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1-1998

Corrosion of Duplex

acom
Stainless Steels in Seawater
by
Bengt Wallén,
Avesta Sheffield AB, Research & Development, SE-774 80 Avesta, Sweden

One of the first new steels was


Introduction UNS 31500 (3RE60 = 17Cr, 4.5.Ni,
Duplex stainless steels were devel- 2.7Mo, 0.030 which was later
oped in the early thirties in Sweden followed by UNS 31803 (2205 =
and in France. The driving force to 22Cr, 5.5Ni, 3Mo, 0.03C, N). How-
the development was the sensitivity ever, none of the duplex steels
to intergranular corrosion of existing existing in the early seventies were
austenitic steels which often con- resistant enough for a general sea-
tained 0.08-0.10% carbon. The water use and not until the so-called
duplex steels had the same carbon superduplex steels were introduced
content but proved much less sensitive did seawater resistant duplex steels
to this type of corrosion. become available. These steels all
Already before the end of 1930 contain at least 25% chromium and
Avesta Jernverk, now part of Avesta have increased levels of molybdenum
Sheffield, had developed the grades and nitrogen.
453 and 453S and in 1932 these Table 1 summarizes various super-
steels constituted 6.5% of the total duplex steels mentioned in the
production (1). The typical composi- approximate order they were
tions of these steels were 25Cr, 5Ni announced in the literature. The list
with 0 and 1.5% molybdenum re- includes steels which are produced in
spectively, i.e. the latter steel was a most product forms and have a great
forerunner of AISI 329. The steels use in seawater applications as well
were first produced as cast products as steels which seem to have been
but also as plate. The main applica- used very little so far. Two of the first
tion area was in the sulphite industry. superduplex steels were UNS 31260
The French correspondence to 453S and UNS 32550 which were intro-
was Uranus 50 containing 21Cr, 8Ni, duced to the market already in the
2.5Mo and 1.5Cu (2). seventies. In the eighties a number
The first duplex steels had about of new superduplex steels were
65% of ferrite in the solution an- introduced, all containing 25-27%
nealed condition and the high ferrite chromium, 3-4% molybdenum,
content resulted in rather bad me- 0.15-0.30% nitrogen and some with
chanical and corrosion properties in copper and tungsten additions.
the heat affected zone after welding. In the following a review over most AVESTA SHEFFIELD
When it was discovered, in the begin- types of corrosion occurring in sea- CORROSION MANAGEMENT
ning of the fifties, that duplex steels water applications is given. With just AND APPLICATION
have a good resistance to stress a few exceptions, only tests using real ENGINEERING
corrosion cracking (3, 4) the devel- seawater have been taken into con-
opment of steels with a better weld- sideration. Whenever possible, the
ability started. 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.

