Applied Surface Science 388 (2016) 160–168

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Applied Surface Science

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Corrosion studies using potentiodynamic and EIS electrochemical

techniques of welded lean duplex stainless steel UNS S82441
Z. Brytan a,∗ , J. Niagaj b , Ł. Reiman a
a
Division of Materials Processing Technology, Management and Computer Techniques in Materials Science, Institute of Engineering Materials and
Biomaterials, Silesian University of Technology, ul. Konarskiego 18a, 44-100 Gliwice, Poland
b
Institute of Welding, ul. Bł. Czesława 16/18, 44-100 Gliwice, Poland

a r t i c l e i n f o a b s t r a c t

Article history: The corrosion characterisation of lean duplex stainless steel (1.4662) UNS S82441 welded joints using the
Received 15 October 2015 potentiodynamic test and electrochemical impedance spectroscopy in 1 M NaCl solution are discussed.
Received in revised form 27 January 2016 The influence of autogenous TIG welding parameters (amount of heat input and composition of shielding
Accepted 28 January 2016
gases like Ar and Ar–N2 and an Ar–He mixture), as well as A-TIG welding was studied. The influence of
Available online 1 February 2016
welding parameters on phase balance, microstructural changes and the protective properties of passive
oxide films formed at the open circuit potential or during the anodic polarisation were studied.
Keywords:
From the results of the potentiodynamic test and electrochemical impedance spectroscopy of TIG
Lean duplex stainless steel
Potentiodynamic test
and A-TiG, welded joints show a lower corrosion resistance compared to non-welded parent metal, but
EIS introducing heat input properly during welding and applying shielding gases rich in nitrogen or helium
TIG can increase austenitic phase content, which is beneficial for corrosion resistance, and improves surface
A-TIG oxide layer resistance in 1 M NaCl solution.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction mechanical properties and corrosion resistance as standard duplex

Corrosion-resistant alloys consist of stainless steels, heat-
resistant steels and creep-resistant steels, where stainless steel has
the highest range of possible applications for various load-bearing
and non-load-bearing constructions. Stainless steel is the most
popular material applied where high corrosion resistance, high sur-
face finish quality, elevated hygienic standards and moderate price
are required. The stainless steel family is composed of a single phase
alloy: austenitic, ferritic, martensitic and precipitation hardening
alloys, as well as double phase alloys: duplex stainless steels. The
duplex stainless steels combine the properties and advantages of
two single phase alloys (viz. ferritic and austenitic) and show better
mechanical properties than the single phase alloys, as well as supe-
rior corrosion resistance. Duplex stainless steels, based on chemical
composition, can be sub-divided into standard duplex alloys, super-
duplex, hyper-duplex and lean duplex stainless steel grades [1,2].
Standard duplex grades contain 22% Cr, 5% Ni and 3% Mo, and the
addition of 0.2% N. The super-duplex group consists of grades with
a higher alloy content i.e. 25% Cr, 7% Ni and 3–4% Mo. The lean
duplex stainless steel family was developed to obtain comparable
∗ Corresponding author.
E-mail address: zbigniew.brytan@polsl.pl (Z. Brytan).
grades, but replacing the expensive addition of Ni and Mn. They
also contain a high content of nitrogen. In duplex stainless steels
Ni, Mn and N stabilise austenite and maintain a balance between
austenite and ferrite at about 50% [3]. The use of manganese can
ensure proper ferrite–austenite phase balance and overall material
performance. It must be noted that manganese is not as effective as
nickel in stainless steel surface passivation, thus resulting in slightly
lower corrosion performance of grades enriched in manganese with
respect to standard Cr–Ni–Mo alloys [4]. The purpose of manganese
addition to lean duplex stainless steel is to increase the solubility
of nitrogen, which is a strong austenite former and has a proven
beneficial influence on the pitting corrosion resistance [3].
Lean duplex stainless steel type S82441 [5] is recently developed
and was only a few years ago introduced to the market. Compared
to the well-known and widely used standard duplex stainless steel
S32205/S31803, steel S82441 contains a higher amount of man-
ganese, but a slightly lower amount of Ni and Mo. In turn, compared
to the lean duplex steel S32101, new grade S82441 contains less
manganese, but more chromium, nickel and molybdenum [6]. The
lean duplex stainless steel with a composition containing approx-
imately 24% Cr and 3.5% Ni, 1.5% Mo and 3.0% Mn has strength and
corrosion resistance superior to that of Cr–Ni austenitic stainless
steel Type 304L and comparable to Cr–Ni–Mo grade Type 316L. The
higher strength of lean duplex stainless steel family allows thinner

