164 Mori and Bauernfeind
Pitting and crevice corrosion of superaustenitic
stainless steels
Loch- und Spaltkorrosion superaustenitischer Stähle
Dedicated to Professor Dr. Herbert Zitter on the occasion of his 75th birthday
Superaustenites are mainly used in offshore applications, oil pro-
duction and chemical industry. Most important types of localised
corrosion of these steels are pitting and crevice corrosion. Investi-
gated materials were N08028, S31254 and three modified alloys.
Chromium content of investigated alloys varied between 20 and
27%, molybdenum between 3.2 and 6.0%, nitrogen between 0.1
and 0.36% and copper between 0 and 1.1%. For means of compar-
ison stainless steel AISI 316L has been included in the study.
Pitting and crevice corrosion of these highly corrosion resistant
steels has been investigated by use of standardized tests. Critical
pitting temperature and critical crevice temperatures were deter-
mined according to ASTM G 48, Methods C and D, respectively.
Electrochemical measurements for determination of pitting poten-
tials were done according to ASTM G 61 as well as for determina-
tion of critical pitting temperatures according to ASTM G 150.
Results are presented as function of MARC (Measure of alloying
for resistance to corrosion) defined by Speidel since linear correla-
tion coefficients were higher when compared to conventional
PREN. Results obtained by different testing methods must not
be compared directly. Every test however is sensitive to microstruc-
tural defects like precipitations and segregations that decrease cor-
rosion resistance. The higher alloyed a material is, the higher is its
tendency to form microstructural defects, and the more difficult is it
to reach its theoretical corrosion resistance at given chemical com-
position.
1 Introduction
Superaustenitic stainless steels have been developed in the
early 1980’s and until today there exists no clear definition of
this term. Several attempts to describe this group of materials
can be found in literature, e.g. from Sequeira [1]: “Superaus-
tenitic stainless steels are defined as austenitic steels with high-
er amounts of chromium, nickel, molybdenum and nitrogen
resulting in an iron content close to or less than 50%.” Some-
times they are called “high molybdenum stainless steels” [2].
Superaustenites are used for very highly corrosive environ-
ments like chemical processing equipment, critical seawater
and severe brackish water-handling systems, desalination
systems, plate heat exchangers, municipal waste incineration
systems and chlorine and chlorine dioxide pulp bleaching
* G. Mori, D. Bauernfeind
Institute of General and Analytical Chemistry, University of Leo-
ben, Austria,
Franz-Josef-Str. 18, A-8700 Leoben (Austria)
DOI: 10.1002/maco.200303746
Materials and Corrosion 2004, 55, No.
G. Mori* and D. Bauernfeind
Die Hauptanwendungsgebiete von superaustenitischen Stählen
sind im Offshore-Anlagenbau bei der Öl- und Gasförderung und
in der chemischen Industrie. Die wichtigsten Arten örtlicher Kor-
rosion sind dabei Loch- und Spaltkorrosion. In der vorliegenden
Arbeit wurden die Legierungen N08028, S31254 und drei neue Le-
gierungen untersucht. Dabei wurde der Cr-Gehalt der Legierungen
zwischen 20 und 27%, der Mo-Gehalt zwischen 3,2 und 6,0%, der
Gehalt an Stickstoff zwischen 0,1 und 0,36% sowie der Cu-Gehalt
zwischen 0 und 1,1% variiert. Als austenitischer Vergleichswerk-
stoff wurde der Stahl AISI 316L untersucht.
Die Beständigkeit gegen Loch- und Spaltkorrosion wurde durch
Standardprüfverfahren ermittelt. Es wurden die kritische Loch-
fraßtemperatur sowie die kritische Spaltkorrosionstemperatur
nach ASTM G 48, Methode C und D, bestimmt. Weiters wurden
elektrochemische Untersuchungen zur Bestimmung des Lochkor-
rosionspotentials nach ASTM G 61 und der kritischen Lochkorro-
sionstemperatur nach ASTM G 150 durchgeführt.
Die Ergebnisse sind als Funktion des von Speidel definierten
MARC (Measure of alloying for resistance to corrosion) dargestellt,
da dieser die besten Korrelationskoeffizienten ergab. Die verschie-
denen Prüfmethoden dürfen nicht direkt miteinander verglichen
werden. Der negative Einfluss von Ausscheidungen und Seigerun-
gen auf die Korrosionsbeständigkeit ist jedoch mit allen Prüfverfah-
ren feststellbar. Je höher legiert ein Werkstoff ist, desto schwieriger
ist es, ihn frei von Ausscheidungen und Seigerungen herzustellen,
und desto schwerer kann er seine theoretische Korrosionsbeständig-
keit bei gegebener chemischer Zusammensetzung erreichen.
systems. The main reason for development of superaustenitic
stainless steels was that these very highly corrosive environ-
ments forced steel producers to develop steels with higher
chromium, molybdenum and nitrogen contents for higher re-
sistance to pitting and crevice corrosion. One big advantage of
superaustenites is that they are cheaper than nickel-base-al-
loys which can be used for these applications as well.
Between 1985 and 1990 superaustenites with a nitrogen
content of about 0.4% were produced. These steels contained
20 to 23% chromium, 15 to 18% nickel, 4 to 5% molybdenum
and about 6% manganese to stabilize face-centered cubic lat-
tice and to maintain nitrogen in solution. The next important
improvement happened in 1992, when the highest alloyed
superaustenitic steel to date (S32654) was introduced, con-
taining 24% Cr, 22% Ni, 7.3% Mo, 0.5% N and only about
3% Mn. Pitting and crevice corrosion resistance of this alloy
is superior to all other stainless steels and similar to nickel-
base alloys [3].
Alloying of nitrogen to austenitic stainless steels has three
main effects. First it stabilizes the austenitic structure and
makes modifications of common alloy compositions possible.
F 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2004, 55, No. 3 Pitting and crevice corrosion of superaustenitic stainless steels 165

