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MORO SABTIWU

MATS63541

November 2015

MORO SABTIWU (9721176)


SCHOOL OF MATERIALS -CCE

Abstract : The effects of aqueous 0.1 Nacl and mixture of 0.1MNacl + 0.01MNa2S2O3 on
pitting behavior of 304 stainless steel (304SS) has been investigated. Potentiodynamic
galvanostatic polarization methods were used to study pitting behavior of 304SS in the
aforementioned solutions. The corrosion potential (Ecorr) and the pitting potential(Epit) for
both scenarios were ascertained.The Ecorr recorded for the Nacl solution and Nacl +
Na2S2O3 solution were -0.196V and 0.229V respectively. The pitting potentials recorded
were 0.224V. and 0.074V for Nacl solution and Nacl + Na2S2O3 solution respectively. Pitting
potential 304SS in Nacl + Na2S2O3 was greater than in Nacl solution only. Images of 304SS
after experiment using optical microscopy was consistent with the extent of pitting observed
from polarisation curves.
1.0 Introduction
Localized corrosion accounts for one of the most dangerous corrosion processes resulting in
degradation of pipes or containers meant for long- term industrial use. Pitting corrosion is of
particular interest due to its tendency to lead to untimely attack of the container materials by
electrochemical dissolution mechanisms that escalate quickly with time. Pitting is highly
unpredictable; stochastic in nature and can be hard to detect since it may be covered by
corrosion products. Small weight loss due to pitting can cause failure of equipment. Several
factors contribute to pit initiation; some of the common factors that influence pitting corrosion
initiation and propagation include: presence of non-uniformities in the metal structure of the
component such as non-metallic inclusions, factors that can cause breakdown of a passive
film(such as acidity, low dissolved oxygen concentrations and high chloride concentrations;
these are likely to turn a protective oxide film less stable, and thereby initiate pit), localized
mechanical or chemical damage to the protective oxide film and localized damage to poorly
applied protective coating. (Bhandaria et al.,2015) The current report will study pitting
behaviour in 304SS in Nacl and Nacl + Na2S2O3 solution. The effect of halides (typically
chlorine which is the most aggressive anion that results in pitting) and sulphide (from S2O32-,)
on pitting are considered below. Composition of 304SS is typically as shown below in fig 1;
Alloy
SS 304

C
0.06

S
0.005

Ni
8.03

Si
0.45

Mo
0.03

Mn
1.40

Cr
18.95

Fe
Bal

Fig.1Adapted from American Journal of Engineering research, Volume 3, Issue 1, January 2014

1.1 Effect of chlorides on pitting


Pitting corrosion can be caused by different halide anions .The presence of halide ions in the
electrolyte strongly affects the anodic process associated with metal passivation. For large
halide ion concentrations, passive film on a metal is susceptible to pitting thus suffering local
damage. Low concentrations, however, produces only increase in the anodic current in the
passivity range .Among the halides, chlorides are known as the most aggressive anions that
promote pitting corrosion in several metals including steels. Corrosion pits on stainless steel
immersed in chloride solution occurs in three distinct stages: nucleation, metastable growth
and stable growth. The amount of chloride concentration tends to vary with severity of the
pitting. Some main reasons for the specific influence of chloride ions on pitting according to
Bhandaria et al(2015), are: Its tendency to increase hydrogen ions activity in the pit
electrolyte, the ability of chlorides to form complexes with hydroxides and cations and, its
ability to result in formation of salt layer(FeCl2, CrcCl3) at low pH at the bottom of the pit.
Other works studied aggressiveness of chloride in marine and offshore installations where

PITTING OF STAINLESS STEEL LABORATORY REPORT

MORO SABTIWU
MATS63541

MORO SABTIWU (9721176)


