acom No.

1-96

Seawater Resistance of a Second Generation

Superaustenitic Stainless Steel
by
Bengt Wallén and Elisabet Alfonsson,
Avesta Sheffield AB,
S-774 80 Avesta, Sweden

water or sodium chloride solutions.

Introduction Natural seawater However, the activity of the biofilm is
During the last 10-15 years a number considerably reduced if the water is
of highly alloyed, very corrosion
Crevice corrosion heated to a temperature somewhat
resistant stainless steels, so called In contrast to sterile chloride solutions, above its usual ambient temperature,
super steels, have been introduced natural seawater contains living normally to 30-35°C. Therefore,
into the market. The basis for this organisms which form a biofilm on many seawaters have their maximum
development has been improved inert surfaces such as passive stainless corrosivity in the 25-30°C range.
production methods and an in- steels. The biofilm has a large cata- A crevice corrosion test, performed
creased knowledge of the effect of lytic effect on the cathodic reaction at the LCCT* seawater laboratories,
alloying elements on different steel (oxygen reduction) in the corrosion has recently been reported (5).
properties. Since conventional stain- process. This results in more noble Unwelded specimens, equipped with
less steels have rather limited re- corrosion potentials (+300 to +350 continuous acrylic resin crevice
sistance to localized corrosion, the mV SCE) than in sterile chloride solu- washers torqued to 8.5 Nm, were
new developments have mostly tions and in an increased cathodic exposed to a water of 25°C during
aimed at improving that property. efficiency at cathodic polarization. 60 days. Different surface conditions
Typical examples of the new super For this reason a natural seawater is
steels are the nitrogen-alloyed 6Mo more corrosive than artificial sea- * LaQue Centre for Corrosion Technology.
austenitic and 25Cr duplex steels.
The largest application area for
these steels has been seawater Table 1.
systems of various kinds. However, Typical chemical composition of the tested alloys.
the older super steels have certain Alloy Typical composition, %
limitations when used in such systems Avesto Sheffield UNS C Cr Ni Mo N Cu Other
(1, 2) and there is still a gap between 316 S31600 0.04 17 11 2.2 - - -
them and the best nickel-base alloys. 316L HyMo S31603 0.02 17.5 11.5 2.7 - - -
In an attempt to fill this gap a second 2205 S31803 0.02 22 5.5 3 0.17 - -
generation superaustenitic steel, 904L N08904 0.01 20 25 4.5 - 1.5 -
Avesta Sheffield 654 SMO®, has been
254 SMO S31254 0.01 20 18 6.1 0.20 0.8 -
developed. The chemical composi-
654 SMO S32654 0.01 24 22 7.3 0.50 0.5 Mn 3
tion of this steel, which is shown in
(Alloy 625) N06625 0.02 22 Bal 9 - - Nb, Fe
Table 1, is characterized by very high
(Alloy C-276) N10276 0.008 16 Bal. 16 - - W, Fe
contents of those alloying elements
most important for the resistance to Note: Alloy name within parentheses means that the alloy is not produced by Avesta Sheffield.
localized corrosion, i.e. chromium,
molybdenum and especially nitrogen. Table 2.
General descriptions of 654 SMO Crevice corrosion in natural seawater, 25°C (5).
and its weldability have been given
Surface condition of crevice area
elsewhere (3, 4).
Alloy Ground, 120 grit
In this paper the corrosion resist-
ance of 654 SMO will be compared As delivered - Pickled
with those of other stainless steels 316 10/12, 1.7 mm 2/2, 1.6 mm 2/2, 2.2 mm
and nickel-base alloys under condi- 254 SMO 0/12 2/2, 0.27 mm 0/2
tions simulating different types of sea- 654 SMO 0/12 0/2 0/2
water and applications. The composi- C-276 0/12 1/2, 0.02 mm 0/2
tions of 654 SMO and other alloys Note: 10/12, 1.7 mm means crevice corrosion in ten out of twelve specimens.
tested are shown in Table 1. Max. depth of attack = 1.7 mm.