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Microbially induced corrosion (MIC) behave similarly and are mostly not
other than that caused by the biofilm
Seawater tests attacked at all. In the tests reported in
has been much discussed but seems When stainless steels are used for ref. 34 however, most specimens have
not to be a problem with the super- handling seawater the main corrosion been attacked by pitting corrosion
steels recommended for seawater risks are crevice corrosion and some- beneath salt deposits which formed
applications (23). One exception, times pitting corrosion in weld areas. on the test plates above the water-
however, is the sulphate reducing Stress corrosion cracking seldom line. The crevice corrosion reported
bacteria, the effect of which is dis- occurs at the water temperatures nor- in ref. 36 was very mild and only
cussed in section "Sulphite polluted mally encountered. One exception, occurred as end grain attack in the
water", page 7. however, is when seawater evapor- holes through which the retaining bolt
ates on a hot wall creating a very was passing.
concentrated chloride solution. This
type of corrosion will be treated in
section "External stress corrosion
Chlorinated seawater cracking", page 8. Immersion tests
In most seawater applications the In this section just crevice and — chlorinated seawater
stainless steels will handle water that pitting corrosion tests will be treated. As can be seen in Table 4 most of
has been chlorinated in order to The most frequent way of testing the these tests have been performed at
avoid fouling problems. Chlorine/ crevice corrosion resistance is to elevated and controlled tempera-
hypochlorite is a strong oxidant which apply some kind of crevice formers tures, and they involve only a few of
displaces the corrosion potential of on the surface of the specimens and all superduplex steels available. The
stainless steels in the noble direction. then immerse them in the water. superaustenitic steel UNS S31254 has
The high potentials, which are in the Pitting corrosion may occur on the almost always been included as a
order of 500 to 600 mV SCE, are creviced specimens but, since crevice reference material. UNS S32750 and
consequently more positive than corrosion is normally the dominant S31254 seem to have practically the
those measured in natural water and type, pitting is often studied on same corrosion resistance. When the
make the risk for initiation of crevice welded specimens without using water is chlorinated to 2 ppm, crevice
and pitting corrosion very great. intentional crevices. Tests of this kind corrosion did not occur at 35°C but
On the other hand, chlorine kills are valuable for the screening of only at 45°C. Welded specimens, not
the biofilm which then loses its ability stainless steels in that they indicate equipped with crevices, were not
to catalyse the oxygen reduction. the probability of localized corrosion attacked at 45°C, however (33, 39).
Therefore the cathodic reaction, i.e. initiation. However, the most reliable The second generation superauste-
reduction of oxygen plus chlorine, is (and most expensive) way of evaluat- nitic steel UNS S32654 resisted both
between two and three orders of ing the crevice and pitting corrosion crevice and pitting corrosion at 45°C
magnitude slower than in natural resistance of a material is to perform (38).
seawater in the presence of a biofilm tests with prototype systems com- A comparison between UNS
(24). This means in practice that the posed of real components. In the S32760 and S31254 is reported in
propagation rate of any localized following both types of tests will be ref. 34. As in the preceding tests the
corrosion is much lower in a chlorin- treated. superduplex and the superaustenitic
ated water as long as the effective steels have about the same corrosion
cathodic area is not very large. resistance. The only exception is at
Since there is no temperature-sensi- the lowest temperature (30°C) and 3
tive biofilm in a chlorinated water a Immersion tests ppm of chlorine where only the super-
higher water temperature will always — natural seawater austenitic steel was resistant. It should
increase the corrosivity of the water, A great number of immersion tests be observed that in these tests pitting
and so will an increase in the chlorine have been reported in the literature corrosion often occurred beneath
concentration. In practice, the chlo- and in Table 3 a compilation of some salt deposits above the water-line.
rine additions are often higher than tests reported in recent years is shown. These attacks will probably lower
necessary. It has been reported that a The table includes the superduplex the potential of the specimens and
residual chlorine level of 0.1-0.2 ppm and superaustenitic steels tested. The consequently make the crevice corro-
is sufficient to reduce the microbial results are presented as "no corro- sion results too positive. It is not likely
activity on a stainless steel surface to sion" = 0, "crevice corrosion" = cc or that the steels are resistant to crevice
close to zero (25, 26). If the chlorine as "pitting" = p. No attempt has been corrosion at 70°C and 1.5 ppm of
demand of most seawaters is added, made to classify the degree of attack. chlorine.
addition of less than 1 ppm at the Table 3 does not include lower
injection point is normally sufficient. alloyed steels like S31803 or N08904.
If intermittent chlorination is used, a However, when these steels have
residual level of 1 ppm used during been tested they have almost always
30 minutes per day seems enough to corroded. In most cases the super-
stop the microbial activity (26). duplex and the superaustenitic steels

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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

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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.

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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.

