Advanced Materials Research Vol.

893 (2014)pp 397-401

Online available since 2014/Feb/19at ~ 1 ~ ~ ~ ~ . s c i net
enf(fic
GI (2014)Trans Tech Publications, Switzerland
doi:10.4028/www.scienfiJic.net/AMR.893.397

Corrosion Behavior Of Austenitic Stainless Steel In High Sulphate

Content
A. lsmail1ra
1
Faculty of Mechanical and Manufacturing Engineering,
University Tun Hussein Onn Malaysia,
Johor, Malaysia

Keywords: 316L, Sulphate-Chloride ratio, Temperature, Breakdown potential, Passive range,

Open Circuit Potential (OCP), Localized corrosion

Abstract. Austenitic stainless steels especially 316L has been used extensively in many sectors
including construction, medical and household appliances due to their highly resistance to corrosion
attack, reasonable cost and excel in mechanical properties. However, in corrosive media, 316L are
susceptible to localised corrosion attack especially in seawater and high temperature. The
corrosiveness of media increased as the anions contents increased. This paper presents the corrosion
mechanism of 316L exposed to high concentration of sulphate in the salinity of seawater. The
solution (media) was prepared according to the same composition as seawater including pH, salinity
and dissolved oxygen. The corrosion mechanism were characterized to breakdown potential (Eb) of
316L which are the potential once reaches a sufficiently positive value and also known as pitting
potential. This is the most point where localized corrosion susceptibility to evaluate and considered
a potential, which could be an appropriate point according to any given combination of
rnateriaUambient/testing methods. The Eb value were identified at 4OC, 20C, 50C and 80C and
compared with Eb value of 3 16L in seawater. The Eb value of 3 16L in high sulphate are higher
compared to seawater in every temperature which elucidate that some anions accelerate corrosion
attack whereas some anions such as sulphate behaves as inhibiting effect to 3 16L.

Introduction
Stainless steels (SS) have been widely used in industrial components for decades especially
austenitic stainless steel 316L due to their well-documented resistance to corrosion but yet, stainless
steel still suffers for corrosion attack especially in corrosive media such as seawater. Corrosion of
SS in seawater is dependent mainly on the salt content (which increase the electrical conductivity)
and its oxygen content. A number of variables can influence and complicate the course of corrosion
in different ways such as chloride, sulphate and temperature.
In the context of corrosion, SS are characterized by their passivity. Under certain conditions,
steel is passive, where the corrosion rate for the metal is relatively low. Iron is considered an active-
passive metal and, therefore, steel behaves similarly. Passivity can be defined as the loss of
chemical reactivity under certain conditions [I]. Steel achieves this by having a passive film form
along its surface. The passive film was formed by reaction of chromium with oxygen to produce
chromium oxide as a protection from surrounding. Therefore, the characterisation of SS is according
to the minimum 10.5% wt% Cr (Chromium) addition to iron [2]. For most SS, the maximum
chromium content is about 30% and the minimum iron content is 50%. The stainless characteristic
arises from the formation of an invisible and very adherent chromium-rich oxide surface film. This
puts the steel in a passive state and when the film is breached, it immediately heals when oxygen is
present. It is highly corrosion resistant and shows little or no corrosion if the passive film remains
intact.

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 398 Advanced Materials and Engineering Materials Ill

As shown in Figure 1, this curve reveals an electrochemical response during anodic polarisation
when the potential is scanned in the positive direction fiom E,,, (also known as OCP) and only very
small currents (typically 4 0 p4/cm2 ) are recorded until Eb, is reached. At this point the current
rises rapidly as a function of potential indicating that corrosion attack has initiated. The current
corresponding to the breakdown potential is denoted as breakdown current (current density, ib (
~lcm~))

The Passive Film. In appropriate conditions, some base metals can develop a surface condition that
inhibits interactions with aqueous media. The condition is described as passivity and its
development is called passivation. The effect is valuable in conferring corrosion resistance on bare
metal surfaces even in aggressive environments. The corrosion resistance of austenitic stainless
steels are depends on the formation of natural occurring transparent oxide films. These films may be
inpaired by surface contaminations such as organic compounds or metallic or inorganic materials
[3]. The formation of these film is by chromium oxide layer and is assumed to be responsible for the
effectiveness of the passivation. In mild solutions, the outer layer is reasonably well defined and
thick relatively to the dimensions of the whole film.