http://dx.doi.org/10.1016/j.apsusc.2016.01.260
0169-4332/© 2016 Elsevier B.V. All rights reserved.
 Z. Brytan et al. / Applied Surface Science 388 (2016) 160–168
sections of LDSS to replace components made with thicker sec-
tions of standard austenitic Cr–Ni and Cr–Ni–Mo stainless alloys.
The high strength, toughness, corrosion resistance, and weldabil-
ity of the lean duplex stainless steel family makes them a good
choice for use in many industrial, load-bearing and domestic goods
applications [5,6].
Lean duplex stainless steels, like the duplex, show good weld-
ability [7–9]. During the welding of duplex stainless steels, one of
the main objectives is to maintain the corrosion resistance of the
welded joints at a level characteristic of the base material. This is
not always easy to obtain because of the thermal cycle of welding.
This should be short enough to prevent microstructural changes,
which usually occur in welds that require multiple passes. For lean
duplex as well as duplex grades it is essential to ensure that an
adequate amount of austenite and ferrite is formed in the weld
metal and heat-affected zone, in order to ensure an adequate bal-
ance between phases [10,11]. The second important factor that
should be taken into consideration during welding of such alloys is
to avoid the precipitation of secondary phases detrimental to the
mechanical and corrosion properties [12,13]. Additionally, proper
post-weld cleaning should be performed to ensure good corrosion
properties [7]. This is because the duplex stainless steels intrinsi-
cally are very prone to inter-metallic phase precipitations (in the
range 325–950 ◦ C). Precipitations of ␴-phase, ␹-phase, chromium
nitrides (Cr2 N, CrN), carbides M23 C6 , M7 C3 and decomposition of
ferrite cause embrittlement and reduce the corrosion resistance of
duplex stainless steels [10–17].
The major difference between conventional TIG (Tungsten Inert
Gas) welding and increasingly popular laser welding is the much
lower total heat input in the case of laser welding. This results
because the laser beam produces a narrow weld seam with fast
energy transfer from the beam into the base material. Comprehen-
sive studies of the influence of surface laser treatment of various
highly alloyed steels grades have shown the improvement of their
intergranular, pitting corrosion and cavitation erosion resistance
and also wear resistance after laser surface melting and surface
alloying [18–20].
Despite the development of laser welding techniques, TIG weld-
ing is still one of the major welding processes used in industry for
high-quality joints made on stainless steels. In order to increase
welding penetration capability of the arc in TIG welding, the acti-
vated TIG process referred to as A-TIG was developed. The A-TIG
process involves the application of a thin layer of activating flux
material onto the surface prior to welding, which influences the
welding arc constriction and results in higher penetration depth
and reduced weld shrinkage and distortion. The main disadvan-
tage of this process can be higher surface roughness, especially for
mechanised welding operations, of the weld bead and the neces-
sity of weld cleaning (wire brushing), after welding due to adhering
slug on the surface [21].
The paper discusses the corrosion characteristic of lean duplex
stainless steel (1.4662) UNS S82441 welded joints using the poten-
tiodynamic test and electrochemical impedance spectroscopy in
1 M NaCl solution. The influence of autogenous TIG welding param-
eters, i.e. the amount of heat input and the composition of shielding
gases like Ar and Ar–N2 and an Ar–He mixture, as well as A-TIG
welding, was studied. The influence of welding parameters on
phase balance, microstructural changes and protective properties
of passive oxide films formed at the open circuit potential or during
the anodic polarisation was studied.
2. Materials and methods
The research was carried out using sheets of lean duplex stain-
less steel grade UNS S82441 of thickness 6.0 mm, with the chemical
161
Table 1
Chemical composition of lean duplex stainless steel S82441.
Chemical composition, wt.%
C Si Mn P S Cr Ni Mo Cu N
0.025 0.36 3.00 0.022 0.001 23.92 3.66 1.61 0.39 0.279
composition as presented in Table 1. The Pitting Resistance
Equivalent Number PREN calculated according to the formula:
PREN = %Cr + 3.3×(%Mo) + 16×(%N) for a given melt is equal to
PREN = 33.7. During TIG and A-TIG welding, the respective shiel-
ding gases were applied: pure technical argon EN ISO 14175-I1-Ar,
the mixes of argon and nitrogen (5, 10 and 15%) with designations
according to standard: EN ISO 14175-N2-ArN-5, EN ISO 14175-N3-
ArN-10 and EN ISO 14175-N3-ArN-15, and also a mixture of argon
and helium in the ratio 50:50 with designation EN ISO 14175-I3-
ArHe-50.
The welding joints were produced using sheet plates of dimen-
sions 100 mm × 50 mm × 6 mm on the TIG mechanised welding
stand consisting of welding source power Lorch V40, a welding
trolley DC20 Promotech with a precisely adjustable travel speed
of torch and an attachment device to position the welded pieces.
The welding speed of all samples was constant and the current
was changed in the range from 50 to 300 A (Table 2). A-TIG weld-
ing was performed using BC-31 flux. All the tests were performed
with a constant speed of 15 cm/min and the constant arc length of
1.5 mm.
The sample surface after welding was cleaned and etched with
a pickling agent Antox, appropriate for stainless steel cleaning. In
most cases, after etching the sample surface was glossy. However, a
thin layer of slag was failed to be removed from the samples welded
at a current of 300 A using the A-TIG method, which was associated
with an overheating of joints and application of activating flux. The
use of a wire brush successfully removed all impurities from the
surface of the samples.
Microstructural characterisation was performed on the cross-
section of the welded samples. Microstructural observations and
geometrical characteristics of the weld bead were carried out
in the light and scanning electron microscope. Light microscope
observations involved etching using Aqua Regia reagent and were
performed at 400× and 1000× magnifications using a LEICA MEF4A
microscope to evaluate phase content. The scanning electron
microscope (SEM) involved in the studies was a SUPRA 25 of Zeiss
equipped with an EDS probe.
The corrosion behaviours of the welded lean duplex stain-
less steels were evaluated by analysing the polarisation curves
and electrochemical impedance spectroscopy. The testing environ-
ment was 1 M NaCl at room temperature. The potentiodynamic
test was carried out on the Potentiostat Atlas 0531 according
to PN-EN ISO 17475:2010 standard. Test samples prior corro-
sion test were ground on abrasive papers to 1200 ␮m/mm2
grain size. The test surface area for corrosion test was 0.2 mm2
in the centre of the welded zone. A silver chloride electrode
(Ag/AgCl of 0.197 V potential) was applied as the reference
electrode; a steel electrode (a rod) was used as the auxiliary
electrode.
Electrochemical studies of corrosion resistance were carried out
in two steps. In the first step, the open circuit potential (Eocp ) after
1 h of immersion in the test solution was determined. The second
stage involved the determination of anodic polarisation curves by
applying potential changes in the anodic and cathodic direction
at an increment of 1 mV/s. The reaction of the polarisation curves
was monitored in the range from Eocp −100 to +100 mV. The val-
ues of corrosion potential (Ecorr ), polarisation resistance (Rp ) and
corrosion current density (icorr ) were determined. The corrosion
162 Z. Brytan et al. / Applied Surface Science 388 (2016) 160–168