Due to the low cathodic reaction nitic and the superduplex steels was
rate in a chlorinated water (see sec- rather small. In another repassivation
Repassivation tion "Chlorinated seawater", page 3) study, S32760 specimens, taken from
In practice, stainless steels which are the area ratio between cathode and 3/4" solution annealed bar, were
used within proven application limits anode surface is very important. compared with S31254 specimens,
may still be attacked during unfore- A small cathodic surface, or a small machined from NPS 6 Sch 80S seam-
seen temporary service upsets, e.g. pipeline diameter giving high ohmic less pipe produced via the powder
by temperature excursions. Once drops, results in low potentials during route. The experimental technique was
initiated the attack may continue to the repassivation while a large cath- similar to that used in the preceding
propagate even when normal service odic surface results in high potentials. study (48).
conditions are re-established. As shown in Table 7 the longest re- Contrary to the previous investiga-
The conditions for repassivation of passivation times for the rolled super- tion this investigation concludes that
crevice corrosion, initiated in sea- austenitic and the superduplex steels crevice corrosion is much easier to
water at 75°C and 300 mV SCE, have were 49 and 129 days respectively. repassivate in the superduplex than in
been investigated in some detail (46, For welded and cast specimens the the superaustenitic steel. The lowest
47). The stainless steels studied were repassivation time was generally repassivation temperature of S32760
superduplex S32750 and superaus- somewhat longer. If small attacks was 42°C which is above the normal
tenitic S31254, both in the form of (<0.2 mm) can be tolerated, and if operating temperatures 130-40°CI.
plate, welded plate and cast mater- cast S32750 is excepted, only the The report concludes that restoration
ial. The repassivation was studied at repassivation at 40°C and 600 mV of the normal process conditions,
three temperatures under conditions SCE is unacceptable. after a short process upset, will result
simulating a chlorinated water. The In the previous investigation the in repassivation within a few hours
results are shown in Table 7. difference between the superauste- even if crevice corrosion initiates.

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The reason why S32760 is much sponds to very low corrosion rates.
easier to repassivate than S31254, However, others have found that in
Environmental
while S32750 is not, is believed to be SRB-containing seawater (Stot - ≤ 190 cracking
due to the tungsten (0.7%) and ppm), even highly alloyed steels like
copper (0.7%) content in S32760. S32760 show some uniform corrosion Hydrogen embrittlement
These additions are said to increase at the free corrosion potential which In 1989, five incidents of cracking
the resistance to the hydrochloric was around -500 mV SCE (52). occurred in cold worked superduplex
acid-containing solution formed As pointed out by Mollica, et al, S32760 and duplex S31803 stainless
within the corroding crevice. Accord- SRB may become active also in sys- steel used as production tubulars in a
ing to data given in ref. 48, S32760 tems handling natural, air-saturated North Sea offshore field (54). The
has surprisingly good resistance to seawater (53). This is especially the failures, which occurred after removal
hydrochloric acid, at least on a level case in areas where the oxygen of the equipment from the well, were
with that of Alloy C-276 and C-22 in diffusion is sluggish, e.g. underneath attributed to hydrogen embrittlement.
fact. barnacles and gaskets. In such a The tubulars were exposed to hot
system the major part of the surface (120°C), inhibited seawater and were
will be covered by a normal, active polarized in the cathodic direction
biofilm but at the small spots where due to galvanic coupling to the out-
Sulphide polluted water SRB are active the sulphide content side carbon steel casing. A labora-
