Journal of Metallurgical Engineering (ME) Volume 3 Issue 1, January 2014

doi: 10.14355/me.2014.0301.02

www.me-journal.org

The Effect of Pitting Corrosion on the Fatigue

Strength of 304 and 316 Stainless Steel Alloys
S .A .Al-Taher1, I .M .Ghayad1*, K .M .Ibrahim1 and Y.E .Barakat3
1-Omer Al-Mokhtar University, Libya., 2-Central Metallurgical Research and Development Institute (CMRDI),
Cairo, Egypt, 3-Tabbin Institute for Metallurgical Studies (TIMS), Cairo, Egypt
saadeldeen86@yahoo.com; ighayad@yahoo.com; khaledabouelela@yahoo.com; ybarakat2013@yahoo.com
Abstract
Pitting corrosion behavior of 304 and 316 stainless steel
alloys was investigated in 3.5% NaCl solution containing 100
ppm thiosulfate ion as pitting corrosion initiator. Experiments
were performed using potentiodynamic polarization and
potentiostatic techniques at room temperature. The shape,
size, and pit depth of the formed corrosion pits were also
determined using the metallurgical light microscope. The
fatigue strength of the pitted samples (either single or
multipitted) was determined using plain-bending fatigue
test machine. The fracture surface was also investigated
using scanning electron microscope (SEM).
The results show that SS 304 is more susceptible to pitting
corrosion and has lower fatigue strength than SS 316 for the
unpitted alloys samples. For both alloys, the single pitted
samples shows that a deterioration percentage in fatigue is
of about 15% while the multi pitted samples shows a
deterioration percentage in fatigue of about 33% compared
to the unpitted samples. The crack through the specimen
surface was noticed to be initiated from the pit and
propagates in two perpendicular sides to each other.
Keywords
Pitting Corrosion; Fatigue Strength; SS 304; SS 316

Introduction
Stainless steel alloys are highly resistance to corrosion.
However; they are susceptible to localized corrosion,
specially pitting attack, with aggressive anions such as
chloride and thiosulfate [Wilde et al (1971); Zhang et al
(2006); Berthom et al (2006); Hou et al (1983); Zuo et
al (2002); Park et al (1997); Kaneko et al (2002)]. The
effects of aqueous environments on the fatigue strength
and mechanisms of fatigue crack initiation have received
little attention despite their importance from an
engineering and design standpoint [Tschiptschin et al
(2005); Lin at al (2004); Kiyotaka et al (2004); Singh et
al (2004); Abubakir et al (2001)].
The premature failure of 12% Cr martensitic stainless
steel blades of the medium pressure stage of a
thermoelectric centre turbo-bower blades occurred by
corrosion-fatigue mechanism, whose nucleation was

associated with the presence of corrosion pits on its

suction side [Tschiptschin et al (2005)]. The addition of
pitting inhibitor could restore the fatigue strength of
AISI 347 stainless steel in salt water back to the level in
atmospheric air by preventing the formation of
corrosion pits and decreasing the corrosion rate [Lin et
al (2004)]. The fatigue strength of 316 NG and 304 TP
stainless steel alloys having some artificial corrosion
pits was much lower than that of specimen without
pits and all fatigue cracks were generated from the pits
[Kiyotaka et al (2004)]. The stress corrosion cracking
(SCC) and subsequent corrosion fatigue cracking (CFC)
behaviour of a heat-treated duplex stainless steel (DSS)
in paper-machine white waters containing chloride
and thiosulfate ions was addressed by Singh ,et al.
[Singh et al (2004)]. It was believed that crack initiation
occurs by pitting within ferrite grains or near grain
boundaries and then propagated by fatigue during
alternate cycling loads produced in normal operation
of the paper machine. Duplex stainless steel (DSS) was
also susceptible to pitting corrosion and corrosion
fatigue at different cyclic stress levels in 3.5% NaCl,
pH=7 at 50oC [Abubakir et al (2001)]
It is obvious that there are few papers focused on the
effect of pitting corrosion on the fatigue life of alloys.
So it is interesting to address the effect of pitting
corrosion either single pit or multi-pits on the fatigue
strength of SS 304 & 316.
Experimantal
Disc specimen, 1.4 cm diameter and 3 mm thickness,
of 304 & 316 stainless steel alloys whose chemical
compositions are shown in Table 1 were used to
investigate pitting corrosion. Specimens were polished
to 200,400, 800 and 1200 grit finish, cleaned, degreased,
dried in air then mounted in the specimen holder to
expose 1 cm2 surface area. The area shielded by the
specimen holder was coated with a protective coat to
prevent crevice corrosion.
A conventional corrosion cell was used where
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Journal of Metallurgical Engineering (ME) Volume 3 Issue 1, January 2014