10

of the specimens were studied and in
the case of "delivery" surfaces, crevice
formers with different surface treat-
ments were used. The results are
summarized in Table 2.
Type 316 was attacked under the
crevice washers in all but two cases,
the maximum depth of attack being
quite high. 254 SMO, and even Alloy
C-276 in one case, suffered crevice
corrosion when the specimens were
ground but not in the other cases.
654 SMO, on the other hand, was
completely resistant in this severe field
test. The test included another seven
proprietary stainless steels and nickel-
base alloys, but only two of these
were fully resistant to crevice
corrosion.
Stress corrosion cracking
At very high temperatures stress
corrosion cracking (SCO may
become a risk. It is quite unlikely,
however, that a cooling water
becomes so hot that such risks are
introduced on highly alloyed stainless
steels. A much more common situation
is when small amounts of cold water
come in contact with a hot steel
surface and, by evaporation, turn into
a very concentrated chloride solution
causing so called external SCC.
This situation is simulated in the
drop evaporation test (6), where a
dilute sodium chloride solution slowly
drips onto an electrically heated
(~300°C) horizontal tensile specimen.
The dripping rate is 6 drops per
minute and the current is adjusted in
such a way that one drop has just
evaporated as the next one arrives. In
this way there will be a cyclic vari-
ation of the specimen temperature
around an average value of about
100°C. The testing time is 500 h and
the threshold stresses, i.e. the lowest
Table 3.
Relative threshold stresses determined
in the Drop Evaporation Test (6).
Alloy R/Rp0.2, 200°C
316 ≤0.1
2205 0.4
904 L 0.7
254 SMO 0.9
654 SMO >1.0
acom No. 1-96
stress at which cracking occurred
when increased in steps of 10% of
the yield strength at 200°C, are
shown in Table 3.
The drop evaporation test is highly
accelerated due to the cycling of
temperature and thereby indirectly
the relative loading. Thus, the test
does not tell whether cracking will
occur or not in a practical situation,
but should on the other hand estab-
lish a realistic ranking order with
regard to SCC under severe eva-
porative conditions. Judging from the
results in Table 3, 654 SMO should
resist SCC under most conditions
experienced in marine environments.
Oxidizing conditions
To avoid production disturbances
caused by fouling, most industrial
seawater systems use chlorinated
water. Chlorine is a strong oxidant
which displaces the corrosion poten-
tial of stainless steels in the noble
direction (+500 to +600mV SCE)
when compared to that in natural
seawater. The high potentials mean
an increased risk for initiation of
pitting and crevice corrosion. While
the influence of the biofilm in natural
seawater is negligible at tempera-
tures above 30-35°C, the effect of
chlorine on the corrosion potential
remains also at higher temperatures.
Thus, the corrosivity of a chlorinated
water always increases with
increasing temperature.
Critical temperatures
A continuously chlorinated seawater
is sterile and artificial seawater or
sodium chloride solutions can be
used as a substitute test medium
provided the potential of the stainless
Table 4.
Critical temperatures in 3% NaCI, +600 mV SCE.
Alloy CPT (weld), °C
254 SMO 60, 68, 72
654 SMO >96, >96, >96
625 88e, 96e, >96
C-276 >96, >96, >96
Note: e = pitting on edge.
11
steel is kept sufficiently high. Two test
methods, developed by Sintef (7, 8)
and building on this philosophy, have
been used by us to determine the
critical pitting (CPT) and crevice
corrosion (CCT) temperatures of
different alloys. CPT was determined
for welded (GTAW) specimens and
CCT for unwelded plate material. In
the latter case the crevices were
formed by commercial gaskets
consisting of rubber-bound aramid
fibre which were bolted to the speci-
mens using a torque of 6 Nm. In both
tests the specimens were exposed in
a 3% sodium chloride solution at
+600 mV SCE, a potential that was
reached after slowly (during 0.5 h)
polarizing the specimens from the
corrosion potential. The temperature
was 20°C at the start of the experi-
ment and was then raised at 4°C/d
until corrosion initiated. Three parallel
specimens of each alloy were
investigated and the results for the
individual specimens are shown in
Table 4.
The only alloy attacked by pitting
was 254 SMO; the other three were
resistant at 96°C which is the highest
temperature investigated. However,
two of the Alloy 625 specimens were
attacked on the edges at somewhat
lower temperatures.
In the crevice corrosion test both
654 SMO and Alloy C-276 were
resistant at 96°C while 254 SMO and
Alloy 625 suffered crevice corrosion
at lower temperatures.
In Figure 1 (page 12) some
examples are shown of the typical
appearance of the crevice corrosion
specimens after exposure. The maxi-
mum test temperatures of the speci-
mens on the photograph were 60°C
(254 SMO) and 96°C (654 SMO,
Alloy 625 and Alloy C-276).
It should be mentioned that the
weight losses of the nickel base alloys
CCT (plate), °C
52,56,60
>96, >96, >96
88, 92, 96
>96, >96, >96
 acom No. 1-96