Table 1. Literature survey of formulas for PREN

Tabelle 1. Literaturauswertung verschiedener Formeln für PREN

Name factor valid for Source

a b c d e f g h

PREN 3.3 13 Austenites [6, 7]

PREN 3.3 16 Austenites [8, 9]
PREN20N 3.3 20 – 27 Austenites [10, 11]
PREN30N 3.3 30 Austenites [9]
PREN 3.3 43 – 53 Austenites [12]
PREN 3.3 70 Duplex steels [12]
PREN 3.5 20 2.5 Superaustenites [13]
PRENW 3.3 30 1.65 Superaustenites [14, 15]
PRENW 3.3 30 1.7 Superaustenites [16]
PREN 3.3 36 7  1.6 Superaustenites [17]
PRENN2 Mn 3.3 51 6  90  1.6 Superaustenites [17]
PRENMn 3.3 30 1 Superaustenites [18]
PREN 3.3 37 4.5 Superaustenites [19]
MARC 3.3 20  0.5 20  0.25 Superaustenites [5]
2
PREN/MARC ¼ %Cr þ a
%Mo þ b
%N þ c
%Mo
%N þ d
%N þ e
%Mn þ f
%W þ g
%C þ h
%Ni
Austenites: 16 – 22%Cr, 0.5 – 20%Ni, 0.1 – 4.5%Mo, 0.02 – 0.2%N
Superaustenites:18 – 25%Cr, 18 – 25%Ni, 4 – 7.3%Mo, 0.2 – 0.9%N
Duplex steels: 20 – 24%Cr, 6 – 11%Ni, 3%Mo, 0.45%N

