Material Science and engineering, EMSE.

ON THE DEPASSIVATION MECHANISM

OF A SUPERMARTENSITIC STAINLESS
STEEL AND THE INFLUENCE OF THE
APPLIED STRESS

C. Chennur, *C. Gayton

ABSTRACT
The depassivation mechanism of industrial and quenched phase and a protection of the austenite phase during free
supermartentitic stainless steels (SMSS) was investigated by corrosion potential occur (2).
potentiodynamic polarization to understand the selective
The aim of the present study was to investigate the factors
dissolution processes in localized corrosion phenomena.
governing the selective dissolution in a chloride environment
Results showed that the depassivation of the industrial steel
of two different supermartensitic steels with different
proceeds in two stages and in one stage for quenched steel. In
chromium (Cr) and nickel (Ni) content. Industrial and
industrial steel, initially the austenite is the only phase
quenched supermartensitic stainless steels are two different
depassivated within the range 1.5 and above pH units,
steels used for this experiment, the industrial supermatensitic
providing a single corrosion peak on the polarization curves
stainless steel has two different phases (70% martensite, 30%
of the SMSS. Eventually, the martensite is also depassivated
retained austenite) and the quenched steel has only one phase
and provides a second corrosion peak at a more cathodic
(99.99% martensite).Later, the dissolution of industrial steel
potential. Observations are done in terms of the partitioning
in a chloride environment with influence of applied stress was
of alloying elements.
also investigated. This study also investigated the role of the
KEYWORDS: supermartensitic stainless steels, localized partitioning of the alloying elements in the depassivation
corrosion, polarization, selective dissolution, constant load. process and the corrosion mode of industrial steel.

1. INTRODUCTION TABLE 1
Initially, the steel is protected by protective passive film
Martensite content and austenite content with different
formed during oxidation reaction. When the steel comes in
alloying elements concentrations in wt% was measured
contact with acidic environment or chloride content accoding to thermocal simulations.
environment then the protective film is depassivated and the
protected steel undergoes Pitting corrosion. Pitting, is a form α' = Martensite phase
of extremely localized corrosion that leads to the creation of
γ = Austenite phase
small holes in the metal. The driving power for pitting
corrosion is the depassivation of a small area. 10 Phase Fe Cr Ni
In acidic environments, supermartensitic stainless steel
becomes susceptible to localized corrosion and stress
corrosion cracking (SSC) in presence of external forces. In
Industrial α' Bal ~15 ~3
mixed sulfuric/ hydrochloric acid (H2 S04 /HCL) solutions in
the presence of a sufficient quantity of the chloride, there are
two anodic peaks in the active-to-passive transition region of γ Bal ~13 ~11
the potentiodynamic polarization curves of SMSS (1). The
martensite phase usually corrodes at the more negative Quenched α' Bal 15 5
potential values, while the austenitic phase dissolves during
the corrosion peak just below the passivation potential. As a
result, both an accentuated preferential attack of austenite

1
Material Science and engineering, EMSE.

2. EXPERIMENTAL PROCEDURES tension machine, later the sample was allowed to

Materials Used: strain hardened by relaxation of and same
electrochemical tests were conducted.
The compositions of industrial and quenc he d
supermartensitic stainless steels used for this 3. RESULTS AND DISCUSSION
study are given in the Table 1. The partitioning of
the alloy elements in the constituent phases is also Depassivation of the quenched sample.
shown in this table.

Specimens used for depassivation test were 10000

cylindrical in shape with surface diameter of

Current density (µA/cm )

2
45mm and this surface was exposed as a worki ng
electrode during the tests. Both industrial and 1000
quenched samples were ground with different
grades of silicon carbide (SiC) paper, polished by
diamond paste (1 µm size), degreased with 100
acetone (CH3 COCH 3 ), dried and finally aged 24h
at room temperature. Industrial supermartens it ic
10
stainless steel specimen used for depassivat i on
test with influence of applied stress was uniaxia l
specimen with diameter of (20mm) and the further 1
polishing procedures were carried out in the same -600 -400 -200 0 200 400
manner.
0.1
pH1.3 pH1.1 Potential (mV)
Test Solutions Used:
Tests were carried out in the NaCl (30g/ l)
Figure 1: Potentiodynamic polarization curves of quenched
solutions were prepared using analytical grade SMSS at pH 1.3 and 1.1 of deaerated NaCl solution.
Nacl and deionized water. Solutions were
acidified using addition of concentrated HCL and
were determined using a combined glass
Depassivation of the industrial sample.
electrode. Solutions with a pH from 2.0 down to
0.5 were tested at nearly every 0.1 interval. All
solutions were deaerated 12h with CO2 gas before
experiments. 10000
Current density (µA/cm2)

