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 Mater. Res. Express 5 (2018) 066535 https://doi.org/10.1088/2053-1591/aac974

PAPER

The effect of cold work by rolling on electrochemical behaviour of Cr-

RECEIVED
4 April 2018
Mn austenitic stainless steel in chloride environment
REVISED
21 May 2018
ACCEPTED FOR PUBLICATION
Sourabh Shukla1 , Awanikumar P Patil and Vipin Tandon
1 June 2018 Department of Metallurgical and Materials Engineering, Visvesvaraya National Institute of Technology (VNIT), Nagpur 440010, India
1
PUBLISHED Author to whom any correspondence should be addressed.
22 June 2018
E-mail: sourabhshukla9876@gmail.com, appatil14@gmail.com and vipintandon3103@gmail.com

Keywords: cold work, x-ray diffraction, strain induced martensite, dislocations, Mott-Schottky, defect densities, electrochemical behaviour

Abstract
The effect of cold work (CW) on electrochemical behaviour of Cr-Mn austenitic stainless steel (AISI
202) in 3.5% NaCl solution was studied through microstructure, x-ray diffraction (XRD), Mott-
Schottky (M/S) techniques, Potentiodynamic polarization (PDP), and Electrochemical Impedence
Spectroscopy (EIS). The XRD spectrum was used to estimate volume fraction of martensite and
dislocation density, whereas EIS and PDP plots were used to evaluate electrochemical behaviour. The
M/S plots were used to estimate defect densities of passive film. It is found that as the cold work is
increased, austenite transform to martensite and dislocation density increases. It is also found that
corrosion resistance of the material decreases as the cold work is increased. When cold work is upto
15%, the material shows passivity. At higher cold work the material looses passivity. It is also found
that defect density of passivating film is more when Cr-Mn stainless steel is subjected to more cold
work. Most importantly, a relationship between dislocation density of the substrate and defect density
of the film has been noticed.

1. Introduction

Excellent corrosion resistance of Austenitic stainless steels (ASS) is due to its Cr-content and ability to form a
film of Cr2O3. Higher the Cr content better is the corrosion resistance [1–4]. M S−1 analysis gives information
about structure of the film [4–6]. It is found that most of the time the passive film of ASSs has a bi-layer structure;
inner layer is made of Cr2O3 and outer layer is made of Fe2O3 [3–6]. The Cr2O3 is a metal deficient oxide and
exhibits a p-type semiconducting behaviour. The Fe2O3 is a metal excess oxide and exhibits an n-type
semiconducting behaviour [7–9]. The M/S analysis also gives information about defect densities of the passive
film in terms of donor densities (ND) for p-type semiconducting oxides and acceptor density (NA) for n-type
semiconducting oxides. It is observed that defect density is (i) a function of Cl− content of test solution
[2, 10–13] and (ii) a function of Cr-content of stainless steel (SS) [9].
For a particular SS and test solution the cold work (CW) is found to adversely affect the corrosion resistance
[14–16]. It is important to understand the reason for this adverse effect on corrosion resistance of AISI 202 in
3.5% NaCl solution. For 304 S exposed to saturated calcium hydroxide solution, the NA and ND were found to
increase from 5×1021 and 1×1021 cm−3 to 11×1021 and 4×1021 cm−3, respectively [17]. It is known that
the cold work increases dislocation density of substrate and in case of SS causes formation of strain induced
martensite (SIM) [18–20]. Therefore, there must be some relationship between the dislocation density and
martensite content of substrate with defect densities (NA and ND) of the passivating film of particular SS in a
particular environment.
The Cr-Mn austenitic stainless steel, referred to as Cr-Mn SS hereafter, is receiving attention in industry due
to its low cost and low Ni content. Literature on effect of cold work on corrosion rate and defect densities of
passive film of Cr-Mn SS is scanty. The present paper therefore investigated the effect of cold work on corrosion
rate of Cr-Mn SS in 3.5% NaCl solution. The attempt is made to correlate dislocation densities with NA of the
passivating film by varying degree of cold work.