Table 2
Welding joints parameters of lean duplex stainless steel S82441.

Current, A Heat input, kJ/mm

TIG A-TIG

Ar Ar + 5% N2 Ar + 10% N2 Ar + 15% N2 Ar + He

50 0.11 – – – – –
100 0.27 0.26 0.26 0.26 – 0.29
150 0.45 0.42 0.44 0.43 – 0.48
200 0.65 0.65 0.65 0.65 0.72 0.68
250 0.89 – – – – –
300 1.17 – – – – –

current density was calculated by applying the Stern–Geary
equation:
ba · bk
icorr =
2.3(ba + bk )Rp
0.026
icorr =
Rp
where: ba and bk – slope coefficients of the anodic Tafel’s line, Rp –
polarisation resistance [ cm2 ].
Electrochemical impedance spectroscopy (EIS) was applied
to determine the electrical characteristics on the welded joints.
This was carried out by recording changes in the resistance and
impedance at variable frequency range from 100 kHz to 0.01 Hz by
the signal of 10 mV. Based on the results, the Bode and Nyquist
relationship, as well as the loss factor, was determined.
structure of the HAZ is practically the same with a slight prevalence
of austenite.
The austenite and ferrite content in the studied welds was mea-
sured based on metallographic observations, according to the ASTM
(1)
E562 standard by systematic manual point count, to determine the
volume of the observed phases. Phase measurement was performed
(2) on a cross section of the weld, near the weld surface (Table 3).
The influence of the heat input increase on the austenite content is
evident on the TIG welding. The presence of nitrogen in the shiel-
ding gas hardly influenced the austenite content at low heat input
and low nitrogen content (5% N2 ), but its influence is evident for
high heat input and high nitrogen content. TIG welding in Ar + He
shielding gas mixture shows the same austenite content as for TIG
welding for comparable heat input. The A-TIG weld compared to
the TIG weld shows a higher austenite content at the same heat
input.