platinum electrode was used as the counter electrode

while saturated calomel electrode (SCE) electrode was
used as reference electrode. Potentiodynamic
polarization and potentiostatic techniques were used
to investigate the pitting corrosion of the tested alloys
using Autolab PG stat 30. After attaining a steady
potential (Ecorr), the specimens were potentially
scanned at a rate of 2 mV/sec. The test environment
was solution of 3.5% NaCl plus 100 ppm S2O3- as a
pitting corrosion initiator.
TABLE 1 CHEMICAL ANALYSIS OF TESTED ALLOYS

Alloy
C
Si
Mn
Cr
Ni
Mo
S
P
Fe

SS 304
0.8
1.1
0.5
18
9.00
0.10
0.025
0.022
Bal

SS 316
0.033
1.033
0.815
19.29
9.00
2.30
0.013
0.027
Bal

visually inspected periodically for evidence of fatigue

cracking and, possible, the progress of the fatigue
crack was recorded. The dye penetration test was used
to detect cracking and to produce bench marks on the
fracture surface, allowing obtaining crack shape at the
end of the test. In general, testing was continued until
the specimen fractured or until it has endured at 107
cycles without any evidence of fatigue cracking. The
fracture surface of some selected samples was
investigated using scanning electron microscope.
Results and Discussion
The microstructure of both investigated alloys
revealed an austenitic structure as shown in Fig.4. The
structure of SS 316 showed finer structure than SS 304
due to the effect of molybdenum additions.

Once the potentiodynamic polarization is obtained,

the pitting potential (Epitting) is determined. The
working electrode is then held at Epitting for at least one
hour to enhance pitting corrosion, then the specimen is
removed from the holder, cleaned, dried and
investigated under a metallurgical light microscope to
determine shape, size, and pit depth. In determining
the pit depth, the microscope is focused on the lip of
the pit, then on its bottom. The difference between the
initial and final readings on the fine focusing knob of
the microscope is the pit depth (ASTM G46).
The schematic drawing of the fatigue test specimens is
shown in Fig.1. The fatigue experiments were carried
out using plane-bending fatigue test machine with a
capacity of 30 N.m. The fatigue samples were divided
into three groups: the first group was for the base alloy
(unpitted), the second group was for samples having
one pit in the middle of the sample surface while the
third group was for samples having multi-pits on the
reduction area of the sample surface.

FIG. 1 FATIGUE TEST SAMPLE CONFIGURATION

The fatigue strength test was carried out where the

cyclic loading frequency was 1350 (cycle/minute) and
the applied bending moment ranged from 5 to 9 N.m
for the base alloy as well as the samples with corrosion
pitting. During the fatigue test, the samples were

SS 304

SS316
FIG. 2 MICROSTRUCTURE OF THE INVESTIGATED STAINLESS
STEEL ALLOYS

Pitting Corrosion Behavior

Fig. 2 shows the potentiodynamic polarization curves
for SS 304 and SS 316 in 3.5% NaCl in the presence of
100 ppm thiosulphate ion. It is clear that 304 SS is
more susceptible towards pitting corrosion than SS 316.
Ecorr of 304 SS is shifted in the active region (-0.250 V)
compared to the 316 SS (-0.180 V). On the other hand,
pitting potentials of 0.140 V and 0.20 V (SCE) are
shown by SS 304 and SS 316, respectively. After
potentiodynamic polarization experiments, the alloys
samples was held for 1 h under potentials of 0.20 V &
0.25 V (SCE) for SS 304 and Ss 316, respectively. These
potentials are slightly higher than the pitting potential
for alloys to enhance pitting corrosion prior to their

Journal of Metallurgical Engineering (ME) Volume 3 Issue 1, January 2014

investigation under the optical microscope.

a

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electrolyte and the related very intense metal

dissolution that leads to the formation of a pit. The
adsorption mechanism refers to the increase in the
transfer of cations from the passive film to the
electrolyte due to the complexing properties of the
aggressive anions and chromium depletion. This
process causes the thinning and final removal of the
passive layer, thus the metal. The stabilization of the
growth of corrosion pits may be influenced by several
complicating factors depending on the state of their
development.

FIG. 3 CYCLIC ANODIC POLARIZATION CURVE OF 304 SS (a)

AND SS 316 (b) IN 3.5% NaCl +100 ppm S2O32-, 25oC, pH= 7.