Secondly, it enhances clearly the strength of austenitic steels
as a very efficient solid solution strengthening element. Final-
ly it improves corrosion resistance especially to pitting and
crevice corrosion.
Superaustenites have such high contents of chromium,
nickel, molybdenum and nitrogen that it is not always possible
to get all alloying elements in solution. Such highly alloyed
stainless steels can therefore contain traces of intermetallic
phases like chi or sigma phase especially at the centre of
the material. Precipitations can also happen when the steel
is exposed to temperatures between 600 and 1000 8C, for ex-
ample during welding.
The most common forms of corrosion of superaustenites are
pitting and crevice corrosion and resistance to these types of
corrosion is determined particularly by the content of chro-
mium, molybdenum and nitrogen. Lorenz and Medawar [4]
were the first who found a relation between chemical compo-
sition and pitting resistance. The pitting resistance equivalent
number (PREN) allows a comparison of different stainless
steels concerning their corrosion resistance. One possibility
to calculate this value is to use the following equation:
PREN20N ¼ %Cr þ 3:3%Mo þ 20%N ð1Þ
Most commonly used formulas of measures for pitting re-
sistance are PREN20N and PREN30N (factor 30 for nitrogen).
One disadvantage of these formulas might be that influence of
additional elements is not taken into account, e.g. the negative
effect of manganese on pitting corrosion resistance. Several
different factors for PREN calculation have been proposed,
so especially the factor for nitrogen varies and synergistic fac-
tors like %Mo
%N have been introduced by some authors [3].
A summary of literature data on different PREN formulas is
given in Table 1 [5 – 19]. Influence of nitrogen increases for
higher alloyed materials. MARC (Measure of Alloying for
Resistance to Corrosion) is a new formula which has recently
been introduced by Speidel [5]. Aims of the present work
were:
1) Characterization and comparison of pitting and crevice cor-
rosion properties of three new superaustenitic stainless
steels with two already established ones according to
ASTM G 48, G 61 and G 150.
2) Search for the PREN formula from literature that describes
their pitting and crevice corrosion behaviour best.
3) Give a qualitative estimation of the influence of precipita-
tions and segregations on the corrosion resistance of super-
austenites.
2 Materials and methods
Two conventional superaustenites (N08028 and S31254)
and three modified alloys labelled A, B and C with higher ni-
trogen contents were tested as well as stainless steel AISI
316L, which was used as a standard austenitic reference ma-
terial. Samples of all six investigated steels were taken from
large scale forged cylinders. All steels which were applied in
this investigation had an austenitic microstructure in the solu-
tion annealed condition. Rectangular specimens with dimen-
sion of 40  20  4 mm (l  w  t) were machined. Chemi-
cal composition and mechanical properties of materials are
summarized in Tables 2 and 3. Metallographic characteriza-
166 Mori and Bauernfeind Materials and Corrosion 2004, 55, No. 3

Table 2. Chemical composition of investigated materials

Tabelle 2. Chemische Zusammensetzung der untersuchten Werkstoffe

Alloy Name DIN C Cr Ni Mo Cu N PREN30N MARC

Material no. [%] [%] [%] [%] [%] [%]
316L X2CrNiMo18-14-3 1.4404 0.012 17 14 2.8 0.1 0.1 29 24
N08028 X1NiCrMoCuN31-27-4 1.4563 0.021 27 31 3.3 1.1 0.1 42 31
Alloy A – – N08028 plus N 43 33
Alloy B – – N08028 plus more N, without Cu 46 35
S31254 X1CrNiMoCuN20-18-7 1.4547 0.011 20 18 6.1 0.7 0.2 46 40
Alloy C – – S31254 plus more N, plus W, without Cu 55 46

Fig. 1. Microstructures of investigated alloys

Abb. 1. Gefüge der untersuchten Werkstoffe
Materials and Corrosion 2004, 55, No. 3 Pitting and crevice corrosion of superaustenitic stainless steels 167

Table 3. Mechanical properties of investigated materials

Tabelle 3. Mechanische Eigenschaften der untersuchten Werkstoffe

Alloy Name DIN Material no. Yield strength Tensile strength Elongation
Rp0.2 [MPa] Rm [MPa] A5 [%]
316L X2CrNiMo18-14-3 1.4404 307 611 49.5
N08028 X1NiCrMoCuN31-27-4 1.4563 311 660 53
Alloy A – – 368 727 56
Alloy B – – 425 789 54.5
S31254 X1CrNiMoCuN20-18-7 1.4547 332 675 57
Alloy C – – 400 770 63

Table 4. Comparison of three different test methods

Tabelle 4. Vergleich der drei verwendeten Testverfahren

Test method Test solution Chloride conc. [M] Temperature [8C] Potential [mVSCE]

