Erosioncorrosion behaviour of lean duplex stainless steels

in 3.5% NaCl solution

Sunday Aribo
n
, Richard Barker, Xinming Hu, Anne Neville
Institute of Engineering Thermouids, Surfaces and Interfaces (iETSI), School of Mechanical Engineering, University of Leeds, LS2 9JT, United Kingdom
a r t i c l e i n f o
Article history:
Received 17 September 2012
Received in revised form
29 November 2012
Accepted 8 December 2012
Available online 20 December 2012
Keywords:
Erosioncorrosion
Lean duplex stainless steel
XRD
SEM
a b s t r a c t
The interaction between corrosion and erosion has often been a subject of debate among scientists and
engineers. The total material degradation when corrosion and erosion interact is often more than the
individual components acting separately. Much effort has been directed towards the study of erosion
corrosion behaviour of carbon steels, standard austenitic and duplex stainless steels, highly alloyed
austenitic and super duplex stainless steels. However, the subject of erosioncorrosion of lean duplex
stainless steels is still rarely reported. This present work studies the erosioncorrosion behaviour of
lean duplex stainless steels UNS S32304 and UNS S32101 in an aerated 3.5% NaCl environment.
The erosioncorrosion behaviour of these alloys is compared with an austenitic stainless steel, UNS
S30403 and a duplex stainless steel, UNS S32205. Sub-surface microstructure modications induced by
work-hardening as a result of the sand impingement were analysed by X-ray Diffraction (XRD) and
Scanning Electron Microscopy (SEM). Results show that lean duplex stainless steels, UNS S32101 and
UNS S32304, have higher resistance to pure erosion than UNS S30403 and UNS S32205; better erosion
corrosion resistance than UNS S30403 austenitic stainless steel; and equivalent erosioncorrosion
resistance to UNS S32205 duplex stainless steel. Also, erosion with 500 mg/l sand at 15 m/s in
de-aerated tap water was able to cause subsurface deformation, phase transformation and an increase
in hardness on the stainless steels.
& 2012 Elsevier B.V. All rights reserved.
1. Introduction
Duplex stainless steels are designed for applications in aggres-
sive oileld and marine environments where both corrosion
resistance and mechanical properties of 300 series austenitic
stainless steels would perhaps be limited [1]. However, high
production costs have always been one major limitation to
selection of these alloys. The recent surge in the prices of nickel
and molybdenum has driven the cost of production of stainless
steels higher. The lean duplex stainless steels with much lower
nickel and molybdenum contents were developed as economic
alternatives to the standard duplex and highly alloyed stainless
steels [24]. These lean duplex alloys have better mechanical
properties and comparable corrosion resistance with the standard
austenitic stainless steels UNS S30403 and UNS S31603 [59].
The lean duplex have competitive price with UNS S31603 [3] and
they become very attractive when the prices of nickel and
molybdenum are unstable [2].
Nevertheless, material degradation becomes more complex
when wear and corrosion interact. Interaction between corrosion
and erosion has been a subject of debate among scientists and
engineers for a while [1016]. The total material degradation
when the two phenomena interact is said to be more than the
individual processes acting separately. Several attempts have
been made in the past to characterise the erosioncorrosion
behaviour of passive alloys [1724]. The consensus is that erosion
affects corrosion kinetics and vice-versa. The resistance of duplex
stainless steels to erosioncorrosion has been attributed to its
ability to repair the passive oxide after it has been damaged under
the liquidsolid impingement [19,21,23,24].
It has been reported that standard duplex and super duplex
stainless steels exhibit good erosioncorrosion resistance due to
their high hardness and the ability of the austenite phase to work
harden under impingement [26]. It was therefore concluded from
the investigation conducted by Lu et al. [26], that erosion
corrosion behaviour of the duplex stainless steels can be related
to the volume fraction of the austenite phase and the ow rate of
the slurry. Meng et al. [25] studied the erosioncorrosion of super
duplex stainless steel, UNS S32760 and compared the properties
to austenitic stainless steels, UNS S31603 in marine conditions.
The super duplex stainless steel was reported to exhibit superior
erosioncorrosion properties. In another study carried out by
Bargmann et al. [22] on the erosioncorrosion of a super auste-
nitic stainless steel, UNS S31254, it was reported that the total
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Wear
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http://dx.doi.org/10.1016/j.wear.2012.12.007
n
Corresponding author. Tel.: 447879197779.
E-mail address: mnsar@leeds.ac.uk (S. Aribo).
Wear 302 (2013) 16021608
material loss is erosion-dominated. According to Bargmann et al.
[22], when the total material loss was analysed, it was found out
that corrosion only contributed about 1% of the total material loss.
Neville et al. [23] compared the erosioncorrosion resistance of a
duplex stainless, UNS S32205, an austenitic stainless steel, UNS
S31603 and a manganese steel. The authors arrived at the
conclusion that the duplex stainless steel exhibits resistance to
erosioncorrosion but that the material removal is predominately
by wear when the passive lm becomes ineffective under the
highly erosive liquidsolid impingement. In another develop-
ment, it was reported that the extent to which the passivating
lm can assist in preventing erosioncorrosion is limited though
it was agreed that it has the ability to do such [21].