3. Results and discussion 3.2. Potentiodynamic test

3.1. Microstructural analysis
Microstructure analysis revealed (Fig. 1) that all welded joints
showed a higher fraction of ferrite than austenite. It was notable
that with less heat input (0.27 kJ/mm), the austenite grains were
smaller, more dispersed and more evenly distributed in the weld
material, than for higher heat input welds. The microstructure of
the heat affected zone (HAZ) is practically the same with some
slight prevalence of austenite with the increase of the heat input.
The weld microstructures (Fig. 2) showed that the addition
of nitrogen of up to 15% (85% Ar + 15% N2 ) did not cause a
greater amount of austenite compared to the microstructure of the
weld metal welded with pure argon shielding gas (100% Ar). The
In order to observe the corrosion resistance of TIG welded lean
duplex stainless steel UNS S82441 with Ar shielding gas at different
heat inputs, potentiodynamic polarisation tests were conducted
in 1 M NaCl at 25 ◦ C; the electrochemical parameters are listed in
Table 4.
The open circuit potential Eocp of lean duplex stainless steel UNS
S82441 TIG welded in pure Ar shielding gas atmosphere is lower
than for non-welded parent metal (i.e. −184 mV). An increase of
heat input from 0.11 to 1.17 kJ/mm during welding in Ar shifted
the Eocp potential to positive values. The highest Eocp potential was
obtained at the highest studied heat input 0.89 and 1.17 kJ/mm,
respectively Eocp was −112 mV and −128 mV. The corrosion poten-
tial Ecorr was also shifted to positive values with heat input during

Fig. 1. Microstructure of welds and HAZ of TIG welded lean duplex stainless steel with Ar shielding gas at different heat inputs.
 Z. Brytan et al. / Applied Surface Science 388 (2016) 160–168 163

Fig. 2. Microstructure of the TIG welds and the HAZ metal made with different nitrogen additions to argon shielding gas.

Table 3
Austenite content in the weld of TIG and A-TIG welded lean duplex stainless steel S82441.

Current, A Austenite content, %/heat input, kJ/mm

Parent metal TIG A-TIG

Ar Ar + 5% N2 Ar + 10% N2 Ar + 15% N2 Ar + He

50 20–25/0.11 – – – – –
100 20–25/0.27 25–30/0.26 30–35/0.26 35–40/0.26 – 40–45/0.29
150 55/ 25–30/0.45 30–35/0.42 30–35/0.44 40–45/0.43 – 40–45/0.48
200 – 30–35/0.65 30–35/0.65 35–40/0.65 40–45/0.65 30–35/0.72 45–55/0.68
250 35–40/0.89 – – – – –
300 40–45/1.17 – – – – –

TIG welding; the overall increase of its value, with respect to non- was also tested by means of a potentiodynamic test for TIG welds
welded parent material, was about 60 mV. and compared to A-TIG welds of lean duplex stainless steel UNS
The corrosion current density icorr of TIG welds in pure Ar gener- S8244. The results of the potentiodynamic test are shown in
ally increased to 0.295–0.62 ␮A/cm2 when compared to the parent Table 5.
material where it was 0.331 ␮A/cm2 . The polarisation resistance The electrochemical parameters of welded lean duplex stainless
Rp is inversely proportional to the rate of corrosion described by steel where 5% N2 was present in shielding gas are better than for
the equivalent corrosion current density icorr and it predominantly a non-welded parent metal for low heat input (0.26 kJ/mm). The
decreased compared to a non-welded parent metal. The main con- introduction of 5% N2 to argon resulted in a decrease of corrosion
clusion from the electrochemical test is that an increase of heat current density icorr and an increase of the polarisation resistance Rp
input during TIG welding in the pure Ar atmosphere had signif- responsible for the lower corrosion rate. When the heat input was
icant effect on corrosion resistance, it was improved when high 0.65 kJ/mm, icorr was slightly higher than the non-welded parent
heat inputs of 0.65 and 0.98 kJ/mm are applied, while too low a metal.
heat input (0.11 kJ/mm) or an excessive input (1.17 kJ/mm) increase The presence of 10 and 15% N2 in the shielding gas
the corrosion current density and the corrosion rate. The higher atmosphere resulted in higher corrosion current density icorr
corrosion rate of low heat input welds can be attributed to higher (0.58–0.65 ␮A/cm2 ), compared to the parent metal (0.3 ␮A/cm2 ),
ferrite content in the duplex microstructure, while high heat input for both analysed heat inputs (0.26 and 0.65 kJ/mm), with the
welds can suffer nitrogen loss, resulting in high ferrite content and exception of the low heat input weld (0.26 kJ/mm) in the 15%
precipitations of chromium reaching nitrides in the ferrite. N2 + Ar atmosphere, where it was lower (0.25 ␮A/cm2 ). The
The influence of nitrogen addition (5, 10 and 15%) to the addition of nitrogen to shielding gas lowered the open cir-
argon shielding gas and application of the Ar + He gas mixture cuit potential Eocp of lean duplex stainless steel UNS S82441
TIG welded; this effect is more visible for a low heat input
(0.26 kJ/mm).
Table 4 The weld with Ar + He shielding gas, where the high heat input
Potentiodynamic test results of TIG welded lean duplex stainless steel UNS S82441
with Ar shielding gas at different heat inputs (kJ/mm).
of 0.72 kJ/mm was introduced during welding, does not have a pos-
itive effect on the electrochemical parameters in terms of lowering
Sample/heat input, Eocp , mV Rp , k/cm2 Ecorr , mV icorr , ␮A/cm2 corrosion current density, but a positive effect was evidenced in
kJ/mm
shifting the Eocp to positive values.
Parent metal/ – −184 85 −214 0.331 The low and high heat inputs A-TIG weld show electrochemical
0.11 −185 50 −213 0.560
parameters (Rp and icorr ) very similar to those obtained for the non-
0.27 −157 59 −186 0.474
0.45 −142 46 −170 0.620 welded parent metal, which proves a beneficial rule of activated
0.65 −173 91 −200 0.295 flux on the phase stabilisation and composition homogenisation
0.89 −112 72 −149 0.345 without affecting the deterioration of corrosion resistance of the
1.17 −128 51 −159 0.521 welded surface.
164 Z. Brytan et al. / Applied Surface Science 388 (2016) 160–168