ASTM G 48-C, D 6% FeCl3 þ 1% HCl 1.38 – OCP (600 – 700)

ASTM G 61 Artificial seawater 0.55 60, 80 –
ASTM G 150 1 M NaCl 1 – 700
OCP ..... open circuit potential

Fig. 2. Chromium and molybdenum rich phases in alloy N08028

Abb. 2. Chrom- und molybdänreiche Phasen in der Legierung N08028

tion of microstructure has been done first (Fig. 1). Alloy 316L
has the finest grain size between 10 and 20 lm. N08028
(Fig. 1b) contains a higher amount of oxide inclusions
when compared to other materials. Furthermore it exhibits
a small amount of chromium-molybdenum rich precipitations
at grain boundaries (Fig. 2). While Alloys A and B do not
show defects in microstructure (Figs. 1c and d), S31254 is
segregated to a certain extent resulting in areas of preferential
attack during etching (Fig. 1e). Finally Alloy C contains pre-
cipitates of a chromium-molybdenum rich phase in longitudi-
nal direction (Figs. 1f and 3). Grain size of investigated super-
austenites is between 100 and 200 lm.
For better comparison of results with literature data only
standardized tests were used during this investigation. Table 4
gives a comparison of all three used test methods. Critical pit-
ting (CPT) and crevice corrosion temperatures (CCT) have
been determined for all six steels in 72 hours exposure periods
according to ASTM G 48, Methods C and D, respectively.
Both methods involve testing of grinded specimens (No.
120-grit abrasive paper) for 72 hours in an acidified ferric
chloride solution (6% ferric chloride with 1% hydrochloric
acid). CPT and CCT are defined as temperatures, where cor-
rosion attack exceeds a minimum depth of 0.025 mm. Tem-
perature was increased in steps of 2.5 8C until corrosion oc-
168 Mori and Bauernfeind
Table 5. Correlation coefficients of measured data for different measures of pitting resistance and investigated standards
Tabelle 5. Aus den Versuchsergebnissen nach ASTM G 48, C+D und ASTM G 61 ermittelte Korrelationskoeffizienten
ASTM G 48, C ASTM G 48, D
All alloys 316L,A,B All alloys
PREN20N 0.92 0.98 0.95
PREN30N 0.93 0.98 0.98
MARC 0.94 0.99 0.98
Fig. 3. Chromium and molybdenum rich phases in Alloy C
Abb. 3. Chrom- und molybdänreiche Phasen in Legierung C
curred. Only freshly prepared specimens have been investi-
gated, which is important to avoid measurement of too
high CPT and CCT values [20].
In addition to CPT determination according to ASTM G 48,
Method C, an electrochemical method according to ASTM G
150 was used as well. For these experiments 1 M sodium
chloride solution was used as testing solution. With this
fast method it is possible to determine the potential indepen-
dent CPT at noble potentials by way of a potentiostatic tech-
nique using a temperature scan. CPT in this case has been de-
termined at a constant potential of þ 700 mVSCE by increasing
temperature by 0.2 8C/min (starting from a temperature ap-
proximately 20 degrees below the estimated CPT) until an ir-
reversible current increase indicated the onset of pitting. The
test solution was deaerated and agitated with argon (99.999%)
and at least 12 hours before the start of the experiments all
specimens were again wet surface grinded with No. 600-
grit abrasive paper. A saturated calomel electrode (SCE)
was used as reference electrode with a potential of
241 mVSHE. All potentials quoted in this study are expressed
versus SCE. After each experiment specimens were examined
under an optical microscope for determination of morphology
of corrosion.
For determination of pitting potential, Epit, an electrochemi-
cal method according to ASTM G 61 was used. Pitting corro-
sion behaviour of all six investigated materials has been in-
vestigated in artificial seawater (pH 7.4) at two different tem-
Materials and Corrosion 2004, 55, No. 3
ASTM G 61
316L,A,B All alloys 316L,A,B
0.98 0.87 0.98
0.98 0.91 0.99
0.99 0.99 0.99
peratures. Due to noble pitting potential of superaustenites
elevated temperatures of 60 and 80 8C were chosen. All sam-
ples were prepared by grinding with No. 600-grit abrasive pa-
per. Scan rate was set at 600 mV/h, starting at open circuit
potential after a holding time of 1 h. Pitting potentials were
determined from anodic polarization curves where a stable in-
crease of corrosion current density occurred. For all investi-
gated materials two different pitting potentials (Epit0.01 at a
current density of 0.01 mA/cm2 and Epit0.1 at 0.1 mA/cm2, re-
spectively) were determined. Protection potential Eprot was ta-
ken from the reverse scan when current density decreased be-
low 0.01 mA/cm2. Again all specimens were examined under
an optical microscope for determination of morphology of
corrosion.
3 Results and discussion
3.1 General
Evaluation of linearity of results was done with PREN20N,
PREN30N, and MARC. Correlation coefficients were deter-
mined for data of all six investigated alloys as well of Alloys
316L, A, and B, which contained no structural defects (Ta-