© 2018 IOP Publishing Ltd

Mater. Res. Express 5 (2018) 066535 S Shukla et al

Table 1. Chemical compositions of Cr-Mn ASS.

Chemical compositions (wt%)

Steel
Cr-Mn ASS C Cr Mn Ni Si P S Fe

0.13 15.32 9.14 0.19 0.46 0.014 0.0104 Balance

2. Experiment

Cr-Mn SS was a 6 mm sheet, whose chemical composition is presented in table 1. The samples
(50×10×6 mm3) were subjected to solutionizing (1 h: 1050 °C: water quench). These samples were then
subjected to reduction in thickness by rolling and designated as 15%, 30%, and 50% cold work (CW). Samples
for microstructure analysis (size of 10×10 mm2) were prepared by polishing through series of emry papers
upto 1500 grit, after which cloth polishing was done by using alumina powder and then electro-etched in 10 wt%
oxalic acid at 1.0 V (90 s). XRD was used to analyse various phases present in samples on or before cold work. It
was also used to estimate volume fraction of martensite. Hardness was measured with Vickers microhardness
tester. Potentiostatic and potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS),
and M/S measurements were used for Electrochemical investigations. Test solution was 3.5% NaCl solution. A
three electrode cell (sample, platinum, and saturated calomel electrode-SCE) was used. Tests were conducted on
Biologic make VMP-300 potentiostate controlled by EC lab software. After setting up the cell and filling test
solution, the working electrode (WE) was allowed to attain a steady state open circuit potential (OCP) for 1.5 h
and its OCP was measured. Then EIS and PDP measurements were conducted sequentially. Frequency range of
106 to 10−2 was used with sinusoidal AC signal of 10 mV for the EIS test at OCP. The PDP test was performed
between −0.5 V (versus OCP) to +0.5 V (versus OCP) at 0.018 mV s−1 scan rate. The M-S measurements were
performed at a scan rate of 50 mV s−1 (from 0.6 VSCE to −0.6 VSCE) [21].

3. Results and discussions

3.1. X-ray diffraction analysis

Figure 1 shows the XRD spectrums of SA and CW samples. Different peaks are identified for ε-martensite,
α′- martensite and γ-phase together with their corresponding planes. The ε-martensite and α′- martensite are
referred to as SIM hereafter. It indicate that all the peaks in spectrum of SA samples shows the γ-phase. In case of
15% cold work, very small peaks of α′(110), α′(200), and α′(211) with peak of ε-martensite (101) observed.
Thereafter, with increasing degree of cold work to 30% and 50%, intensity of α′(101), α′(200), α′(211) and
γ(220) peaks increase and intensity of γ(111) decreases. This observation agrees well with the findings
of Jinlong et al [16].
Effect of cold work on intensities of peaks of various phases is worked out and is listed in table 2 together with
values of R, i.e., material scattering factor [19, 22]. These intensities and values of R were then used to estimate
fraction of martensite in various cold worked samples using equation (1) [23] .

j ⎡ (Ia ¢ ) ⎤
j

( )å
1
n ⎢ (R j ) ⎦⎥
i = 1⎣
a¢
Va¢ = (1)
j ⎛ I gj ⎞ j ⎡ (Ia ¢ ) ⎤
j

( )å
1
n
⎜ ⎟
i = 1⎝ R gj ⎠
+ ( )å
1
n i = 1⎢
⎣ (R j ) ⎥⎦
a¢

Where, I represents the integrated intensity, n represents number of peaks of different phases and R represents
the material scattering factor. Table 2 shows the values of R [19, 22] used in the present estimation whereas
values of volume fraction of martensite was given in table 3. It was found that, as compared to solution annealed
sample, on increasing cold work, volume fraction of martensite increases. At 15% cold work, 19.08% martensite
has been observed, whereas at 30% cold work martensite increases to 37.51%. On further cold work upto 50%,
volume fraction of martensite increases to 55.54%, i.e., fraction of martensite becomes more than volume
fraction of austenite. As it is mention in one of the literature that intersection of two deformation bands form
ε-martensite platelets [24] and intersection of two ε-martensite platelets gives α′-martensite [25]. In order to
check effect of cold work on hardness, cold work samples were subjected to hardness measurement by Vickers
microhardness tester. These hardness values are also tabulated in table 3. Hardness also shows same trend as
shows by volume fraction of martensite. It is evident that as percentage of cold work increases, hardness also
increases. This is attributed to increase in the volume fraction of martensite.