Table 5
Potentiodynamic test results of TIG and ATIG welded lean duplex stainless steel UNS S82441 with Ar + N2 , Ar + He shielding gas at different heat inputs (kJ/mm).

Shielding gas Heat input, kJ/mm Eocp , mV Rp , k/cm2 Ecorr , mV icorr , ␮A/cm2

Parent metal – −184 85 −214 0.331

Ar + 5% N2 0.26 −28 109 −76 0.199
Ar + 5% N2 0.65 −105 82 −140 0.346
Ar + 10% N2 0.26 −101 58 −133 0.587
Ar + 10% N2 0.65 −138 53 −163 0.636
Ar + 15% N2 0.26 −81 85 −122 0.252
Ar + 15% N2 0.65 −146 54 −171 0.652
Ar + He 0.72 −137 49 −169 0.538
A-TIG 0.29 −181 85 −201 0.373
A-TIG 0.68 −164 92 −190 0.349

Table 6
Impedance parameters of TIG welded lean duplex stainless steel S82441 with Ar shielding gas at different heat inputs (kJ/mm).

Sample/heat input, kJ/mm Rs ,  cm2 CPE1 , ␮F/cm2 n1 R1 , k cm2 CPE2 , ␮F/cm2 n2 R2 , k cm2

Parent metal/ – 0.1120 40.3 0.182 20.2 31.4 0.08 45.4

0.27 0.0678 1.37 0.005 1.4 1.08 0.03 17.2
0.45 0.0593 3.79 0.010 19.8 4.17 0.07 35.7
0.89 0.0499 2.38 0.008 4.52 1.21 0.03 50.6

3.3. Electrochemical impedance spectroscopy (EIS)

The results of impedance measurements carried out in a wide

frequency range from 100 kHz to 100 MHz, providing informa-
tion related to the tested corrosion system and electrochemical
processes occurring therein. The interpretation of electrochemical
impedance measurements involves the use of electrode-equivalent
circuits (EEC). The individual elements of EECs correspond to elec-
trochemical properties of the tested corrosion system and allow
one to determine the corrosion parameters, including charge trans-
fer impedance. Modelling the impedance of more complex real
systems requires the use of the complex EECs system with con-
stant phase elements (CPE). The CPE element has a fixed phase shift
angle and its impedance describes the expression: ZCpe = 1/Y0 (jω)n ,
where Y0 and n are the parameters related to the shift phase angle.
The value of the parameter n describes the corrosion process on the
surface of the material, and the smaller the value of this parameter,
the more heterogeneous the process. The factor n is an adjustable
parameter of values from −1 to 1, where a value of −1 is character-
istic for an inductance, a value of 1 corresponds to a capacitor and
a value of 0 corresponds to a resistor [22].
The EECs used to fit the experimental data are presented in Fig. 3.
Element Rs corresponds to the electrolyte resistance i.e. 1 M NaCl
solution, while element R2 corresponds to charge transfer resis-
tance in phase interface and is inversely proportional to corrosion
rate and surface area undergoing corrosion. The constant phase ele-
ments CPE2 , CPE1 were introduced to characterise a “capacitance
dispersion” related to capacity of the material surface area of a com-
plex surface roughness, inhomogeneous reaction rates on a surface
and non-uniform current distribution. Element R1 corresponds to
electrolyte resistance present in porosity in this material zone.
Fig. 3. Equivalent electrical circuit used to fit the impedance data.
TIG welded joints of lean duplex stainless steel UNS S82441 with
Ar shielding gas were studied by means of the EIS; the resulting
parameters are given in Table 6. The EIS Bode-phase angle plots
(Fig. 4) shows high phase angles over a large frequency range, which
is typical of passive materials, probably due to the presence of a
passive layer on the stainless steel surface.
The Nyquist plots (Fig. 4a) show a significant change in the
slope of the curve of welded surfaces relative to non-welded parent
metal, which shows a slower corrosion process of welded sur-
faces. The greatest difference in the changes of the corrosion rate
and hence the slowest corrosion process was observed for samples
welded at heat input 0.89 kJ/mm. The Bode plot analysis (Fig. 4b and
c) confirms the resistive nature of the studied surfaces, as evidenced
by the phase angle value being close to 0 and the almost constant
value of log Z in the high-frequency range. Moreover, the Bode
phase angle plot (Fig. 4c) for non-welded parent metal is charac-
terised by a well-defined phase angle maximum with its peak at
approximately 100 Hz. However, for TIG welded samples the phase

Table 7
Impedance parameters of TIG and ATIG welded lean duplex stainless steel S82441 with Ar + N2 , Ar + He shielding gas at different heat inputs (kJ/mm).