ble 5). Comparison shows that application of MARC results
in a slightly higher correlation coefficient and for this reason
all results of further investigations are presented as function of
Materials and Corrosion 2004, 55, No. 3 Pitting and crevice corrosion of superaustenitic stainless steels
Fig. 4. Influence of microstructure on CPTG 48 as function of
MARC
Abb. 4. Einfluss der Mikrostruktur auf die kritische Lochkorrosi-
onstemperatur nach ASTM G 48 als Funktion von MARC
Fig. 5. CPTG 150 (1 M NaCl, 700 mVSCE) as function of MARC
Abb. 5. CPTG 150 (1 M NaCl, 700 mVSCE) als Funktion von MARC
MARC. In the case of superaustenites PREN can contain also
other elements like carbon, manganese, nickel and tungsten
and some mixed and non-linear terms. While in MARC there
are several additional terms included for different elements
which give a better linearity, there still remains the question
why copper is not included in the formula and particularly
why the severe detrimental element sulphur is ignored as
well. Concerning sulphur the main problem may be a big in-
fluence of size and distribution of sulphide inclusions making
it difficult to determine a certain negative factor only depen-
dent on total sulphur concentration and not on its distribution.
Results also show that the main scientific progress to find a
measure for pitting resistance as function of chemical compo-
sition was achieved from Lorenz and Medawar [5] by estab-
lishing PREN good accuracy. The implementation of nitrogen
to the formula was certainly a second big progress for this
measure, together with knowledge that nitrogen has to be con-
sidered with a high factor, when applying PREN to highly al-
loyed materials. All later developed formulas for PREN
yielded only to minor improvements.
3.2 Pitting corrosion
3.2.1 Critical Pitting Temperature (CPT)
CPT determined in acidified ferric chloride solution ac-
cording to ASTM G 48, Method C, is shown in Fig. 4 as func-
tion of MARC. Linear regression lines considering all mea-
169
sured data as well as only data of alloys free from defects
in microstructure are included. Alloys N08028, S31254 and
C with segregations, non-metallic inlusions and/or depleted
zones near precipitations show a significant decrease of pit-
ting resistance due to their microstructural defects. Especially
the two highest alloyed materials S31254 and Alloy C do not
reach their theoretical pitting resistance that is indicated by the
steeper grey line and the arrows in Fig. 4.
A general problem of higher alloyed steels is the higher dif-
ficulty to receive a sufficient homogeneity in microstructure.
All six investigated materials have been delivered from indus-
trial steelworks proving that even standard superaustenites
like N08028 may contain defects of microstructure. Very
highly alloyed superaustenites can reach an even higher cor-
rosion resistance, if their microstructure is free from defects.
Since it is increasingly difficult to bring an increasing amount
of alloying elements into solid solution and to maintain the
material free from segregations and precipitations, one might
argue that maintainance of a defect-free quality of materials
could yield to a higher corrosion resistance. The use of an even
higher alloyed material then could be disclaimed instead of
applying a defect-free material. Consequently one possibility
for steelworks producing superaustenites to improve their pro-
ducts is to ensure and maintain a microstructure free from de-
fects.
Results on CPT according to ASTM G 150 are presented in
Fig. 5. Fig. 6 shows two typical plots for such an experiment
and it is obvious that there is a sudden increase of the current
density when temperature reaches CPT. In case of reference
material 316L, CPT has not been determined because its pit-
ting potential at room temperature is approximately
150 mVSCE and ASTM G 150 is performed at a much more
noble potential of 700 mVSCE yielding to immediate pitting
of 316L above 0 8C [18]. In contradiction Alloy C with the
highest PREN/MARC value did not show any pitting even
at boiling point of test solution. The PREN/MARC window,
where testing according to ASTM G 150 yields to quantitative
results is therefore narrow. Neither conventional stainless
steel grades with a MARC below 25 (PREN30N below 29
for investigated alloys) nor several highly alloyed superaus-
tenites with a MARC higher than 40 (PREN30N above 46)
can be investigated by ASTM G 150 at proposed potential
of 700 mVSCE. A change of potential however decreases com-
parability of data and may be one of the reasons why this stan-
dard is less wide-spread. On the other side it is an effective
Fig. 6. CPTG 150 determination of N08028 according to ASTM
G 150 (two experiments)
Abb. 6. CPTG 150 von N08028 ermittelt nach ASTM G 150 (2 Ver-
suche)
170 Mori and Bauernfeind Materials and Corrosion 2004, 55, No. 3