were higher than those of the stain-

less steels in both tests. For specimens
that, in either test, were not attacked
by localized corrosion at 96°C the
weight losses were <0.001 g/m 2.h
(654 SMO), 0.12-0.16 g/m 2.h (Alloy
2.
C-276) and 0.17 g/m h (Alloy 625).
Similar observations have been made
in neutral chlorine dioxide stages in
pulp bleaching plants. The higher
corrosion rates of the nickel-base
alloys are explained by a lower
transpassive potential than measured 654 SMO
on stainless steels, leading to uniform
transpassive corrosion (9).
The preceding tests should give a
proper ranking of the resistance to a
continuously chlorinated seawater.
However, the critical temperatures
cannot be used for predicting the
temperatures at which the alloys can
be used in a real seawater applica-
tion. The slow temperature increase
strengthens the passivity and results in
too high critical temperatures. Thus,
the CCT of 254 SMO in the labora- Alloy 625 Alloy C-276
tory test was 52-60°C while practical Figure 1.
experience shows that 30-35°C is the Crevice corrosion specimens exposed at +600 mV SCE in 3%
highest temperature that can be used NaCI.
without risking crevice corrosion in
flange connections (2).

Plate heat exchangers
From the corrosion point of view, one
of the most demanding applications
is the plate heat exchanger (PHE). The
construction inherently contains very
tight crevices created by the rubber
sealings and numerous, usually less
corrosive, metal-metal crevices where
the corrugated plates make contact.
The severity of this application is
illustrated by the fact that not even
6Mo superaustenitic steels have a
guaranteed resistance in continuously
chlorinated seawater even at lower
temperatures (10).
Plate heat exchanger conditions
have been simulated in our labora-
tory using multiple crevice washers
made of nitrile rubber of the same
kind as used in the sealings. The
washers, which were 8 mm thick,
were bolted to the specimens with a
force that caused compression to
75% of their original thickness. The
specimens were immersed in a
heated sodium chloride solution of
pH 8 and a potential of +500 mV
SCE was applied immediately. The
testing time was 30 days. By per-
forming the experiments at different
temperatures, the CCT (the lowest test
temperature at which crevice corro-
sion occurred) was determined to
within 5°C. Different chloride con-
centrations are currently being
studied and in Table 5 the results for
25 000 ppm are shown.
Table 5.
Critical crevice corrosion tempera-
tures, PHE conditions, 25000 ppm Cl-,
+500 mV SCE.
Alloy CCT, °C
254 SMO ≤30
654 SMO 60
625 ≤30
C-276 65
The CCTs determined in this test
are much lower than those in the
preceding test. This is probably due
to the fact that the PHE test started
directly at a high temperature and at
a high potential, and that the crevices
formed by the rubber are extremely
severe. Furthermore, the chloride con-
centration of the electrolyte is higher
in the PHE test. The test confirms the
practical experience that 254 SMO
has unsatisfactory resistance for use
in plate heat exchangers operating
with continuously chlorinated, full
strength seawater. 654 SMO on the
other hand has a resistance close to
that of Alloy C-276, which is success-
fully used in many heat exchangers.
Field test
In addition to the laboratory tests a
field test has been performed in
chlorinated seawater at the CEA
seawater laboratories in France (11).
Welded specimens were equipped
with crevice formers made of a com-
mercial gasket material consisting of
rubber-bound aramid fibre. The
torque used to bolt the crevice
formers to the specimens was 40 Nm.
Different alloys were tested using four
parallel specimens of each. The
specimens were immersed in full
strength seawater, heated to 45°C

12
 acom No. 1-96

and containing 10 ppm of residual

chlorine, and exposed during 95
days. The results are summarized in
Table 6. The typical appearance of
the exposed specimens can be seen
in Figures 2-5.
The test conditions are very severe
and both the temperature and the
chlorine concentration exceed those
found in most seawater systems. Only
654 SMO was completely resistant,
confirming the excellent results in the
laboratory tests. Besides crevice
corrosion under the gasket material,
both nickel-base alloys exhibited a
very distinct corrosion circle around
and exactly at the mouth of the
crevice formed by the gasket.
Figure 2. Figure 3.
654 SMO exposed to chlorinated sea- 254 SMO exposed to chlorinated sea-
Table 6.
water, 10 ppm Cl2, 45°C. water, 10 ppm Cl2, 45°C.
Crevice corrosion in chlorinated sea-
water, 10 ppm Cl2, 45°C (11).