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Figure 1. XRD spectrum of test steel in SA and CW condition.

Table 2. Effect of cold work on relative XRD peak intensity and values of R.

Relative peak intensity %

Reflection
plane SA 15% CW 30% CW 50% CW R values

{111}γ 100 100 100 30.45 212

{200}γ 34.12 32.75 16.74 — 95
{220}γ 9.19 38.65 88.10 100 52
{311}γ 14.28 19.23 20.11 3.08 67
{222}γ 3.90 4.32 2.94 1.09 21.5
{110}α′ — 12.34 57.85 32.57 279
{200}α′ — 1.94 42.39 82.57 40
{211}α′ — 1.67 50.25 56.25 79

Table 3. Effect of cold work on estimated fraction of martensite, hardness

and dislocation densities of Cr-Mn test steel.

Volume Dislocation
fraction Hardness density (ρ),
Sample (%) (HV) m−2 ×1017

SA 0 244.20 3.106
SA+15% CW 19.08 363.32 4.780
SA+30% CW 37.51 495.92 7.925
SA+50% CW 55.54 602.62 10.023

XRD data was then used to estimate dislocation density (ρ) of test samples using following equations [26]:
r = (rd ´ rs )1 / 2 (2)

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Figure 2. SEM microstructure of (a) SA and CW samples at (b) 15%, (c) 30%, and (d) 50%.

Where, ρd and ρs represents dislocation density on account of domain size and strain broadening, respectively.
3
rd = (3)
D2
Ke 2
rs = (4)
b2
Where, D=Crystallite size, b—Burgers vector, k=6π, e-microstrain, b—Burgers vector (b=a/ 2 ) and a—
lattice parameter. Table 3 shows ρ values as a function of increasing cold work. From table 3, it can be observed
that as the degree of cold work increases, the dislocation density increases.

3.2. Microstructural analysis

Figures 2 and 3 show the SEM and Optical microstructure of SA and cold work samples. The grains of SA
samples are equiaxed and these of cold work samples are elongated; the elongation increases with increasing cold
work. In cold work samples there are deformation band in few grains and number of grains showing
deformation bands increases with increasing cold work. On cold working, deformation bands are formed [24].
On further cold working ε-martensite platelets form at point of intersection of two deformation bands [25]. On
further cold working, the α′-martensite forms at point of intersection of two ε-martensite platelets [25]. There is
55.5% SIM in 50% CW Cr-Mn SS but the SIM is not distinctly identifiable in the optical microstructure. This
may be because it is uniformly distributed in the matrix and makes the surface relatively darker on etching.

3.3. Mott-Schottky analysis

Mott-Schotky (M/S) analysis yields information about the structure of the passivating film and is also used to
estimate defect density of the passivating film [2–6]. In general, passivating film of ASSs are bilayered [6]. The
inner layer is Cr2O3 and outer layer is Fe2O3. The Cr2O3 is a p-type semiconductor and Fe2O3 is a n-type
semiconductor. Such a bilayer structure is manifested in M/S plots as a V-shaped graph with a smooth valley as
schematically shown in figure 4 for Stainless steels. The slope of linear regions on either side of the valley yields
defect densities of the film. The linear region on left side of valley has negative slope and indicates p-type oxide
film. The linear region on right side of valley has positive slope and indicate n-type oxide film. This feature helps
identify structure of the passivating film. The p-type oxide film has cation vacancies, which are considered as a
charge acceptor. Therefore this type of defect density is termed as acceptor density (NA). The n-type oxide film

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Figure 3. Optical microstructure of (a) SA and CW samples at (b) 15%, (c) 30%, and (d) 50%.

Figure 4. Schematic Diagram of M-S plots for ASS.

has excess cation (in intersticial space) or oxygen deficient, which are considered as donor of the charge.
Therefore it is termed as a donor density (ND). The slope of the linear region of the M-S plot is then used to
estimate defect densities.
Defect densities of passive film are calculated from space charge capacitance (C) using equations (5) and (6)
[27–29].