Results and Discussion

In anodic polarisation tests, the electrode potential of the material is scanned from the free
corrosion potential (Ecorr),also known as the Open Circuit Potential (OCP), in the more positive
direction at a fixed rate. When passivity is exhibited, the current initially remains very small. Once
the potential reaches the breakdown potential (Eb) (at which the passive film breaks down due to the
overpotential driving force), the current increases suddenly. The breakdown potential of the material
provides information on the resistance of materials to passivity breakdown [4]. Each anodic
polarisation scan was reversed once the current reached a set current (ire,) of 5 0 0 ~ A / c m The~.
degree of the increase in current beyond ire., gives an indication of the propensity for corrosion
propagation [5]. An indication of the extent of propagation is therefore obtained by consideration of
,,,i which represents the maximum current attained should the current not begin to fall
immediately after scan reversal.
This experiment was conducted to quantify the effect of sulphate to corrosion attack on 3 16L.
For passive alloy including austenitic stainless steels (3 16L), corrosion resistance is provided by a
very thin surface film, known as passive fihn that is an invisible film of oxide, formed by the metal
reacting with the ambient environment. Normally these films are fi-ee of pores, but their stability
may be weakened locally in the environment contained aggressive anions. Figure 1 shows 3 16L in a
solution that has higher sulphate content compared to seawater but same salinity at 4"C, 20C, 50C
and 80C. The cyclic polarisation performs in positive hysteresis at all temperatures indicates that
after passive film destroyed, the material does not repair itself. Therefore, the corrosion attack
propagate and localised corrosion will start. The breakdown potential at every temperature are
higher compared to 3 16L in seawater. This indicates that sulphate has an inhibiting effect on pitting
corrosion [6,7]. In addition, the presence of sulphate causes the distribution of available pit sites to
be shifted to a higher potential, which causes pit propagation in both metastable and stable states
PI.
Figure 2 present the cyclic polarisation of 3 16L in seawater. This is to compare the performance
of 3 16L between seawater and seawater with high sulphate content. Similar to 3 16L in seawater of
high sulphate content, the polarisation presents as positive hystheresis in 4"C, 20C, 50C and 80C.
There is a significant reduction in Eb as the temperature increases which explain that reduction in
corrosion resistance of material to corrosion attack. In addition, the positive hysteresis in all
solutions proved that sulphate ion inhibite 316L from further localised attack. Apart of that, the
positive hystheresis could indicate that the passive film damage is not repaired and allowed pits to
initiate [9]. However, the Eb value presents lower than the Eb value in high suphate content which
reveals that 3 16L are more susceptible to localised attack in seawater compared to high sulphate
 Advanced Materials Research Vol. 893 399

containing chloride solution. The drastic change in the nature and the properties of oxide films on
passive alloys i n water in increasing temperature is attributed to a breakdown of passivity [10,11].

Figure 1: Cyclic polarisation of 316L in high sulphate content

In both solutions, the Open Circuit Potential (OCP) values of 3 16L shifted towards inore active
values as the temperature increased, while the breakdown corrosion potential presented the opposite
tendency. Figure 3 presents potential as a hnction of current for 3 16L in high sulphate content and
in seawater. The co~nparisonas shown in Figure 4 clearly shows that 3 16L has higher Eb value in
high sulphate content compared to seawater. This explained that 316L has better corrosion
resistance in high sulphate content compared to seawater. The severity of localised corrosion attack
is shown in Figure 5 by optical microscope observation.

log rt.4 ccdt

400 Advanced Materials and Engineering Materials Ill

Figure 2: Cyclic polarisation of 316L in seawater

Figure 3: Cyclic polarisation of Potential versus Current for 316L in (left) high sulpahe
content and (right) seawater

+Seawater

Figure 4: Comparison of breakdown potential of 316L in high sulphate content

and seawater
 Advanced Materials Research Vol. 893 401

Figure 5: Optical microscope image of corrosion attack on 316L in high sulphate content

Summary
It is generally accepted that the risk for pitting decreases with increasing sulfate ( ~ 0 4 content
~3 in
seawater. There are also indications that higher sulfate/chloride ionic ratio is needed to inhibit the
pitting corrosion of stainless steels at higher chloride concentrations [12].Stainless steel 316L are
prone to localised corrosion attack or pitting corrosion in seawater compared to high suphate
content of seawater. Non halide anions such as sulphate ( ~ 0 4 can~ 3reduce risk to pitting in chloride
containing solutions. Their inhibiting effect depends on their concentration and chloride content of
the solution. However, some anions may behave as inibition due to competitive adsorption with
chloride ions on metal surface. Due to these competition, some anions behaves as protection to
metal whereas some anions may behaves contradictly.

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