Alloy Crevice corrosion

254 SMO 7/8, 0.98 mm
654 SMO 0/8
625 8/8. 0.47 mm
C-276 7/8, 0.31 mm
Note: 7/8, 0.98 mm means crevice corrosion
in seven out of eight crevice sites.
Max. depth of attack = 0.98 mm.

Reducing conditions
Sulphide pollution
Sulphate reducing bacteria (SRB)
receive their energy by reducing
sulphate ions to hydrogen sulphide
while simultaneously oxidizing or-
ganic substances. They grow under
anaerobic conditions and thrive in
e.g. marine sediments containing
decomposing organic matter. Several
investigations show that hydrogen
sulphide stimulates the anodic re-
action in the corrosion process of
stainless steels and that their pitting
potentials decrease with increasing
sulphide concentration (12, 13).
-2
However, more than 10 M (~320
ppm) seems to be needed to impede
the stability of the passive film and
to reduce the pitting resistance of
type 316 and 304 steels in neutral
solutions (14).
Figure 4.
Alloy 625 exposed to chlorinated sea-
water, 10 ppm Cl2, 45°C.
In order to investigate the effect of
very high sulphide concentrations on
crevice corrosion a test was per-
formed in natural seawater at the
CEA laboratories in France (11).
Around 1000 ppm of sulphide was
added to the water. The pH of the
test medium was 6-8 and the 95
days exposure was performed at
ambient temperature. The specimens
were of the same type as described
above in connection with the
chlorination test performed at CEA.
Figure 5.
Alloy C-276 exposed to chlorinated sea-
water, 10 ppm Cl2, 45°C.
Stainless steels, ranging from 316L to
654 SMO, were included in the test.
The corrosivity of the water was
very low in spite of the high sulphide
concentration and there was no
crevice corrosion even on the 316L
specimens. No doubt, this steel grade
should have suffered severe crevice
corrosion if exposed to natural
seawater without sulphide. The only
kind of attack observed in this test
was very shallow pitting on the 316L
specimens in connection with welds.