1 2 ⎡ KT ⎤
= ⎢E - EFB - ⎥ n‐type semiconductor (5)
C2 eeo eND ⎣ e ⎦

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Figure 5. M-S plots of SA and CW samples of Cr-Mn ASS.

Table 4. Effect of cold work on charge

carrier densities of passivating film of
Cr-Mn test steel.

Sample NA, cm−3 ×1021

SA 8.10
SA+15% CW 9.52
SA+30% CW 12.45
SA+50% CW 14.01

1 2 ⎡ KT ⎤
= ⎢E - EFB - ⎥ p‐type semiconductor (6)
C2 eeo eNA ⎣ e ⎦

Where, C is capacitance at space charge region, ε—dielectric constant (12 for passive film in ASS) [21],
ε0—vacuum permittivity (8.854×10−12 Fm−1), e—electron charge (1.6×10−19 C), k—the Boltzmann
constant (1.38×10−23 JK−1), ND—donor density, NA—acceptor density, T—temperature in K, E—applied
potential and Efb—flat band potential.
For n-type semiconductor, plot of 1/C versus E is linear and its slope is positive. The slope is inversely related
to donor density. On the other hand, p-type semiconductor yields a negative slope and has inverse relationship
with the acceptor density.
M/S analysis were carried out to estimate defect densities of passive film of Cr-Mn SS in NaCl solution.
Figure 5 shows M/S plots of Cr-Mn SS at different cold work in 3.5% NaCl solution. As compared to schematic
of M/S plot (figure 4), the plots in figure 5 show only left hand side of valley. It means the plots in figure 5 only
shows left hand side part of valley that has negative slope. The plot does not rise after reaching a minimum value.
The other part of valley with positive slope is absent. In case of SS, it is known that part of valley with negative
slope indicates formation of inner layer of Cr2O3 and part of valley with positive slope indicates formation of
outer layer of Fe2O3 [6]. Therefore, from the M/S plots it can be deduced that film on Cr-Mn SS in NaCl solution
has only mono layer of Cr2O3, not a bilayer (Cr2O3 and Fe2O3). The slope of the linear region was used to
estimate acceptor density (NA) as shown in table 4. Table 4 conclude that on increasing cold work degree, NA also
increases. Similar plots are reported by C M Rangel et al for AISI 304 S in boiling solution of
H3BO4(270 g L−1)+NaCl(2 g L−1) of pH 2.2 [30] and X Fenga et al [31] for 304 s in 0.05 M Cl− solution
of pH 9.
Figure 6 shows effect of cold work on dislocation density and charge carrier density. It can evident that as
percentage of cold work increases, dislocation density and charge carrier density increases. This clearly means
that there is some relationship between dislocation density of substrate with defect density of the passive film of
Cr-Mn SS in 3.5% NaCl solution. X Fenga et al investigated how cold work affects corrosion of 304 S in chloride
solution. Their results show that the charge carrier density increases with increase in deformation level [31]. Due

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Figure 6. Effect of degree of CW on dislocation density and charge carrier density.

Figure 7. Nyquist and Bode plots of SA and CW samples of Cr-Mn ASS.

to increase in cold work, dislocation density and stored energy increases, which then increases driving force for
electrochemical reaction and as a consequence corrosion rate increases [32].
C M Rangel et al found that on cold working of 304 ASS, the NA of film increases from 3.5×1021 (cm−3) to
6.5×1021 (cm−3) in H3BO4+NaCl solution [30]. J-B Lee et al [33] observed that on addition of nitrogen to 316L, the
defect densities of passivating film decreases and it reduces metastable pitting tendency. X Fenga et al found that on
increasing cold work from 0.4% to 40%, the defect density of passivating film of 304 in 0.05 NaCl solution of pH 9 [31].
Hence, it can be seen that as cold work increases, more dislocation are generated and more strain induced
martensite is formed, this increases charge carrier densities of passivating film and subsequently the corrosion
rate of test steel increases.