G 150 a strictly constant potential of 700 mVSCE is used while

Fig. 7. Areas of pitting and transpassive corrosion as function of
potential and temperature for stainless steels and paths of several
standardized testing methods [22]
Abb. 7. Bereiche von Loch- und transpassiver Korrosion von rost-
freien Stählen in Abhängigkeit von Potential und Temperatur sowie
Prüfwege verschiedener genormter Verfahren der Korrosionsprü-
fung [22]
method for determination of CPT of certain alloys since it
shows sharp and distinct increase of current density when
reaching CPT.
In comparison to ASTM G 48, the electrochemical method
ASTM G 150 gives higher CPT values by about 20 8C. The
reason for this is, that in ASTM G 150 the specimen is initially
exposed to the test solution at a temperature well below its
estimated CPT, and that allows to build up a passive layer
[21] and improves corrosion resistance. On the other hand dur-
ing ASTM G 48 procedure the specimen is exposed directly to
the test solution at the actual test temperature where pitting
already can occur.
A second significant parameter is exposure time. ASTM
G 150 experiments have to be conducted with a heating
rate of 1.0 8C/min. Comparing this with “heating rate” of
ASTM G 48, which could be said to be 1.67 8C/d (5 8C per
3 days of testing) or equal to 0.001 8C/min, heating during
ASTM G 150 is about 1000 times faster and leaving less
time for pit initiation and equilibration. This leads to higher
CPT values measured by ASTM G 150. Another essential dif-
ference between these two methods is that in case of ASTM
during ASTM G 48 the potential increases from 620 to
700 mVSCE between 20 and 80 8C [22]. In Fig. 7 [23] the paths
of the tested specimens as function of temperature and poten-
tial are plotted for ASTM G 48, ASTM G 150, and potentio-
dynamic testing procedure according to ASTM G 61. Every
standard has a different approach to determine a measure
for pitting resistance. A direct comparison is therefore not use-
ful not only since exposure times and conditions in different
tests vary significantly.
It should kept in mind however that both, ASTM G 48 and
G 150, are suitable methods for ranking the relative pitting or
crevice corrosion resistance of different alloys. Nevertheless
these tests say nothing about the maximum temperature for
use of alloys in real environments.
3.2.2 Pitting potential (Epit)
Fig. 8 shows results of potentiodynamic measurements on
investigated materials in artificial seawater at a pH of 7.4.
From there pitting and protection potentials were taken and
are summarized in Table 6. The occurrence of pitting corro-
sion already can be derived from the shape of the current re-
sponse during electrochemical measurements. A pronounced
hysteresis indicated severe pitting in any case. Pitting at an
early stage resulted in no hysteresis since aggressive electro-
lyte in small pits can not be generated in a short time of pit
propagation. In general pitting potential decreases with an in-
crease of temperature for all types of stainless steels and the
particular effect of temperature depends on the grade and type
of the steel [24]. The results presented in Fig. 8 show that both,
pitting and protection potential, increase with higher content
of alloying elements. Austenitic reference material 316L
shows a pronounced hysteresis and only pitting without trans-
passive corrosion happened (Fig. 9). N08028 and Alloy A
show a hysteresis due to pitting except Alloy A at lower tem-
perature where pitting was just initiated before occurrence of
transpassive corrosion. Low pitting potential of N08028 com-
pared to the similar Alloy A at 60 8C is caused by its oxide
inclusions and chromium-molybdenum rich precipitations.
At higher temperatures there is less difference due to more
aggressive conditions.
Alloy B did not contain any defects in microstructure and
for this reason pitting potential reaches its theoretical noble