Shielding gas Heat input, kJ/mm Rs ,  cm2 CPE1 , ␮F/cm2 n1 R1 , k cm2 CPE2 , ␮F/cm2 n2 R2 , k cm2

Parent metal – 0.1120 40.3 0.182 20.2 31.4 0.08 45.4

Ar + 5% N2 0.26 0.0419 0.569 0.00125 8.2 81.4 0.567 8.4
Ar + 5% N2 0.65 0.0193 0.605 0.0019 5.1 0.534 0.0264 114
Ar + 10% N2 0.26 0.0411 1.91 0.00291 7.1 14 0.117 17.8
Ar + 10% N2 0.65 0.0440 0.771 0.0035 0.4 0.668 0.00835 82.1
Ar + 15% N2 0.26 0.0421 1.42 0.00365 2.1 1.03 0.028 22.4
Ar + 15% N2 0.65 0.0327 1.29 0.00297 1.2 1.99 0.0291 17.6
Ar + He 0.72 0.0400 0.69 0.0030 0.5 0.575 0.009 71.9
A-TIG 0.29 0.0646 725 0.438 760 577 0.299 815
A-TIG 0.68 0.0235 1.18 0.00306 6.51 2.68 0.0569 688
 Z. Brytan et al. / Applied Surface Science 388 (2016) 160–168
Fig. 4. EIS of lean duplex stainless steel S82441 – the parent metal and TIG welds
at Ar shielding gas at different heat inputs (kJ/mm), (a) Nyquist plot, (b) Z modulus
and (c) Bode phase-angle plot.
angle located in the 0.3–2.0 Hz range presents a slight upward cur-
vature and the second peak starts to be visible.
The EIS results obtained for non-welded UNS S82441 parent
metal (PM) compared to the welded metal at various heat inputs
(0.27–0.89 kJ/mm) shows an increase in phase angles at low fre-
quencies, indicating that the passive layer becomes increasingly
more protective, less porous and having a decreasing amount of
surface defects. Analysing EECs circuit element values of both n1
and n2 elements and in both cases of CPE1 and CPE2 shows that,
165
in the test system, they behave like a resistance element. The
resistance of the oxide layer on welded metal increased with weld-
ing heat input from 17.2 k cm2 to 50.6 k·cm2 , while the parent
metal resistance was 45.4 k cm2 . When summarising the R1 resis-
tance of an electrolyte present in porosity on steel surface and
the R2 resistance of charge transfer at the interface, the overall
resistance of parent metal in non-welded conditions is still higher
(65.6 k cm) than in welded conditions (18.6–55.5 k cm2 ). The
clear improvement of oxide layer resistance with the increase of
heat input from 0.27 to 0.89 kJ/mm must be associated with the
higher volume fraction of austenite. High heat input during weld-
ing influences the slower cooling after welding, so a greater amount
of austenite can precipitate in volume. The austenite content in
the welded zone increased from 20–25% at heat input 0.27 kJ/mm
to 35–40% at heat input 0.89 kJ/mm (Fig. 1 and Table 3). Higher
austenite content positively stabilised the passivation process of
ferritic-austenitic welded microstructure and formed on the sur-
face oxide layer that became more homogenous and resistant.
The influence of nitrogen addition (5, 10 and 15%) to the
argon shielding gas and Ar + He gas composition was studied
for variable heat input during welding of lean duplex stainless
steel UNS S82441. The EIS parameters are given in Table 7. The
impedance parameters of lean duplex stainless steel welded in the
argon–nitrogen shielding gas show a variable influence on the sur-
face oxide layer resistance with the increase of welding heat input
and the addition of the nitrogen to the shielding gas. When welding
with higher heat input of 0.65 kJ/mm, the surface oxide layer shows
lower resistance R1 than for a heat input of 0.26 kJ/mm associated
with the electrolyte resistance present in surface porosity, demon-
strating fewer surface defects and a more homogenous formation.
The dissolution of nitrogen in the weld results in an increased
austenite content that forms during cooling from a welding tem-
perature with the increase of welding heat input and the addition
of the nitrogen to the shielding gas (Table 3).
The impedance spectra of TIG welded lean duplex stainless
steel S82441 with heat input of 0.65 kJ/mm at different argon-
nitrogen shielding gas composition (5, 10 and 15% N2 ) is presented
in Fig. 5. When the increased addition of nitrogen is present in
the argon shielding atmosphere during welding, on the Nyquist
plot a clear change in the slope of the curve can be observed. The
most favourable change in the corrosion rate was observed for 15%
N2 addition. The Bode-phase angle plots also confirm the resistive
nature of the test samples, as evidenced by the phase angle value
of close to 0 and the almost constant value of log Z in the high-
frequency range. The Bode phase angle plot (Fig. 5c) for 15% N2
addition to argon shielding gas during welding shows the shift of
the phase angle maximum peak present at approximately 100 Hz
to higher frequency values, while at low frequencies the plot tends
to stabilise between  angle 50–60◦ .
The presence of 5% N2 in the argon-nitrogen shielding gas
increase the oxide layer resistance when high heat input was