3.4. Chemical stability of passive film (EIS measurement)

EIS test were performed to investigate influence of cold work on resistance of the passive film of Cr-Mn SS.
Figure 7 shows (a) Nyquist diagram and (b) Bode plots for SA and cold work samples. It is evident that the
Nyquist plots are in form of unfinished semicircle. Similar nyquist plots are also described as unfinished
capacitance arc [34]. This suggest that larger the diameter of semicircle, better will be the resistance of the film. It
is also suggest with increasing cold work, the resistance of film is decreasing. In the bode plots, the adverse effect
of cold work is reflected at low frequency end. As it is evident the phase angle at low frequency end decreases with
increasing CW, indicating that the film becomes more defective as CW is increased. This observation is in
agreement with the findings of M/S plots. The EIS data was then curve-fitted to find equivalent circuit giving the
best fit. The equivalent circuit adopted in this work is given in figure 8, where Q and C defines a constant phase
element (CPE). Figure 9 show the Nyquist plot of 30% and 50% CW. It compares the experimental curve with

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Figure 8. The best fit equivalent circuit (EIS spectra).

Figure 9. Nyquist plots of: (a) experimental curve with simple circuit fitted curve for 30% CW, (b) experimental curve with second
time constant fitted curve for 30% CW, (c) experimental curve with simple circuit fitted curve for 50% CW, (b) experimental curve
with second time constant fitted curve for 50% CW .

curve obtained from simple circuit and second time constant circuit. It is observe that the experimental curve is
not being fitted with the curve of simple circuit for both 30% and 50% CW. On the other side, both curve is being
fitted with second time constant curve.The CPE is included [35, 36] because it takes into account the
heterogeneities of the electrode surface. The equation for impedance is given by:
1
Z CPE = (Jw )-n (7)
Q
Therefore, total impedence is given as:
⎡ 1 + R2 C j w ⎤-1
Z total = Rsol . + ⎢Q (Jw )n + ⎥ (8)
⎣ R1 + R2 + R1 R2 C j w ⎦

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Table 5. Equivalent circuit parameters obtained from EIS plots.

Sample Rsol. (Ω.cm2) Q (10-6 Ω.cm−2.sn) a1 R1 (Ω.cm2) C (10−3 Ω.cm−2.sn) a2 R2 (Ω.cm2)

SA 8.016 62.68 0.76 14 276 1.21 0.98 69 410

SA+15% CW 7.166 67.72 0.85 13 790 1.25 0.99 55 393
SA+30% CW 8.308 77.32 0.85 7829 1.42 0.97 42 684
SA+50% CW 7.89 85.20 0.82 5530 1.89 0.99 27 986

Figure 10. PDP plots of SA and CW of Cr-Mn ASS.

This circuit consist of the ohmic resistance of the solution (Rsol) which is in series with passive film
admittance (Q), in parallel with the passive layer resistance (R1), which in turn is in series with a parallel
connection of the charge transfer resistance (R2) and double layer capacitance (C). Therefore in this work, some
physical interpretation has been adopted: the resistance at high frequency time constant (R1, Q) corresponds to
surface area covered with outer layer of passive film. Similarily, low frequency time constant (R2, C) was assigned
to area covered with inner compact layer which becomes active (i.e., metal/film interface and active pits due to
Cl− ions) [4]. The EIS results obtained by using this circuit explain the corrosion activity as well as passivity of
Cr-Mn SS in NaCl solution. Table 5 shows the fitted parameters and highlights the effect of cold work. It is
observed that as degree of cold work increases, the values of R1 and R2 decrease, i.e., impedance of the passive
film decreases. The R1 value is almost 20% of R2 value. It signifies that the charge transfer reaction occurring at
metal/film (M/F) interface are much slower than that occuring at film/surface (F/S) interface. With increasing
cold work, the resistance of the film decreases meaning that the film should have more defects. This is what has
been found in M-S analysis. Thus both the results complement each other.