Investigation of pitted samples under the optical

microscope shows that the number of pits obtained for
SS 304 is markedly higher than that obtained for SS
316. SS 304 showed 15 pits/cm2, while SS 316 gave 6
pits/cm2. The maximum pit depth obtained for SS 304
was about 0.1 mm, while 0.04 mm is obtained for SS
316. These results are in agree with the those of
potentiodynamic polarization experiments which
showed SS 304 to be more susceptible towards pitting
corrosion than SS 316. Fig.3 represents illustrative
examples of pits formed on both alloys.
Theories for passive film breakdown and pit initiation
have been categorized into three main mechanisms
that focus on passive film penetration, film breaking
and adsorption [Pardo et al (2008)]. The penetration
mechanism involves the migration of aggressive Clions from the electrolyte through the passive layer to
the oxidemetal interface under the influence of the
high electrical field strength of most passivating films.
The film-breaking mechanism starts with cracks in the
passive layer under induced corrosion activity,
exposing small areas of the bare metal surface to the

FIG. 4 OPTICAL MICROSCOPIC PHOTOGRAPHS OF PITS

FORMED ON 304 AND 316 SS ALLOYS.

The role of thiosulfate in enhancing pitting corrosion is

clarified on the premise that thiosulfate is able to
prevent passivation of an active stainless steel surface
and able to stabilize metstable pits intiated below the
actual pitting corrosion potential. Thiosulfate increases
the possible potential range of corrosion pits to grow
by lowering the repassivation potential. Hydrogen
sulfide originating from thiosulfate is proposed to
accelerate the anodic dissolution inside corrosion pits
and crevices by forming sparingly soluble metal
sulfides and by acidifying the local environment
[Garner (1985)].
The higher resistance of SS 316 towards pitting
corrosion can be attributed to the existence of
molybdenum (2.5%) in the alloy. Molybdenum may
have effect on more than one step in a pitting event.
Firstly, Mo modifies the passive film rendering it more
stable against breakdown caused by the attack of
aggressive Cl ions. Secondly, the presence of Mo
within the alloy significantly improves the
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Journal of Metallurgical Engineering (ME) Volume 3 Issue 1, January 2014

repassivation behavior or deactivation of growing pits.

This leads to the formation of a more protective
surface oxide film [Loto and Mater (2013)].
Fatigue Behavior of SS 304
Fig.5 represents fatigue specimens with one and
multipits on the reduction area. The fatigue limits of
SS 304 and SS 316 under the different investigated
conditions (base metal, one pit and multi-pits) are
compared in Fig.6. The SS 316 free pitting samples
showed a fatigue limit of approximately 390 MPa
compared to 350 MPa for SS 304. For SS 316, with the
existence of one pit on the reduction section of the
sample, the fatigue limit decreases to 328 MPa.
Meanwhile, with multi-pits, the fatigue limit decreases
to 255 MPa. Therefore it could be said that an existence
of one pit on the surface of SS 316 results in the
deterioration of the fatigue limit within a percentage
of 16%. This deterioration percentage reached 33%
with the existence of multi-pits on the surface of SS
316. On the other hand, an existence of one pit on the
surface of SS 304 alloy deteriorates the fatigue strength
with a percentage of 15% while the existence of multipits results in the deterioration of the fatigue strength
of the SS 304 with a percentage of about 31%.

a-Base metal

b- One pit

(a)

C- Multi- pits
(b)
FIG. 5 FATIGUE SPECIMEN WITH ONE PIT (a) AND
MULTIPITS (b) ON THE REDUCTION AREA

It is seen that the presence of either one pit or multipits on the surface of both alloys exerts approximately
the same effect on their fatigue behavior. With one pit,
the deterioration percentage was ~15% and with multipits this percentage was increased to ~33%. As a result,
it could be concluded that the deterioration effect of
existing either one pit or multi-pits depends mainly on
pitting corrosion effect rather than the alloy under
investigation. In conclusion, this data is very
important for the designer in order to determine the
service life of machine components and structure due
to economic and environmental reasons [Murakami
(2002); Wulpi (2000); Klesnil and Lukas (1980);
Koterazawa (1990)].

10

FIG. 6 COMPARISON OF FATIGUE STRENGTH OF SS 304 AND

SS 316 IN THE ABSENCE AND IN THE PRESENCE OF PITS ON
THE SAMPLE SURFACE.
Pits where cracks intiated
316 SS
304 SS

FIG. 7 EFFECT OF EXISTING ONE PIT ON THE SAMPLE

SURFACE ON FATIGUE STRENGTH OF THE INVESTIGATED
ALLOYS

Journal of Metallurgical Engineering (ME) Volume 3 Issue 1, January 2014

Plastically deformed
zone around the crack tip
for SS 304

Plastically deformed zone

around the crack tip for
SS 316

FIG. 8 PLASTIC DEFORMED ZONES AROUND THE CRACK TIP

OF THE STUDIED ALLOYS.