SCHOOL OF MATERIALS -CCE

November 2015

chlorides are very common; they also realized many metal cations exhibit considerable
solubility in chloride solutions because it is an anion of a strong acid. In a chloride-containing
environment, the presence of the oxidizing agent (oxide) is extremely detrimental and it can
further enhance localized corrosion. (Bhandaria et al.,2015)
1.2 Effect of Sulphidess on Pitting in steel
Sulphur compounds greatly affect pitting of stainless steel. These compounds, H2S, HS-, S2-,
thiosulphate(S2O32-) activate pitting in stainless steel. The compounds(such as S2O32-) can
be involved in the oxidation or reduction reactions resulting in production of sulphur or the
sulphide according to the reaction; S2O32-(aq) + 6H++ 4e-2S + 3H2O(l) ---- Equation(1) .
The Sulphur produced gets adsorbed/chemisorbed on metal surface, producingM+-S-M+-chemical bonds. The absorption can be much localized, such that sulphur atoms
become tightly bonded at the defects in the passive oxide film. The Adsorbed sulphur
influences the growth of the passive film by blocking the sites of adsorption of hydroxyl ions,
which are the precursors in the formation of the passive layer. In the presence of Cl-, S does
not participate in initial breakdown of the passive film which is caused by Cl-.However, after
formation of stable pits, sulphur or sulphide adsorbs on the bare metal surface impeding
repassivation. (Bhandaria et al.,2015)
1.3 Measuring susceptibility of pitting using pitting potential
Several electrochemical studies on pitting corrosion have shown the relationship between
pitting potential and electrochemical process associated with corrosion (Frankel
(1998) and Melchers(1994), cited in Bhandaria et al(2015)). For a given electrochemical cell
(metal-electrolyte system), when the electronic potential is measured, it was observed that a
threshold value of the anodic potential exists, below which pitting does not occur. Different
approaches used to study pitting behaviour include: Measurements of current density vs.
time at constant potential ,Measurements of potential vs. time at constant current ,The
scanning reference electrode technique, the critical pitting temperature test ,repassivation
time technique, measurements of the anodic polarization curve using a potentiostatic device,
Measurements of the anodic polarization curve by galvanostatic methods and pit
propagation rate test. The potetiodynamic and galvanostatic methods will be replicated in
this experiment as described blow.
2.0 Experimental Methodology
2.1 Sample
Materials; 304 stainless metal sheets of dimensions: 29.9mm X 8.6mm X 0. 8mm
Electrolytes: (a) 0.1 M NaCl(aq) (b) 0.1 M NaCl + 0.01 M Na2S2O3 solutions, 1 mV/s
Electrodes: standard calomel electrode (SCE), Platinum(Pt) electrodes (no salt bridges),
Calculated immersed surface area of 304 steel in Nacl (aq) = 280.16mm2
Calculated immersed surface area in Nacl(aq) + Na2S2O3 (aq) =317.76mm2
Conditions; No de-aeration required, room temperature(25oC)
2.2 Potentiodynamic Polarisation
The electrochemical cell was set up as shown below in figure2 by immersing standard SCE
which served as a reference electrode, Pt electrodes served as counter and partially
immersing a thin wire(conductive) held the 304SS electrode (working electrode) in the about
100ml in aforementioned electrolytes in a beaker. For stability and reproducibility reasons, a
perforated cardboard was place on top of beaker to restrict movement of electrodes whiles
ensuring they were positioned close to each other without touching. The electrochemical cell

PITTING OF STAINLESS STEEL LABORATORY REPORT

MORO SABTIWU
MATS63541

November 2015

MORO SABTIWU (9721176)


SCHOOL OF MATERIALS -CCE

was then connected to a potentiostat (palm sense 3) and then connected to a computer
station where readings could be read from corrosion software PS Trace (as shown in figure
1). The set up was left for some time to stabilise and the OCP recorded. A potentiodynamic
sweep (cyclic voltammetry program) was initiated anodically from 500 mV below the
recorded OCP, then after a reverse scan was achieved by manually pressing the reverse
scan button when the current of 1 mA was attained. The experiment was stopped at
potential of 300 mV when the current became cathodic (i.e. 300 mV below the new Ecorr).
The aforementioned electrolytes were used in turns. Result from experiment was used to
ascertain, the Ecorr, Epit and Erep from polarization curves.
Computer
+
PS Trace Software

Potentiostat

Perforated Card board

R
E

304SS
( W E)

C
E

Working Electrode(WE)
Counter Electrode (CE)
Reference Electrode (RE)

Electrolyte
Fig. 2: A schematic of appararatus used for experiment
3.0 EXPERIMENTAL RESULTS AND DISCUSSION
The results from the potentiodynamic polarization are shown and discussed below. Data
from the PS tracer software plot potentiodynamic polarization curves (graph of Potential
against current density to study the pitting behavior Figure 2) to study the pitting behavior of
304SS in the aforementioned electrolytes. The graph shows the potentiodynamic
polarization curve of 304SS in the two solutions superimposed on each other. The results
from experiment are tabulated below in table 1.
Sample

0.1 Nacl solution

0.1Nacl solution Nacl + NaS2O3

OCP(Versus CSE)

-0.097V

-0.104V

The corrosion potentials(Ecorr)

-0.196 V

0.229V

0.224V

0.074V

Erep(Versus CSE)

0.081V

-0.229V

(Epit - Ecorr )(Versus CSE)

0.42V

0.303V

Parameter

(Versus CSE)

pitting potentials (Epit)(Versus CSE)

Table1: Result summary from potentiodynamic polarization plots


From figure 3, it is evident that the OCP values lags by -100mV and this could be as a result
of malfunctioning potentistat. The readings of experiment in thiosulphate solution were
therefore adjusted by 100mv. The plot also indictates 304SS was affected by pitting in both
cases. The presence of Cl- ions in both cases could have resulted in breaking of passive

PITTING OF STAINLESS STEEL LABORATORY REPORT

MORO SABTIWU
MATS63541

November 2015

MORO SABTIWU (9721176)