Electrochemical Tests: 1000

The experiments were conducted in an
electrochemical cell, with a large area platinum 100
counter electrode. A saturated calomel electrode
(SCE) was used as a reference connected through 10
a salt bridge. Using potentiostat, potentials and
current were recorded. All measurements were 1
performed at room temperature (3). All potent ia ls -800 -600 -400 -200 0 200 400
are given on the SCE scale potential. Each 0.1
prepared electrode was immersed into the soluti on pH0.6
pH0.8
at open-circuit potential (OCP) for 15min, and
pH1.1 0.01
then a potentiodynamic scan at a constant scan
pH1.3
rate of 1mV-1 was applied until the current reached pH1.5 0.001
the value of 0.5 mA. All the electrochemical tests pH1.8 Pote ntial (mV)
were repeated to ensure the reproducibility of
results. For the experiment with the influence of Figure 2: Potentiodynamic polarization curves of industrial
SMSS at various pH of deaerated NaCl solution.
applied stress, a fixed tensile stress of 750 Mpa
was applied without any interruption on uniaxial

2
Material Science and engineering, EMSE.

The Graphs are drawn current density vs potentia l, Selective dissolution of the industrial sample for
the depassivation pH (pHd ) is of the order of 24h.
magnitude of the passive current density. The 10000
depassivation of quenched sample in deaerated

Current density (µA/cm )

2
NaCl acidified by HCL is investigated through
1000
polarization curves as represented in Figure1. It
shows polarization curves for only certain pH
tested at 1.3 and 1.1. The polarization curves 100
possess a single corrosion peak which represents
the dissolution of martensite phase of quenc he d
10
sample. Only the behavior of martensite phase i.e.
single peak at pH 1.3 and pH 1.1 are observe d.
Dissolution rate of quenched sample in pH 1.1 is 1
faster than in pH 1.3. Moreover the curve of pH -600 -400 -200 0 200
1.1 attains high current density peak compared to Martensite Austenite 0.1 Potential (mV)
pH 1.3. Depassivation rate increases with
decrease in pH of solution and higher the Figure 3: Potentiodynamic polarization curves of industrial
resistance to increase in current density better SMSS at pH 0.6 of deaerated NaCl solution.
shall be the corrosion resistance (4). Higher the
acidic environment, maximum the current can be
attributed to the corrosion of martensite.

The depassivation of industrial sample in

deaerated NaCl acidified by HCL is investiga te d
through polarization curves as represented in
Figure2. From pH 1.8 down to 1.5, polarizat i on
curves possess a unique corrosion peak; the
acidification of the solution at lower pH values
provides the emergence of another corrosion peak
at more cathodic potentials. For curves, pH 1.5
and above a single peak shows selective
dissolution of austenite phase and the martensite
phase is protected but with acidification of the
solution from pH 1.3, the first maximum current (a)
shows the dissolution of martensite phase and
second one to austenite phase. To know the
phenomenon of both peaks in the polarizat i on
curve, industrial sample was exposed at pH 0.6 for
24h at each potential of maximum corrosi on
current (-380mV and -280mV). Figures 4(a) and
(b) show SEM micrographs of the martensite
phase and austenite phase remaining after
respective selective dissolution of the martensite
at -380mV and the austenite at -280mV. For pH
1.3 and below the first current maximum can be
attributed attributed to the corrosion of the
martensite phase and the second one to the
austenite phase. Besides, it seems that the single
(b)
corrosion peak on the polarization curves for pH
1.5 and above occurs at the corrosion potentials of Figure 4: SEM micrographs showing the selective
the austenite phase, suggesting that for these pH dissolution of phases in industrial SMSS at deaerated NaCl
levels the austenite is corroded while the pH = 0.6 for 24h: (a) Martensite phase dissolution at -
martensite is passivated. 380mV and (b) Austenite phase dissolution at -280mV.

