NACE Paper No.

MECCOCT18-12582

INVESTIGATION OF THE ELECTROCHEMICAL PROPERTIES OF AN ECONOMICAL

LEAN DUPLEX STAINLESS STEEL ALLOY

Farid M. Abdallah
Dept. of Mechanical Engineering, King Fahd University of Petroleum & Minerals (KFUPM)
Dhahran 31261, Kingdom of Saudi Arabia
Ihsan-ul-Haq Toor1
Dept. of Mechanical Engineering & Center of Research Excellence in Nanotechnology, King
Fahd University of Petroleum & Minerals (KFUPM)
Dhahran 31261, Kingdom of Saudi Arabia

ABSTRACT
The electrochemical properties of sintered lean duplex stainless steel alloys prepared by
mechanical alloying were investigated in chloride solution. Potentiodynamic polarization
(PDP), Electrochemical Impedance spectrometry (EIS) and Linear polarization resistance
(LPR) techniques were used to investigate the corrosion properties of these alloys in
chloride solution at room temperature. The mechanically alloyed specimens were sintered
at three different temperatures for optimization and subsequently densification and
microhardness were measured. XRD was used to analyze to confirm the presence of
optimized phases of ferrite and austenite in the developed alloys. Further investigation
for intermetallic phases in these alloys were conducted and it was found that no
secondary phases were present in the designed alloys. The corrosion performance
measured in chloride solution showed that alloy 4 exhibited the best corrosion resistance
when measured in terms of pitting potential and passive current density.

Keywords: Lean Duplex stainless steel; PDP; EIS; LPR; XRD; microhardness;
secondary phases;

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 INTRODUCTION
Lean duplex stainless steels are mainly classified in stainless steel (Fe-Cr alloys)
category and consist of distinguished properties such as the ability to resist corrosion.
Thanks to their ability to form a thin chromium rich passive layer which act as protective
layer against corrosion attacks. On the other hand, duplex stainless steel consists of dual
phase microstructure of ferritic and austenitic stainless steel. Hence, they acquire both
characteristics of strength and toughness from ferritic and austenitic structure
respectively. Their unique characteristics put them as major contenders over their
counterpart ferritic and austenitic SS for different industrial applications such as
pharmaceuticals, aeronautics, chemical, food manufacturer, oil and gas, petrochemical
and automotive industries.[1–4] They also comprises of the major features of stainless steel
behavior such as high toughness, high strength, high corrosion resistance properties, low
thermal expansion and good weldability that made them a good choice for numerous
applications areas as well as in condition where temperature is elevated . [5,6]
Recently, several works have been done to develop and investigate on the properties PM
duplex stainless steels (DSS) group through different combination of alloy elements and
processing route to acquire better mechanical and corrosion properties. Garcia et al. [7,8]
investigated on the corrosion behavior of DSS alloys sintered in nitrogen. He used pre-
alloyed ferritic (AISI 430L) and austenitic (AISI 316L) SSs powder as a raw material and
sintering atmosphere as N2-H2 (95% and 5%). Observation shows that the increase in
austenite/ferritic phase ratio had a positive impact on the corrosion properties where
corrosion potential shifted to more noble and decrease in passive current density.
Dobrzanski et. al [9,10] studies the corrosion properties of vacuum sintered DSS alloys by
mixing austenitic (AISI 316L) and martensitic (AISI410) pre-alloyed powder and
controlling the amount of alloying elements such as Cr, Ni, Mo, and Cu to obtain a
biphasic structure of DSS alloy. He consolidated the powder sample at 800MPa and
sintering temperature of 1260oC. The results showed an alloy with better pitting corrosion
resistance had a balance of austenite/ferrite phase. However, the microstructure of DSS
alloy influenced the corrosion propertied due pore morphology and density properties.
Ihsan-ul-Haq Toor [11] studied the effect of Sintering Holding Time on the Corrosion
Properties of Nano-Structured Fe-18Cr-2Si Alloy Prepared by spark plasma sintering
technique. The Sintering temperature was selected as 1100oC at applied pressure of
50Mpa and holding time were varied as 5min, 10min and 15min. He found that resistance
to corrosion measured in terms of corrosion potential (Ecorr), pitting potential (Epit) and
passive current density (ip) was increased with an increase in holding time.
Ahmed et.al [12] examined the effect of sintering temperature on the corrosion properties
of nanostructured Fe‐18Cr‐2Si alloy prepared by SPS technique. Spark plasma sintering
was performed at three different temperatures 900, 1000, and 1100 oC with a holding time
of 10 min and an applied pressure was adjusted at 50 MPa. The corrosion properties of
the alloys were found to be related with densification of material which was influenced by
sintering temperature. The higher densification was achieved at 1100oC, hence, the
pitting potential, corrosion potential and passive current density were also higher.

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The purpose of this study is to evaluate and investigate the corrosion of performance of
the newly designed DSS alloys by electrochemical techniques such as PDP, EIS, ENA in
chloride and acidic environments and the results were bench marked against standard
AISI 304 stainless steel.