Table 6. Pitting and protection potentials of investigated alloys according to ASTM G 61 in artificial seawater at pH 7.4 [mVSCE]
Tabelle 6. Lochfraß- und Repassivierungspotentiale der untersuchten Legierungen nach ASTM G 61 in künstlichem Meerwasser bei pH
7,4 [mVSCE]

Material MARC 60 8C 80 8C
Epit0.01 Epit0.1 Eprot0.01 Epit0.01 Epit0.1 Eprot0.01

316L 24 156 182  160 90 114  150

N08028 31 391 468 150 292 344 90
Alloy A 33 819 928 200 307 396 80
Alloy B 35 810 904 500 413 905 80
S31254 40 843 922 800 648 842 100
Alloy C 46 819 968 675 822 950 705
Epit0.01 ..... pitting potential at an anodic current density of 0.01 mA/cm2
Epit0.1 ..... pitting potential at an anodic current density of 0.1 mA/cm2
Materials and Corrosion 2004, 55, No. 3 Pitting and crevice corrosion of superaustenitic stainless steels 171

Fig. 8. Current density-potential curves in artificial seawater according to ASTM G 61, pH 7.4
Abb. 8. Stromdichte-Potentialkurven in künstlichem Meerwasser gemäß ASTM G 61, pH 7,4

value corresponding to its chemical composition and certain
environmental conditions. No hysteresis was obtained at
60 8C (Fig. 8d) and several areas of transpassive corrosion at-
tack can be found apart from areas with distinct pits. Repas-
sivation happened at much less noble potential at 80 8C com-
pared to 60 8C and number and size of pits were big therefore
(Fig. 10).
S31254 has the highest molybdenum content of all six in-
vestigated steel grades and was segregated to a certain extent.
Therefore specimens show some pits instead of transpassive
corrosion. In the case of Alloy C no hysteresis was obvious at
both temperatures and only transpassive corrosion was domi-
nant.
Pitting potential Epit0.01 is plotted versus MARC in Fig. 11,
respectively. The full symbols represent specimens only suf-
fering pitting corrosion, whereas the empty symbols represent
those only with transpassive uniform corrosion. The grey
symbols indicate joint presence of pitting and transpassive
corrosion. At 80 8C pitting potentials show a distinct linearity
up to Alloy C, which was not corroded at 900 mVSCE. Pitting
potentials at 60 8C show a plateau above a MARC of 33 (equal
to a PREN30N of 43). This plateau between 850 and
900 mVSCE represents both, oxygen formation and transpas-
sive corrosion. The latter was indicated by a sudden change
of electrolyte colour to dark yellow. At a MARC between 33
and 43 (similar to PRENs between 43 to 50) simultaneous pit-
172 Mori and Bauernfeind Materials and Corrosion 2004, 55, No. 3

Fig. 9. Pitting corrosion of 316L stainless steel according to ASTM G 61, pH 7.4, 60 8C
Abb. 9. Lochkorrosion von 316L geprüft nach ASTM G 61, pH 7,4, 60 8C

Fig. 10. Morphology of corrosion on Alloy B according to ASTM G 61, pH 7.4, left: pitting at 80 8C, right: transpassive corrosion at 60 8C
Abb. 10. Form des Angriffs der Legierung B geprüft nach ASTM G 61, pH 7,4, links: Lochkorrosion bei 80 8C, rechts: transpassive
Korrosion bei 60 8C