Under certain circumstances sulphate can be rather high. If the ratio be- tory investigation showed that tubing
reducing bacteria (SRB) may become tween the "free" surface and the SRB which did not crack contained less
active and start producing hydrogen affected areas is large, the latter than 10 wt ppm of hydrogen while
sulphide. It is known that this sub- areas will be strongly polarized in components that cracked contained
stance stimulates the anodic reaction the anodic direction. in excess of 15 ppm. The cracking did
in the corrosion process of stainless By means of anodic polarization not occur in service but was generally
steels and that their pitting potentials curves Mollica and Ventura deter- induced by the occurrence of local
decrease when the concentration mined the critical crevice corrosion overload during handling.
increases (49, 50). However, hydro- potentials for a range of stainless Other investigations conclude that
gen sulphide is a strong reductant steels in a water containing 350-500 appreciable hydrogen embrittlement
which displaces the corrosion poten- ppm of total sulphide (51). They in S32760 exposed to seawater may
tial in the negative direction thus found that even in the case of 316L occur only if the steels are polarized
decreasing the risk for localized and S31803, the crevice corrosion to -900 mV SCE or lower but only if
corrosion. To illustrate which effect is potentials were more positive than the material is cold worked to more
dominant a 95-day test was carried the free corrosion potentials (-450 to than 35HRC and if very high stresses
out in ambient temperature seawater -500 mV SCE) which excludes the are present (55). Superduplex S31260
containing about 1000 ppm of total possibility of spontaneous crevice is also considered to be safe for hy-
2
sulphide (Stot- = H2S + HS- + S -), a corrosion initiation. However, there is drogen embrittlement if the cathodic
concentration which is higher than a high probability of crevice corro- protection potential in seawater is
what is normally found in SRB-con- sion if 316L and S31803 are polar- more positive than -900 mV SCE (56).
taining waters (37). There was no ized to around 0 mV at 15 or 30°C However, galvanic coupling to car-
crevice or pitting corrosion on any while the superaustenitic steel S31254 bon steel should result in potentials
of the steels tested, 316L and S31803 needs to be polarized to 300-350 mV considerably more positive (57, 58).
included. It is therefore concluded SCE at 30°C. Neville and Hodgekiss The effect of hydrogen on bolting
that the low corrosion potentials also detected pitting and crevice materials for sub-sea use has been
( ~ -500 mV SCE) bring chemical corrosion in highly alloyed steels like studied using different techniques (59,
cathodic protection to the stainless S32760 and S31254 after polariza- 60). Slow strain rate tests and fatigue
steels. tion to very positive potentials (≥1000 crack growth tests at high stress ratios
Furthermore, there was no sign of were applied on a range of alloys
mV SCE) in a water containing ≤190
uniform corrosion on the specimens subject to cathodic protection (-1030
ppm of total sulphide (52).
and the weight losses correspond to mV SCE) in artificial seawater. The
corrosion rates less than 0.001 mm/y. two methods gave similar ranking of
Mollica and Ventura determined materials regarding the embrittling
anodic polarization curves for a effects of hydrogen and they show
range of steels in SRB-containing a similar sensitivity to the effects of
seawater with a total sulphide con- hydrogen. As can be seen in Table 8
tent of 350-500 ppm (51). At the free the superaustenitic stainless steels,
corrosion potentials, i.e. -450 to -500 even in 30% cold worked condition
mV SCE, all steels, including 316L and (Rp 0.2 > 1000 MPal has no or little
S31803, were passive and the corro- liability to hydrogen embrittlement,
sion current densities were in the while the superduplex steel shows
2 2
order of 10- µA/cm . This corre- some hydrogen effect.