13

The corrosion potentials were around
-500 mV SCE for all specimens and
the reason for the low corrosivity of
the water may be the reducing
properties of the sulphide ions,
bringing chemical cathodic protection
to the steels.
Mixed aerobic and
anaerobic conditions
As pointed out by Mollica et al, SRB
may become active also in systems
handling natural, air-saturated
seawater (15). This is especially the
case in areas where the oxygen
diffusion is sluggish, e.g. underneath
barnacles or gaskets. In such a
system the major part of the surface
will be covered by a normal, active
biofilm. At the small spots where SRB
are active, however, the sulphide
content might be very high and the
pH reduced. Simultaneously, if the
ratio between the "free" surface and
the SRB affected areas is large, the
latter will be strongly polarized in the
anodic direction.
In order to simulate the worst case
that can develop under these mixed
aerobic and anaerobic conditions, a
laboratory test was performed.
Specimens, equipped with crevice
formers of the multiple crevice type
(PTFE, 1.58 Nm), were exposed for
three days in a 3% sodium chloride
solution which was continuously
bubbled with hydrogen sulfide at
20°C. As a reference test 254 SMO
was exposed to the same solution
which was bubbled with nitrogen
instead of hydrogen sulphide. The
potential of the specimens was kept
at +350 mV SCE which corresponds
to the highest values to be expected
in natural seawater in the presence of
a biofilm. The results are presented in
Table 7.
The corrosion conditions have been
very severe. The solution pH varied
between 4.0 and 4.8 in the different
experiments and the sulphide con-
centration was 2000-3000 ppm.
Substantial crevice corrosion was
observed on 254 SMO and Alloy 625
and widespread but shallow crevice
corrosion on Alloy C-276 too. The
only completely resistant alloy was
654 SMO. The corrosive effect of the
acom No. 1-96
Table 7.
Crevice corrosion in H 2S saturated sodium chloride solution, 20 000 ppm Cl-,
20°C. +350 mV SCE.
Alloy Crevice corrosion
254 SMO 4/4, 0.75 mm
654 SMO 0/4
625 4/4, 0.41 mm
C-276 4/4, 0.07 mm
254 SMO 0/4
Note: 4/4, 0.75 mm means crevice corrosion under four out of four crevice formers.
Max. depth of attack = 0.75 mm.
hydrogen sulphide is further illustrated
by the fact that 254 SMO was
resistant in the solution that was
bubbled with nitrogen.
Conclusions
• The seawater resistance of the new
superaustenitic steel 654 SMO has
been on a level with that of Alloy
C-276 under all conditions
investigated.
• Under strongly oxidizing con-
ditions, such as in chlorinated sea-
water, nickel-base alloys may
suffer significant uniform corrosion,
while stainless steels do not.
• A sulphide polluted seawater is
much less corrosive than natural or
chlorinated seawater even at high
sulphide concentrations.
• Very corrosive conditions exist if a
part of a construction is exposed to
highly sulphide polluted water and
simultaneously polarized to noble
potentials.
This paper was first presented at the "Stainless Steel 1993" conference in
Florence, Italy, in 1993 and it has also been published in "Werkstoffe und
Korrosion", No. 6, 1995.
14
Remark
Uniform corrosion, pitting
N2 bubbling
References
1. B. Wallén. S. Henriksson, Werkstoffe
und Korrosion 40 (1989), p. 602.
2. R. Johnsen, Proc. 11th Scand. Corrosion
Congress, Stavanger (1989), Högskole-
sentret i Rogaland, Stavanger, Norway
(1989), Paper No. F-52.
3. B. Wallén, M. Liljas, P. Stenwall, Werkstoffe
und Korrosion 44 (1993), p. 83.
4. M. Liljas. P. Stenwall, Proc. 12th Int.
Corrosion Congress, Houston (1993),
NACE, Houston, Texas (1993), Paper
No. 538.
5. R. M. Kain, Proc. 12th Int. Corrosion
Congress, Houston (1993), NACE, Houston,
Texas (1993), Paper No. 347.
6. P-E. Arnvig, W. Wasielewska, Paper
presented at the Danish Metallurgical
Society's Winter Meeting, Esbjerg (1993).
7. J. M. Drugli, U. Steinsmo, P. O. Gartland,
T. Rogne, NACE Corrosion/93, Paper
No. 645.
8. P. O. Gartland, U. Steinsmo, J. M. Drugli,
NACE Corrosion/93, Paper No. 646.
9. D. A. Wensley, D. C. Reid. H. Dykstra.
NACE Corrosion/90, Paper No. 537.
10.S. Henrikson, Proc. 9th Scand. Corrosion
Congress, Copenhagen (1983), Korrosions-
centralen ATV, Glostrup, Denmark (1983),
p. 349.
11.D. Féron, B. Wallén, NACE Corrosion/93.
Paper No. 498.
12.G. Herbsleb, W. Schwenk, Werkstoffe und
Korrosion 17 (1966), p. 745.
13.R. C. Newman, H. S. Isaacs, B. Alman,
NACE Corrosion/89, Paper No. 186.
14.D. A. Moreno, J. R. Ibars, C. Ranninger,
H. A. Videla, Corrosion 48 (1992), p. 226.
15.A. Mollica, A. Trevis, E. Traverso,
G. Ventura, G. De Carolis, R. Dellepiane,
Corrosion 44 (1988), p. 194.
 acom No. 1-96

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15
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Dear Reader,
First of all, I would like to thank you for your interest in ACOM.
The success of this publication depends to a certain extent on the active
interest of its readers, and ACOM is fortunate enough to have an avid follow-
ing all over the world. Secondly, I would like to express my thanks for the many
readers' letters addressed to ACOM. Although every effort is made to answer
such correspondence, time constraints may limit the number of replies. I would
therefore like to take this opportunity to ensure you that all letters are appreci-
ated, even if I do not have time to respond personally.
My first year as Technical Editor of ACOM was characterised by an unusually
excessive work load, which unfortunately resulted in some publishing delays for
the first issues. This year will probably be just as busy, but I will do my best to
ensure that our publication reaches readers at more regular intervals.
The contents of ACOM will also to some extent be changed, or rather
expanded, to include special feature issues, in which several articles (or at least
more than one) will cover the same subject. Regular readers will perhaps
recognise this format, which has occasionally been used for earlier issues.
This issue is focused on our most recent development, Avesta Sheffield's
extremely corrosion resistant 654 SMO ® grade, whereas future issues will cover,
among other things, duplex grades and corrosion testing.

Jan Olsson
Technical Editor

Avesta Sheffield AB (publ)

R&D
SE-774 80 Avesta
Sweden
Tel.+46 (0)226 810 00
Telefax+46 (0)226 810 77 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.

All rights reserved.

Comments and correspondence can be directed to Jan Olsson, Technical
Editor, Avesta Sheffield AB, R&D, S-774 80 Avesta, Sweden.
Tel. +46 (0)226 812 48. Telefax +46 (0)226 810 77.

ISSN 1101-0681