applied to 114 k cm2 , which is double the resistance of the parent
metal in non-welded conditions (Table 7). Similarly, the addi-
tion of 10% N2 raises the surface oxide layer’s resistance to about
80 k cm2 . The presence of 15% N2 in argon–nitrogen shielding
gas shows a negative impact on the surface oxide layer resistance
(17.6–22.4 k cm2 ). The excessive addition of nitrogen during TIG
welding together with a fast cooling rate from the welding tem-
perature may lead to chromium-rich nitrides (Cr2 N) precipitation
within the ferrite grains due to supersaturation during cooling. The
chromium nitrides precipitate particularly in the HAZ and weld
metal subject to rapid cooling or nitrogen loss, resulting in high
ferrite content. The presence of chromium-rich nitrides has been
widely reported to decrease the pitting corrosion resistance of
welded duplex stainless steels [23,24]. Precipitations of nitrides
lead to local chromium and nitrogen depletion zones, which may
166 Z. Brytan et al. / Applied Surface Science 388 (2016) 160–168
Fig. 5. EIS of lean duplex stainless steel S82441 TIG welded with heat input of
0.65 kJ/mm at Ar + N2 shielding gas (5, 10 and 15% N2 ), (a) Nyquist plot, (b) Z modulus
and (c) Bode phase-angle plot.
meaningfully lower corrosion resistance in the surrounding ferrite
matrix, thus becoming preferential pitting sites.
Fig. 6 shows the impedance spectra of lean duplex stainless
steel S82441 weld by the TIG method at Ar + He shielding gas and
A-TIG welded at different heat inputs (kJ/mm). The TIG welding
with a shielding gas composition of Ar + He and a high heat input
of 0.72 kJ/mm improved the resistance of the surface oxide layer
(Table 7, R2 = 71.9 k cm2 ). The EIS plots of A-TIG welds show com-
parisons to the parent metal characteristic, while the TIG welds in
Fig. 6. EIS of lean duplex stainless steel S82441, TIG welded at Ar + He shielding gas
and A-TIG welded at different heat inputs (kJ/mm), (a) Nyquist plot, (b) Z modulus
and (c) Bode phase-angle plot.
an Ar + He shielding gas atmosphere are similar to those obtained
at Ar + 15% N2 shielding gas. The Bode phase angle plot (Fig. 6c) for
Ar + He shielding gas composition during welding shows a similar
shift of the phase angle maximum peak at approximately 100 Hz to
higher frequency values and the angle stabilisation in the low fre-
quency range. The helium addition to argon shielding gas produces
a hotter arc and conducts more heat to the base metal to increase
 Z. Brytan et al. / Applied Surface Science 388 (2016) 160–168
weld penetration and improve the weld puddle fluidity. The result
of helium addition is a higher amount of introduced heat and
resulting slower cooling after welding. Improved fusion and slower
freezing times allowing any trapped gas more time to escape may
be responsible for the lower level of porosity and fewer surface
defects.
The resistance of the oxide layer on the A-TIG welded surface
was one order of magnitude higher (688–815 k cm2 ) than for
the surface of parent metal in non-welded conditions (Table 7).
Activated TIG welding shows a beneficial thermal cycle for duplex
stainless steel, which introduces more heat than the conventional
TIG welding, and thus a slower cooling and formation of a higher
amount of austenite.
During the welding of lean duplex stainless steel, as reported in
the literature [25]. A-TIG welds show a lower ferrite content than
the TIG welds. These phenomena are explained by the nitrogen loss
reduction taking place in A-TIG welding and consequently with a
higher amount of nitrogen, the stronger is the austenite formed.
Increased austenite content in A-TIG welded significantly increases
the passivity of the formed oxide layer, which may be related to the
protective effect of the activating flux from external atmosphere.
The activating fluxes based on oxides like SiO2 , TiO2 , Cr2 O3 , ZrO2 ,
Al2 O3 etc. enhance the penetration depth due to the amount of
molecular oxygen evolved in the boiling of oxides. For A-TIG weld-
ing of stainless steels Cr2 O3 , TiO2 , and SiO2 oxides provide the
best penetration depth [26]. Sandor et al. reported that for various
single-phase austenitic and duplex stainless steel grades, the A-TIG
welds show a higher critical pitting temperature (CPT) than the TIG
welds, but still lower than the parent metal [27]. A-TIG welding of
lean duplex stainless steel has not been greatly discussed in the lit-
erature, but having in mind the characteristic of this process, the
main materials’ behaviour can be transferred to such alloys and
grade UNS S82441.
4. Conclusions
The results of the potentiodynamic test and electrochemical
impedance spectroscopy of TIG and A-TiG welded joints of lean
duplex stainless steel UNS S82441 can be summarised as follows:
