. 80°C at
0 mV SCE (78). If a normal type of
cathodic protection, i.e. with sacrifi-
Mild start-up period cial anodes, is applied the potential
It is well known from CCT determi- will be very low (~ -1000 mV SCE).
nations in 6% ferric chloride that the Since the cathodic current density is
critical temperatures will be higher if determined by the limiting current
the same specimen is used until the density for oxygen reduction the
critical temperature is reached than anode consumption rate will be high
if new specimens are used at each in natural as well as in chlorinated
temperature. The explanation to this water.
is that the specimens become pas- In a non-chlorinated seawater, the
sivated by the oxidizing solution at activity of the biofilm results in high
lower temperatures where no local- 2
reduction currents (∼10 µA/cm ) even
ized corrosion occurs. The improved at 0 mV SCE. However, in a chlorin-
passive layer thus obtained has a low ated water, where no active biofilm is
passive current which reduces the risk present, the reduction current at 0 mV
for crevice corrosion initiation (76). is two to three orders of magnitude
9
lower resulting in a very low anode
consumption rate (24, 79). This know-
ledge 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 compo-
nents, 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 pro-
pagating crevice attack but opin-
ions differ here.
• Sulphide containing seawater is
less corrosive than natural seawater
but mixed aerobic-anaerobic con-
ditions may be more corrosive.
• Superduplex steels are more sensi-
tive to hydrogen embrittlement,
caused by cathodic protection,
than superaustenitic steels.
• Superduplex steels seem somewhat
more sensitive to external stress
corrosion cracking than superaus-
tenitic steels.
• Experience from large scale off-
shore 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 applica-
tion limits can be extended by
different methods.

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1997 (in Norwegian)
11
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