Fig. 11. Pitting potential Epit0.01 of superaustenites according to

ASTM G 61 at pH 7.4 as function of MARC: (*,~) pits,
(*,~) pits and transpassive corrosion, (*,~) transpassive corro-
sion
Abb. 11. Lochfraßpotentiale Epit0,01 superaustenitischer Stähle Fig. 12. Specimen with crevice corrosion
nach ASTM G 61 bei pH 7,4 als Funktion von MARC: (*,~)
Lochkorrosion, (*,~) Loch- und transpassive Korrosion, (*,~) Abb. 12. Probe mit Spaltkorrosion
transpassive Korrosion

ting, transpassive corrosion and oxygen evolution occurred.
These MARC/PREN values are of course dependent on envir-
onmental conditions. The arrow in Fig. 11 symbolizes the
amount of possible improvement of pitting potential of
N08028 in case of an optimised solid solution austenite with-
out microstructural defects.
3.3 Crevice corrosion
CCT values determined in acidified ferric chloride solution
according to ASTM G 48, Method D, are presented in Fig. 12
as function of MARC and Fig. 13 shows a typical picture of a
specimen after crevice corrosion testing, with its sharp, deep
Materials and Corrosion 2004, 55, No. 3 Pitting and crevice corrosion of superaustenitic stainless steels
Fig. 13. Comparison of CPT and CCT according to ASTM G 48,
Methods C and D
Abb. 13. Vergleich von CPT und CCT ermittelt nach ASTM G 48,
Methoden C und D
attack near the edge of the crevice former and a slight decrease
of attack in radial direction towards the center of the crevice
former. In comparison to CPT defects in microstructure seem
to have smaller effects on CCT. Nevertheless Fig. 12 indicates
a worse corrosion resistance of materials S31254 and Alloy C,
which both contain molybdenum segregations and/or precipi-
tations.
For more precise and quantitative results concerning the ef-
fect of microstructure and purity of alloys the number of in-
vestigated materials and qualities should be increased. Since
exposure time, test solution and experimental procedure are
the same for Methods C and D according to ASTM G 48,
a direct comparison of CPT and CCT is reasonable
(Fig. 12). There is almost a parallel linear dependency of
both critical temperatures on MARC, with CCT being about
20 8C lower than CPT. The long exposure time in ASTM G 48
is a disadvantage for acceptance or delivery testing, but the
standard includes options for using both higher torque and
shorter exposure times. Frequently used values for torque
and exposure times are 1.58 Nm and 24 hours, respectively.
Longer exposure time (72 hours) and a higher torque lead
to a decrease of CCT [20].
4 Conclusions
The following conclusions and confirmations were found in
the present work:
1) Different ASTM standards for determination of CPT must
not be compared and there is no simple relation between
CPT values obtained from different standards because of
completely different testing conditions. CPTG 150 is easily
to determine, only a narrow window of MARC/PREN ex-
ists however, where quantitative results for materials are
obtained at the recommended potential. This is the biggest
disadvantage of this test.
2) Modified Alloys A and B exhibit very attractive corrosion
resistance to chloride media at reasonable prices. Defects
in microstructure like precipitations, segregations or non-
metallic inclusions have a very detrimental effect on pitting
corrosion resistance of superaustenites, whereas there is a
smaller negative influence on resistance to crevice corrosion.
3) The higher alloyed a stainless steel is, the larger is its ten-
dency to form defects, especially precipitates and segrega-
173
tions. Very highly alloyed steels like superaustenites exhibit
a high corrosion resistance. It is however, increasingly dif-
ficult to reach their theoretical corrosion resistance by pro-
ducing them without defects. In extreme situations a better
homogeneity can result in a higher benefit with respect to
corrosion resistance than a higher alloyed material.
4) The beneficial effect of nitrogen for pitting resistance is lar-
ger for highly alloyed superaustenitic steels when com-
pared to conventional austenitic CrNiMo-grades. This
can be expressed in modified formulas for PREN. One
of the more recently published formulas called MARC
gives good linear correlation for CPT and CCT, respec-
tively. PREN30N however is an adequate, more wide-spread
and simple measure for pitting resistance.
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(Received: June 4, 2003) W 3746