- The open circuit potential Eocp of TIG welds in pure Ar shielding
gas atmosphere is lower than for the non-welded parent metal.
An increase of heat input from 0.11 to 1.17 kJ/mm during weld-
ing in Ar shifts the Eocp potential to positive values. The corrosion
current density icorr of TIG welds in pure Ar generally was higher
compared to the parent material. The increase of heat input dur-
ing TIG welding in the pure Ar atmosphere has no linear positive
effect on the corrosion resistance, but it was improved when high
heat inputs of 0.65 and 0.98 kJ/mm were applied, while low heat
inputs (0.11 kJ/mm) and excessive inputs (1.17 kJ/mm) increase
corrosion current density and the corrosion rate. The main con-
clusion deriving from the electrochemical test and EIS spectra
for TIG welds in Ar shielding gas is that there is good agree-
ment between these two techniques. The higher corrosion rate
of TIG welds in Ar atmosphere when low heat input is applied
can be attributed to higher ferrite content in duplex microstruc-
ture, while high heat input welds can suffer nitrogen loss resulting
in high ferrite content and precipitations of chromium reaching
nitrides in the ferrite. The EIS results evidence a clear improve-
ment of oxide layer resistance to increase of heat input from 0.27
to 0.89 kJ/mm, which must be associated with the higher volume
fraction of austenite. High heat input during welding influences
the slower cooling after welding, so a greater amount of austen-
ite can precipitate in volume. Higher austenite content positively
stabilises the passivation process of ferritic–austenitic welded
167
microstructure and the layer formed on the surface oxide, which
became more homogenous and resistant.
- The nitrogen present in the argon atmosphere lowers corrosion
rate at a content of 5%, but the presence of 10 and 15% N2 in the
shielding gas atmosphere resulted in a higher corrosion current
density icorr compared to the parent metal, for both analysed heat
inputs (0.26 and 0.65 kJ/mm) with the exception of the low heat
input weld (0.26 kJ/mm) at 15% N2 + Ar atmosphere, where it was
lower. The EIS analysis revealed that the addition of 10% N2 in an
Ar atmosphere at a high heat input (0.65 kJ/mm) also improved
oxide layer resistance, but this was not confirmed by lower corro-
sion current density icorr in the electrochemical test. The excessive
addition of nitrogen during TIG welding together with a fast
cooling rate from welding temperature may lead to chromium-
rich nitride (Cr2 N) precipitation within the ferrite grains due to
supersaturation during cooling. The chromium nitrides precip-
itate particularly in the HAZ and weld metal subject to rapid
cooling or nitrogen loss, resulting in a high ferrite content. Gener-
ally speaking, to obtain an improvement of corrosion resistance
of TIG welds at N2 + Ar atmosphere, a proper balance between
nitrogen addition and heat input must be retained.
- The weld with Ar + He shielding gas, where the high heat input of
0.72 kJ/mm was introduced during welding, did not have a posi-
tive effect on the electrochemical parameters in terms of lowering
corrosion current density, but a positive effect was evidenced in
the EIS analyses where the oxide layer resistance was roughly
doubled with respect to non-welded parent metal. The disagree-
ments of test results between both applied methods – (i.e. the
potentiodynamic test and EIS) must be clarified in further studies.
- The A-TIG welds showed improved corrosion resistance, compa-
rable to the non-welded parent metal due to lower ferrite content
compared to the TIG welds, resulting from a much slower cooling
rate after welding, when the diffusion process of austenite for-
mation and homogenisation of chemical composition take place.
A good agreement between the potentiodynamic test and ESI
analysis was obtained.
- Both electrochemical techniques applied to evaluate the corro-
sion properties of the welded joint evidenced a strong influence
of welding parameters – heat input and applied shielding gas
composition on the corrosion resistance. It must be remembered
that during the potentiodynamic test, the sample surface was
altered, while the EIS introduced smaller perturbations to the
tested system. These perturbations can influence the steady-state
conditions of the system and EIS with respect to the potentiody-
namic test having a reduced magnitude or severity of introduced
perturbations; thus, smaller deviations from the natural steady-
state conditions may be introduced.
Acknowledgements
The authors gratefully acknowledge the financial support from
the Polish National Science Centre: DEC-2011/01/B/ST8/06648.
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