EXPERIMENTAL PROCEDURES
DSS alloys named alloy D1 and D3 were designed with variation in their compositions as
shown in the Table 1. The composition of these alloys was designed by help of Schaeffer
diagram to get a duplex structure composed of nearly 45-55% ferrite and austenite
phases. [13,14]
Spark plasma sintering technique was carried out for consolidation of ball milled powder
of designed Duplex stainless steel alloys. The sintering process was conducted in a fully
automated SPS machine (Type HP D-5, FCT Systeme, Rauenstein, Germany). The
applied current of the SPS machine was passed through a 20mm graphite die which was
used in holding the milled powders.
Ball milled powder of DSS alloys (D1 & D3) were sintered by Spark plasma sintering
techniques (SPS). The sintering parameters were 1000oC sintering temperature, heating
rate 100oC/min, holding time 10 minutes, the pressure of 50MPa and cooling rate of
200oC/min.
The microstructures of the designed alloys were analyzed by optical microscope and SEM
images captured from SEM model: JEOL JSM-6064LV-80MM equipment at 20kV.
Density measurement was calculated by Archimedes principle through weight
measurements with the help of density measurement kit provided by Mettler Toledo. The
weight of the sample in air and in water was calculated six times to ensure the
reproducibility of the data.
The specimens were spot welded; mounted, grinded up to 600 grit emery paper, polished
by fine alumina particles of 50 microns for electrochemical analysis. A three-electrode cell
(a specimen as a working electrode, a graphite counter electrode and a saturated calomel
reference electrode) was used for the tests. The specimens were cathodically cleaned for
5 min at - 0.8 VSCE to remove the primary oxide film. All the electrode potentials values in
the text are referred to the SCE scale.
Potentiodynamic polarization tests were performed per ASTM G 5 standard at a scan rate
of 0.5 mV/s and impedance investigations were performed using a GAMRY reference
3000 potentiostat at ambient temperature (25oC).
Electrochemical impedance analysis was firstly performed at initial delay of 120 seconds.
Passive films were then formed potentiostatically on designed DSS alloys at DC
potentials selected based on the passive region of anodic curve. Each electrochemical

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measurement was repeated at least three times. An excitation voltage of 10 mV (peak-
to-peak), 10 point / decades and an applied frequency ranging from 10 kHz to 0.01 Hz
have been used.
The specimens with exposed surface area of 0.2 cm 2 were used for polarization tests.
The solution used were 0.2M NaCl solution which were de-aerated for 2hours before the
experiment started and then continuous de-aeration was performed throughout the
experiment.

Table 1
Chemical composition in wt. % of designed DSS alloys
Designed Fe(balance)-Cr18 -Mnx-Mo1-Si1-N0.22-Cuy-Niz (x = 6, 3, y=0, z= 0,3 )
Alloys
Fe Cr Mn Mo Si N Cu Ni

Alloy D1 Bal. 18 6 1 1 0.22 0 0

Alloy D3 Bal. 18 3 1 1 0.22 0 3

RESULTS AND DISCUSSION

Density calculations for sintered sample

The calculated percentage densities of sintered alloys in the Figure 1, shows that the
percentage density for all alloys were almost similar except some insignificant fluctuations
were observed. The maximum percentage density achieved was approximately 96.73%
for alloy D3. The density variations do not show any dependable factor.

Microstructure analysis of Sintered sample

Optical microscope and FE-SEM was used to investigate the microstructure of sintered
DSS alloys specimen at 1000oC. The Optical micrographs in Figure 2 shows the presence
of ferrite (dark) and austenite (bright) phases which indicated the duplex microstructure
of the sintered alloys.

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 Density of DSS alloys sintered at 1000oC

% Density 96.72% 96.73%

D1 D3

Figure 1: Percentage density of DSS alloys sintered at 1000oC.

Ferrite phase ( Dark ) Austenite phase ( Bright )

Figure 2: Optical microscope images of sintered DSS alloys at 1000 oC.

Electrochemical investigations of sintered DSS alloys

Different electrochemical measurement techniques such as potentiodynamic polarization
PDP and electrochemical impedance spectrometry EIS were carried out to determine
corrosion performance of sintered specimen in 0.2M NaCl solution.