FIG. 9 SEM OF THE FRACTURE SURFACE SHOWING THE

STRIATION FEATURE OF 316 SS.

(a)

(b)
FIG. 10 SEM ANALYSIS OF THE FRACTURED SURFACE OF 316
SS.

The effect of pitting on crack initiation and

propagation during the fatigue test has been studied.
It is noticed that pitting has a big role in creating a

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crack through the specimen surface. Fig. 7 shows the

characterization of the zone near the crack tip of the
investigated samples. It is obvious that the zone
around the crack tip is relatively brighter than the
zone far away from the crack tip. This bright zone is
considerably plastically deformed due to the applied
dynamic load during the fatigue test. It is assumed
that the material at the crack tip plastically deformed
where local stress exceeds a critical value, 0. Thus the
plastic zone is formed as shown in Fig. 8. In the
remaining volume of body, the stress is lower than 0
and the behavior is elastic. The presence of plastic
zone will naturally also change the stress distribution
outside the zone (with respect to the elastic case). If the
plastic zone is small compared with the dimension of
the body and the crack length, it is possible to assume
that the stress distribution further from the crack tip is
identical to that from the elastic zone. This solution is
called small-scale yielding and corresponds in the
majority of cases to real fatigue cracks. This
phenomenon was clear in the fractured samples of
both SS 316 and SS 304.
According to the fracture mechanics theory, the plastic
zone should have a dog bone shape across the
thickness of the samples. Although a slight tendency
towards this shape was experimentally observed, the
most frequently observed shape is a mixture of
idealized plane stress and plane strain, which is the
same throughout the whole thickness [16-19].
Moreover, the real shape of plastic zone may be
considerably irregular and asymmetrical with respect
to the crack plane.
After the original crack is formed, it becomes an
extremely sharp stress concentration that tends to
drive the crack ever deeper into the metal with each
tensile stress application, assuming that the maximum
cyclic stress is of a magnitude high enough to
propagate the crack. The local stress at the tip of the
crack is extremely high because of the sharp notch and
with each crack opening, the depth of the crack
advances by one striation. Striations are very tiny,
closely spaced ridges that identify the tip of the crack
at some point in time. The studied SS 316 and SS 304
showed a fracture surface with a striation feature. Fig.
9 illustrates this feature for 316 SS where the striated
area is indicated by the arrow. More closely
investigation to the fracture surfaces of the alloy is
illustrated in Fig.10. This fracture surface could be
characterized as ductile fracture surfaces due to the
existence of a large some areas of dimples (ductile
fracture), (Fig. 10a). These dimples indicate the soft
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Journal of Metallurgical Engineering (ME) Volume 3 Issue 1, January 2014

austenite phase existing in the microstructure. As well

some micro-cracks has been observed in the fracture
surface (Fig.10b). It is suggested that these cracks can
be formed due to the work hardening that can
transform a part of the austenite phase to the
martensite during the fatigue test. The martensite
phase is considered a hard phase and fractured in a
brittle manner and sometimes causes micro-cracks
inside the metal [Garner (1985)].
Conclusions
1. SS 304 is more susceptible to pitting corrosion than
SS 316 as evidenced by both potentiodynamic
polarization
experiments
and
microscopic
examination. The higher resistance of SS 316
towards pitting corrosion can be attributed to the
existence of molybdenum (2.3%) in the alloy
which leads to the formation of a more protective
surface oxide film.
2. The presence of pits on the surface of either SS 304
or SS 316 leads to a remarkable decrease in the
fatigue strength of both investigated alloys
compared to the base metal. Pitting corrosion has
a big role in creating a crack through the specimen
surface. Pitting as a surface defect enables the
crack to initiate at this point. Thereby, the crack
initiated from the pit and propagates in opposite
directions to each other.
3. The fracture surface of both SS 316 and SS 304
could be characterized as ductile fracture surface
due to the existence of a large some areas of
dimples (ductile fracture) indicating the soft
austenite phase existing in the microstructure.
There were also some micro-cracks observed in
the fracture surface formed due to the work
hardening that can transform a part of the
austenite phase to the martensitic during the
fatigue test.

A.P. Tschiptschin, CRF Azevedo, Eng. Fail. Anal. 12 (2005)

49-59.
A. Pardo, M.C. Merino, A.E. Coy, F. Viejo, R. Arrabal, E.
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