SCHOOL OF MATERIALS -CCE

layer in both cases. The Epit in S2O32- containing electrolyte was less than in the Nacl
solution indicating a high tendency of pitting in the S2O32- solution. This could be as a result
of the production of sulphide ions in solution according to equation (1) which prevented
repassivation in the 304 steel, hence the decline in Epit due to unbated piting corrosion. The
Erep in the S2O32- experiment was almost equal to the Ecorr, suggesting a redued tendency
for 304SS to repassivate due to action of sulphide ions and thus pitting continues to occur,
However, it might also be as as a result of the shortened test time. The difference between
Epit and ECorr, (Epit ECorr) in Nacl solution is greater than in S2O32- solution. This gives a
relative measure of the passivation ability. (Epit ECorr) represents the passive domain for
many alloys. The greater the difference between Epit and ECorr, the greater the passive
range and hence, the greater resistance to corrosion (Hamdy et al., 2007). Hence pitting
tendency is more likely in the thiosulphate. The range between ECorr between Epit from the
plot appears to give an estimate of pit induction time; longer in Nacl solution. The High Erep
in the Nacl solution suggest a deeper or steeper pit and compares well with the images
obtained from optical microscopy.
0.4

Potential [V](CSE)

0.2

Epit
Epass

0
-0.2
-0.4

Ecorr
-0.6
I1 304-0.1 M NaCl, 1mV/s

I2 304-0.01 M NaCl + 0.01M Na2S2O3, 1mV/s

-0.8
-8

-6

-4

-2

Log Current Density, i [mA/mm2]


Figure 3: Potentiodynamic polarization curve for 304SS in 0.1M Nacl solution and o.1Nacl + Na2S2O3
solution.

Numerous
shallow pits

Pit (deep)

Figure 4a: pitting in 0.1 Nacl Solution

Figure 4a: pitting in 0.1 Nacl + Na2S2O3 Solution

Figure 4: Optical microscopy images of 304SS after experiment. The observation in (a) is a single deep
champion pit consistent with high Epass as seen on polarization curve. In (b) numerous shallow pits
were observed consistent with the higher Epit on polarization curves

PITTING OF STAINLESS STEEL LABORATORY REPORT

MORO SABTIWU

Potential/V

MATS63541

MORO SABTIWU (9721176)


SCHOOL OF MATERIALS -CCE

November 2015

Potentiometry / OCP (POT)

0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0

200

400 Time/s

600

800

Figure 5: Galanostatic polarization curve for 304SS in Nacl solution.


Part B
From figure 5, The potential rose 300mV at t=0, suggesting initiation thickening of passive
layer and then a sudden drop to 150mV in after about 20s suggesting damage to passive
film due to action of chlorides ions on passive film; this trend of meta-stableness was
observed for about 190s until potential dropped significantly to 10mV suggesting stabilization
of pit (consistent with the deep champion pit in figre 4a) and it remained stable upto about
235s and tried to repassivate. From 235s to the end of test time, a metastable stage was
still observed within which a minimum potential of 70.6mV(at about 390s) and maximum
of 429mV(at about 853s) upto 883s end of test time.
4.0 Conclusion
Nacl solution contains aggressive Cl- anions that promote pitting corrosion in several
304 steels by breaking passive layer
The combined pitting effect of environment containing chlorides and sulphide for
type 304SS at 25oC is very severe, because chlorides break passive layer and
sulphides prevent repassivation, thus pitting may occur unabated.
References
Hamdy, A. S., Saeh, A. G., Shoeib, M. A., & Barakat, Y. (2007). Evaluation of corrosion and erosion
corrosion resistances of mild steel in sulfide-containing NaCl aerated solutions. Electrochimica acta,
52(24), 7068-7074.
M. Abdallah, S.M. Abd-Elhamim, B. Electrochem. 12 (1996) 449. [19] B. Bavarian, A. Moccari, D.
Macdonald, Corr. 38 (2) (1982) 104.
Jyoti Bhandaria, Faisal Khanb, , , Rouzbeh Abbassia, Vikram Garaniyaa, Roberto Ojedaa(2015),
Modelling of pitting corrosion in marine and offshore steel structures A technical reviewJournal of
Loss Prevention in the Process Industries, Elsevier, Volume 37, September 2015, Pages 3962
doi:10.1016/j.jlp.2015.06.008
T.H. Abood The influence of various parameters on pitting corrosion of 316L and 202 stainless steel
Department of Chemical Engineering of the University of Technology, University of Technology (2008)
Roberge, P. R. "Corrosion kinetics and applications of electrochemistry to corrosion." Corrosion
engineering: principles and practice. McGraw-Hill, New York (2008): 87.

El Meguid, EA Abd, N. A. Mahmoud, and SS Abd El Rehim. "The effect of some sulphur compounds
on the pitting corrosion of type 304 stainless steel."Materials chemistry and physics 63.1 (2000): 6774.

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