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Potentiodynamic polarization, PDP of Sintered alloys
The Figure 3 represents potentiodynamic polarization curves of sintered specimens D1
and D3 in de-aerated 0.2M NaCl solution. The general passive behavior of sintered alloys
was observed for all alloys. The results of potentiodynamic polarization in Figure 3 and
Table 3 show that alloy D1 have shown higher corrosion potential (Ecorr) values than
specimen D3(-803mV). D1 showed higher passive current density (icorr) value i.e less
corrosion resistance properties. The pitting potential (Epit) values were observed to
increase in the trend of D1 < D3. The maximum value of E pit was observed in alloy D3
which consist higher amount of Ni (noble element).
The phenomenon in the Figure 3 can be explained by the influence of alloying elements
on the corrosion properties of sintered alloys. The higher Epit value was recorded for D3
with Ni-content and then followed D1- with no Ni-content. Azuma et.al [21] reported that Ni
increase increases corrosion resistance thus Epit increases. The lower Epit was reported
for D1 which has a higher amount of Mn (active element) than D3. Mn has a negative
impact on corrosion resistance hence the increase in Mn decrease the pitting potential.
[5,22–24] The passive current density i
pass of alloy D3 was less hence good corrosion
resistance properties due to Ni content. Nickel increase had a positive impact on the
pitting potential [21,25], hence the Epit was highest for D3(3%Ni). The decrease in Mn
amount in alloy D3 has also increased the Epit values. It is believed that Mn enhances
formation of Mn sulfide and oxide which initiates pitting formation hence decrease pitting
potential [5,7,22–24,26]. This reason can also be attributed to the lower pitting potential of D1
alloys which consist of 6% Mn in its composition.

Electrochemical Impedance Spectrometry, EIS of sintered alloys

In the Figure.4, the electrochemical impedance spectrometry analysis was carried out in
0.2M NaCl solution under open circuit potential at room temperature. The Nyquist
impedance spectra during EIS analysis in Figure.4 shows the semicircle spectra of the
sintered specimens. The larger the semicircle spectra the higher is the polarization
resistance i.e better corrosion resistance property of the alloy. The impedance values are
recorded higher for alloy D3 and the lowest for alloy D1 as shown in Table 3 calculated
from one-time constant phase element (CPE) equivalent circuit.
The higher polarization resistance of alloy D3 is due to higher amount of Ni [21,25] which
makes its passive film more stable than D1. Alloy D1 has a small spectra due to higher
Mn (6%) content which decreases the stability of passive film from inclusions such as
MnS and MnO. [5,7,24] Toor et.al [23] reported on the effect of Mn on passivation of stainless
steel to be caused by nanosize MnO precipitates formed on the passive film. These
precipitates act as pitting initiation site which later propagates and reduces the resistance
of the passive film.

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 0.00
Alloy D1 Alloy D3
0.2M NaCl solution, deareated 2hr , scan rate= 0.5mV/s, 25oC
-0.20

-0.40 Epit
E(VSCE)

-0.60
Ecorr
-0.80
ipass

-1.00

icrit
-1.20
1.00E-11 1.00E-09 1.00E-07 1.00E-05 1.00E-03 1.00E-01
Current Density (A/cm2)

Figure 3: Potentiodynamic polarization (PDP) curve of sintered DSS alloys in 0.2M

NaCl

Table 2
Corrosion measurements values of DSS after PDP in 0.2M NaCl
Specimen Ecorr (mV) icorr (A/cm2) ipass (A/cm2) Epit (mV)
at -525 mV

Alloy D1 -762 2.48 E-10 1.82 E-6 -505

Alloy D3 -803 9.08 E-10 1.07 E-6 -467

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 1.20E+05
Alloy D1 Alloy D3
0.2M NaCl solution, deareated 2hr, 25oC
1.00E+05

8.00E+04
Zimag (ohm)

6.00E+04

4.00E+04

2.00E+04

0.00E+00
0.00E+00 4.00E+04 8.00E+04 1.20E+05
Zreal (ohm)

Figure 4: EIS spectra of sintered alloys in the 0.2M NaCl.

A CPE equivalent circuit in Figure.6 was established to simulate the measured impedance
values of sintered alloys in 0.2M NaCl solution. The Equivalent circuit composed of model
parameters such as polarization resistance Rp, solution resistance Rs, n represents a
coefficient related with the homogeneity of the system and pseudocapacitance of the
system Yo (where n=1 for an ideal capacitor) . The CPE impedance representation is
given by
ZCPE = 1/Yo(j𝜔)n

Table 4
EIS analysis data from fit of CPE equivalent circuit
Specimen Polarization Resistance Solution resistance
Rp (Ohm)
(Ohm)

Alloy D1 2.06 E5 32.81

Alloy D3 2.28 E5 36.71

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 1.20E+05
Alloy D1 Alloy D3 D1-Fit D3-Fit

1.00E+05 0.2M NaCl solution, deareated 2hr, 25oC

8.00E+04
Zimag (ohm)

6.00E+04

4.00E+04

2.00E+04

0.00E+00
0.00E+00 4.00E+04 8.00E+04 1.20E+05 1.60E+05 2.00E+05
Zreal (ohm)

Figure 5: EIS spectra with a CPE equivalent circuit fitting of sintered alloys in the
0.2M NaCl.

Figure 6: CPE equivalent circuit tested in EIS data of sintered alloys

CONCLUSION
The influence of alloying element was the main influence on the corrosion behavior of
designed DSS alloys. Nickel content had a greater impact on the corrosion properties of

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alloy D3. On the other hand the decline in corrosion properties of D1 alloy was influence
by incorporation of higher amount of Mn

ACKNOWLEDGEMENTS

The authors are grateful to acknowledge KFUPM and financial support from DSR for
accomplishment of this work.

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