7
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Table 8. it was then believed that quite high


6
Slow strain rate (3.6 · 10- 1/s) results and fatigue crack growth rates, at a temperatures could be used without
stress intensity of 15 MPa √m in air and in seawater with cathodic protection risking crevice corrosion (8, 9, 67, 68).
(-1030 mV SCE) for some stainless steels (59, 60). However, the offshore industry mostly
Alloy Mechanical data* Slow strain rate Crack growth restricted the use of superduplex and
TTF Area red rate x 10-8 superaustenitic steels to 30-35°C and
Elong. Rp 0.2 Rm rel. to air rel. to air m/cycle 1 ppm of residual chlorine (69).
The first deliveries of super steels
UNS C.W. % % MPa MPa % % Air Sea water
to the seawater systems on offshore
S31254 30 8.0 1067 1163 99 ± 2 106 ± 3 2.5 2.5
platforms took place in the mid-
S34565 52.5 361 792 97 ± 3 93 ± 3 4.1 4.9
eighties and some years later the first
S34565 30 5.4 1278 1303 96 ± 3 77 ± 4 6.0 7.0
corrosion failures were reported (70,
S32750 35.3 631 952 89 ± 4 77 ± 2 3.0 6.0
71). Since then corrosion has been
* Determined by slow strain rate test in air reported from superaustenitic as well
as superduplex systems (72). In almost
all cases the failures have been due
Fatigue tests of cathodically pro- using artificial seawater as an elec- to crevice corrosion. Threaded
tected (-1030 mV SCE), threaded trolyte, the specimens consist of connections have been especially
bolts made of S31254 and carbon electrically heated C-rings, having a vulnerable and a warning against
steel were performed in seawater constant temperature (65). The two their use was given quite early (39).
(61). The results confirm the good tests give the same ranking order Crevice corrosion has also been
behaviour of the superaustenitic steel between different steel grades, i.e. observed on the sealing surfaces of
even when cold deformed to 30%. S31254 > S32760 > S31803. flanges. In most cases the attacks can
Both materials give fatigue life curves A third test, by means of which it is be explained by temperatures widely
well above design curves given in possible to determine the approxi- exceeding the design temperature,
different construction codes. mate temperature limits for external e.g. in connection with coolers or with
SCC, has recently been developed heat tracing used on outdoor piping
External stress (66). It is shown that when evapora- (71). In some cases, however, crevice
tion takes place at elevated tempera- corrosion has occurred at tempera-
corrosion cracking
Duplex stainless steels are considered tures, the solution mainly consists of tures appreciably lower than 30°C.
to possess much better stress corro- very concentrated magnesium chlo- Unfortunately it has not been possible
sion cracking (SCO resistance than ride having a low pH. For instance, to quantify how many of the approxi-
standard austenitic steels like 304 evaporation at 132°C results in a mately 50 000 delivered S31254
-
and 316 and e.g. S31803 is consid- brine containing 9.5M Cl at pH 1.5- flanges that have corroded in sea-
ered resistant to SCC in neutral, 2.5. In the new test method C-rings, water systems where the design limits
oxygen bearing chloride solutions, of loaded to slightly above the yield have never been exceeded. However,
the same strength as seawater, up to strength, are immersed in this electro- the corrosion cases reported have
around 150°C (62). Some years ago, lyte up to 4000 hours. The tempera- resulted in the Norwegian offshore
however, a big high pressure separa- ture is varied until the limit for SCC is standard (Norsok) stipulating max.
tor, made of S31803, on a North Sea found. This method gives the same 15°C and max. 1.5 ppm chlorine for
platform cracked after only a few ranking order as the two preceding superaustenitic and superduplex
years in service in spite of a tempera- tests and the lowest temperatures at steels if crevices are present (73).
ture of max. 100°C (63). The cracking which cracking was observed are In the following some ways of ex-
occurred under the thermal insulation 110°C for the superaustenitic steel tending the application limits of the
which had been soaked with sea- S31254 and 100°C for the duplex super steels in seawater systems will
water. The water evaporated on the steels S32750 and S31803. be discussed.
hot steel surface leaving a very con-
centrated chloride solution able to Use of more
cause the cracking. resistant material
A test method, designed to simulate Application limits In almost all cases the failures ob-
such evaporative conditions, was of super steels served in practice have been crevice
developed in the seventies (64). In this corrosion while pitting corrosion on
so-called drop evaporation test a Practical experience free surfaces or in welds seems to
dilute sodium chloride solution slowly Before the experience from real occur very seldom and only at very
drips onto an electrically heated applications was known, especially high temperatures. Therefore, one
specimen. The dripping frequency in the offshore industry, many steel way to solve the crevice corrosion
is so adjusted that the solution producers were somewhat optimistic problems is to use a more resistant
evaporates completely before the regarding the conditions under which material in the pipe components
next drop arrives. In a similar test, their super steels could be used, and exposed to crevices. It has been