3
Material Science and engineering, EMSE.

Depassivation mechanism rate of Depassivation of the industrial sample with

supermartensitic stainless steel increases with
influence of fixed applied stress (750Mpa)
influence of external stress. On Compari s on
between figure 5 and 2, both phases are 10000
depassivated at more negative potential and rate
of corrosion is faster with influence of stress. For
1000
high pH solutions i.e. at pH 1.8 and pH 2.0,
austenite is the only phase shows the peak and
martensite remains passivated. With decrease in 100
pH of solution i.e. below 1.8, martensite attains
the first peak with maximum current and second
one to the austenite phase. 10

Influence of Cr content
1
The primary cause of the difference of -800 -600 -400 -200 0 200 400
depassivation peak between the austenite phase
and martensite phase must be the difference of Cr 0.1
content, the element known to form passive
film(4). The Cr content of the two phases of each Potential (mV)
0.01
grade is given in Table 1. Because of the
partitioning of alloying elements between the two pH2.0 pH1.8 pH1.5
pH1.3 pH1.1
phases, the martensite contains more Cr than the
austenite. For high pH martensite forms a good
passive film compared to austenite, so the Figure 5: Potentiodynamic polarization curves of industrial
SMSS at various pH solutions with influence of applied
protection of martensite and dissolution of
stress 750Mpa.
austenite takes place in low acidic solutions. But,
in acidic solution the the film is easily
depassivated. On comparing the depassivat i on
mechanism of two SMSS, which do not have 4. CONCLUSION
exactly the same Cr content, shows that they do
not have the same depassivation mechanism.
Based on the present electrochemical study of 2
Influence of Ni content different supermartensitic stainless steel in
strongly acidified deaerated NaCl solutions, it can
Ni is the element known for good resistance to
initiation of the corrosion (4). The Ni content has be concluded:
 For pH 1.5 and above, the austenite is the only
an influence on the propagation rate of the
phase depassivated, which results in a single
corrosion. Table 1 shows that austenite enriched
corrosion peak on the polarization curve, If
in Ni leads to good resistive to corrosion than
the solution is more acidic then the martensite
martensite. For lower acidic solutions austenite
undergoes corrosion because of low Cr content is also depassivated and provides a second
corrosion peak at more negative potentials.
and poor passivation but it is attacked by
 In high acidic solutions, once the protecti ve
corrosion after a higher pitting potential. The
higher the pitting potential, better shall be the film of the martenite is depassivated then a
preferential corrosion of martensite and
corrosion resistance of the grade. Outside the pits,
protection of austenite occurs during free
the passive layer is always present to protect the
stainless steel. For highly acidic solutions i.e. corrosion potential and with pass of time
dissolution of austenite at high potential also
from Figure 3 the dissolution of martensite at
potential -380mV is faster than dissolution of take place.
 Cr content provides wide protective film, Ni
austenite at potential -280mV but after reaching
content lowers the corrosion rate and the
potential near -2800mV the austenite starts to
loose Ni ions in the solution and leaving the partitioning of Ni and Cr provides the
separation of the two corrosion peaks.
solution to green in color.

4
Material Science and engineering, EMSE.

 Behavior of phases not only depend on

aggressive environment but also on the
external loads (6).
 Higher the applied load and lower the pH of
solution, this combination multiplies the
corrosion rate of steel.

5. REFERENCES

1. Supermartensitic Stainless steels ’99: Brussels,

Belgium, May 27-28, 1999

2. E. Symniotis, Corrosion 46, 1 (1990)

3. The Electrochemistry of corrosion, edited by gareth

hinds from the original work of J G N Thomas.

4. Stainless Steel and corrosion, Stainless Europe,

Arcelor Mittal.

5. R. F. Jargelius-Petterson, Corrossion science 7

(1996)

6. A. Laitinen, H. Hanninen, Corrosion 52 (1996):

p295