3.5. Potentiodyanamic analysis (PDP)

Figure 10 shows the PDP diagram of solution annealed and cold worked of test steel samples in NaCl solution.
Cathodic part of the plot is curved indicating diffusion controlled cathodic reaction. Usually such curves are
attributed to oxygen reduction reaction. In NaCl solution of pH=8, the pH is too high for hydrogen reduction
reaction to occur. Anodic part of plots show active corrosion for 30% and 50% cold work sample and somewhat
passivating behaviour for 15% cold work and SA sample. It means that 30% and 50% cold work has caused loss
of passivity of otherwise passivating alloy. The current density in passive region is increasing with increasing
overpotential. Tafel extrapolation was applied as anodic and cathodic part to obtain Ecorr and icorr. It also yielded
anodic tafel slope (βa) and cathodic tafel slope (βc). Anodic part of these plots show rapid increase in anodic
current density after passive range; corresponding potential is taken as pitting potential (Epit). The
electrochemical data thus obtained is tabulated (table 6). The anodic parts of all the plots are linear, indicating
the anodic reaction to be under activation control. Anodic part of PDP plots suggest that the film formation and
metal dissolution are the main anodic reactions [37, 38].

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

Table 6. Electrochemical data drawn from PDP plots.

Sample Ecorr (mV) Icorr (A cm−2) βa (mV/dec) βc (mV/dec) Epit (V)

SA −488.52 1.086 81.41 72.60 0.037

SA+15% CW −523.25 2.888 95.45 150.0 −0.159
SA+30% CW −561.93 10.261 102.2 198.82 —
SA+50% CW −696.64 20.236 138.5 479.5 —

Film formation reaction:

2Cr + 3H2 O  Cr 2O3 + 6H+ + 6e- (9)
Metal dissolution reaction:
M + H2 O  MOH ad + H+ + e- (10)
MOH ad  MOH+ +e (11)
MOH+  M2 ++ OH- (12)
M+ Cl-  MCl ad + H+ + e- (13)
MCl ad  MCl+ + e- (14)
MCl+  M2 + + Cl- (15)
Increasing icorr with increasing cold work suggests that the resistance of passivating film is decreasing with
increasing cold work. This observation is in agreement with observation of Nyquist and bode plots that with
increasing cold work more defective film forms and film impedence decreases. It is attribute to increasing
dislocation density and formation of SIM in the material on cold work. Considering the fact that dislocation
density of SIM is much higher than dislocation density of cold worked austenite [39], the contribution of SIM to
the rise in icorr is relatively more. It is also observed from M-S plots that defect density of film is increasing on
cold work. The defects in the film are responsible for cation migration from M/F interface to F/S interface. So
higher the defects in the film, higher will be cation generation at M/F interface, higher will be cation migration
from M/F to F/S and higher will be dissolution rate. This is what is observed in the present investigation.
Therefore, it can be concluded that cold work influences dislocation density of substrate, which in turn
influences defect density of the passivating film. Consequently, the passive film with higher defect density causes
more corrosion. From the potentiodynamic polarization results, it is evident that test steel in solution annealed
and 15% CW conditions exhibits passivity. But when cold work is 30% and 50%, the Cr-Mn SS does not show
passivity. This suggest that on cold working more than 15%, the Cr-Mn SS will not passivate and consequently
undergo more corrosion. The practising engineers should bear this in mind when using Cr-Mn SS for
fabrication.

4. Conclusion

1. The cold work (CW) causes transformation of austenite to strain induced martensite (SIM).
2. The amount of SIM increases with increasing cold work.
3. The cold work also increases dislocation density (dd) of substrate and the dd increases with increasing
cold work.
4. Mott-schotky (M-S) analysis suggests that the defect densities of the passivating film increases with
increasing cold work.
5. M-S analysis also shows that the passivating film has p-type semiconducting behaviour.
6. The EIS results show that the film resistance decreases on increasing cold work.
7. The Cr-Mn ASS looses passivity when cold work is more than 15%. Therefore, such a situation should be
avoided.

ORCID iDs

Sourabh Shukla https://orcid.org/0000-0003-4954-7405

Awanikumar P Patil https://orcid.org/0000-0002-4511-7558

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Mater. Res. Express 5 (2018) 066535 S Shukla et al

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