8
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shown that a piping system consisting The same effect can be observed in lower resulting in a very low anode
of S31254 pipes and S32654 flanges seawater too. Laboratory tests, simu- consumption rate (24, 79). This know-
has resisted chlorinated (2 ppm) lating a chlorinated water, show that ledge is now used in practice in the
seawater at a temperature of 45°C. a slow increase of the potential up so-called RCP method where a
So using superaustenitic 6Mo or to the level of a chlorinated water resistor limits the current from the
superduplex pipes and 7Mo flanges results in higher a CCT than if the sacrificial anode. Very low anode
is a possible way to overcome most high potential is applied from the consumption rates are reported for
crevice corrosion problems. (71). start (76). Similarly, aged specimens, the protection of stainless steel piping
Another way is to weld overlay the having a reinforced passive layer, in chlorinated seawater even at high
parts of a component forming the have a CCT which is at least 10°C temperatures (78).
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
Conclusions
• Immersion tests in natural and
material, fillers containing very high the continuously chlorinated (2 ppm)
chlorinated seawater show that
amounts of chromium and molybde- water from the start (38).
superduplex and superaustenitic
num have to be used (74, 75). This means, in practice, that the
6Mo steels have about the same
corrosion resistance of a seawater
Table 9. resistance to initiation of crevice
piping system is dependent on the
Critical crevice temperatures for and pitting corrosion.
way its first contact with the seawater
Ni-base overlays on S31254 plate • Prototype tests, with real compo-
is managed. The best way is to start
MTI-2 method (74). nents, confirm that the difference
with a low temperature and to use no
between the best grades of the two
Composition, % Type of CCT or intermittent chlorination during the
types of steel is small but that there
Cr Ni Mo Other filler °C first weeks. The worst way is to ex-
are variations between grades
21.7 61.8 8.9 Nb SMAW 25
pose the system to a hot, continuously
belonging to the same group.
chlorinated water from the start.
20.9 63.9 8.6 Nb PTA 25 • Superduplex and superaustenitic
17.1 64.3 15.5 SMAW 25 6Mo steels seem to have about the
15.5 58.2 16.0 W PTA 30 Cathodic protection same ability to repassivate a pro-
20 18 6.1 Cu Plate 45 The critical temperatures for crevice pagating crevice attack but opin-
21.3 56.3 13.7 Nb SMAW 65 and pitting corrosion in seawater are ions differ here.
23.3 59.6 15.3 SMAW 80 strongly dependent on the potential. • Sulphide containing seawater is
22.4 60.6 15.4 GTAW 85 In a chlorinated seawater (∼600 mV less corrosive than natural seawater
24.8 57.8 14.8 SMAW 90 SCE) the CCT is around 30°C for but mixed aerobic-anaerobic con-
superduplex and 6Mo superaustenitic ditions may be more corrosive.
SMAW: Shielded metal arc
PTA: Plasma transferred arc steels. If the potential is kept low • Superduplex steels are more sensi-
GTAW: Gas tungsten arc the CCT is much higher, e.g. 80°C at tive to hydrogen embrittlement,
0 mV SCE (78). If a normal type of caused by cathodic protection,
cathodic protection, i.e. with sacrifi- than superaustenitic steels.
Mild start-up period cial anodes, is applied the potential • Superduplex steels seem somewhat
It is well known from CCT determi- will be very low (~ -1000 mV SCE). more sensitive to external stress
nations in 6% ferric chloride that the Since the cathodic current density is corrosion cracking than superaus-
critical temperatures will be higher if determined by the limiting current tenitic steels.
the same specimen is used until the density for oxygen reduction the • Experience from large scale off-
critical temperature is reached than anode consumption rate will be high shore installations shows that
if new specimens are used at each in natural as well as in chlorinated crevice corrosion has occurred in
temperature. The explanation to this water. both superaustenitic 6Mo and
is that the specimens become pas- In a non-chlorinated seawater, the superduplex seawater systems but
sivated by the oxidizing solution at activity of the biofilm results in high that many failures are due to
lower temperatures where no local- 2
reduction currents (∼10 µA/cm ) even service conditions exceeding the
ized corrosion occurs. The improved at 0 mV SCE. However, in a chlorin- design limits.
passive layer thus obtained has a low ated water, where no active biofilm is • For both types of steels the applica-
passive current which reduces the risk present, the reduction current at 0 mV tion limits can be extended by
for crevice corrosion initiation (76). is two to three orders of magnitude different methods.

9
acom No. 1-98

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This article was first presented as a
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tember 1996 72. Lövland P., *Synspunkter på materialvalg
plenary paper at "Duplex Stainless
59. Bardal E. et al, "Effect of hydrogen on for process- og sjövannsystemer"', Material- Steel '97". Published with the kind
bolting materials for subsea use", Fatigue teknologi for petroleumsindustrien, Norske permission of the copy right holder,
90, Volume III, p. 1875-80, 15-20 July Civilingenjörers Förening, 9-10 January "Stainless Steel World".
1990 1997 (in Norwegian)

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.

11
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