Materials selection for high sand production oilelds is always
a challenge because of the material degradation attributed to
erosion and erosioncorrosion. Lean duplex stainless steels are
being considered for the carcass of exible pipes in deep water
oileld. Materials selected for such application is required to be of
high strength, high erosion and erosioncorrosion resistance.
However, despite an abundance of literature [1017,19,2130]
on the subject of erosioncorrosion behaviour of other passive
alloys, there is limited information available for the lean duplex
stainless steels, UNS S32101 and UNS S32304 which are being
considered for such application [3,4]. In this paper, the results of
an experimental study of erosioncorrosion behaviour of lean
duplex stainless steels, UNS S32101 and UNS S32304 are
reported. Comparison is also made with duplex stainless steels
UNS S32205 and austenitic stainless steel UNS S30403.
2. Materials studied and experimental procedures
Lean duplex stainless steel alloys UNS S32101 and UNS S32304,
duplex stainless steel UNS S32205 and an austenitic stainless steel
UNS S30403 with chemical compositions and microstructures
shown in Table 1 and Fig. 1 respectively were used for this
investigation. The stainless steel samples were cut from at plates
(3 mm thick) into a square shape of 20 mm20 mm. Samples for
erosion and Total Weight Loss (TWL) measurements were metallo-
graphically ground to a surface nish with a 600 grit (1200P) SiC
paper. Samples for anodic polarisation were further polished with
15 mm diamond paste, degreased with acetone and washed in
distilled water. An electrical wire was soldered to one face of each
specimen for electrochemical measurements and then embedded
into epoxy resin.
A submerged jet impingement rig with a re-circulating system
is adopted (Fig. 2). A mixture of sand and uid is passed through a
dual-nozzle arrangement having diameter of 4 mm diameter. The
jet impinges onto the samples from a 5 mm stand-off distance at
an angle of 901.
An electrochemical method was used in conjunction with
weight loss analysis to isolate the contribution due to corrosion
and erosion. Anodic polarisation tests were conducted to measure
the changes in corrosion rate under impingement condition.
The potential of the working electrode was scanned from to
100 mV more negative than the open circuit potential to
250 mV more positive than OCP at a scan rate of 0.25 mV/s.
The corrosion current density was determined from the Tafel plot
at the intersection between the extrapolated anodic and cathodic
branches of the potential scan [31]. The corrosion current deter-
mined was used to calculate the corrosion rate using Faradays
Law. In order to isolate the pure erosion component of the
damage, the change in weight was measured in a nitrogen purged
impinging jet. Water was sparged for 12 h with nitrogen gas (N
2
)
to de-aerate the environment. Nitrogen gas was also bubbled into
the tap water throughout the duration of the experiment. A 3.5%
NaCl in aerated condition was used to study the erosion
corrosion and total weight loss. 500 mg/l silica sand with shape
and size distribution shown in Fig. 3(a,b) operating at 15 m/s and
a temperature of 50 1C was employed for impingement. Pure
Table 1
Properties of alloys used for the research.
Grade Type C Cr Ni Mo Cu Mn N Fe Tensile strength
(N/mm
2
)
0.2% Yield strength
(N/mm
2
)
Microhardness (HV)
500 g
304L/UNS S30403 Austenitic 0.020 18.20 8.15 0.39 0.33 1.61 0.07 Balance 635 240 17075
UNS S32101 Lean duplex 0.019 21.26 1.60 0.24 0.26 4.81 0.23 Balance 784 480 26075
UNS S32304 Lean duplex 0.020 23.36 4.80 0.30 0.25 1.32 0.12 Balance 745 450 25775
UNS S32205 Duplex 0.017 22.43 5.73 3.15 0.24 1.4 0.18 Balance 841 510 27875
Fig. 1. Microstructure of the stainless steels showing the austenitic phase of UNS S30403 and the duplex (austenite and ferrite) microstructure of UNS S32101 both etched
in glyceregia (15 cc HCl, 10 cc glycerol, 5 cc HNO
3
).
S. Aribo et al. / Wear 302 (2013) 16021608 1603
erosion was determined at 50 1C as well as at 20 1C. Some alloys
were also tested for weight loss under erosion and erosion
corrosion conditions after they have been pre-eroded at 20 1C
for 4 h. The total weight loss tests were performed for 4 h and
each test was performed at least three times. The specimens were
weighed before and after the experiments to determine the
weight loss.
3. Results and discussion
3.1. Weight loss measurement
Material degradation in the form of mass loss for all the alloys
tested is shown in Fig. 4. Pure erosion loss (E
o
) and the total weight
loss are presented. Pure erosion after sand impingement at 20 1C
shows that UNS S30403 has the highest material loss of (4.95 mg)
and UNS S32304 the least material loss of (3.01 mg). UNS S32101
and UNS S32205 have material losses of 3.78 mg and 4.33 mg
respectively. Erosion at 50 1C shows higher material loss for all the
alloys. Total weight loss of the alloys under erosioncorrosion
conditions at 50 1C shows that UNS S32205, UNS S32101 and UNS
S32304 have comparable material loss 6.78 mg, 6.80 mg and
6.95 mg respectively. UNS S30403 with 8.20 mg has the highest
material loss. The higher material loss of UNS S30403 under pure
erosion is most likely due to the lower hardness and lower yield
strength of the alloy. Despite its better response to strain-
hardening in the form of an increased hardness after erosion, the
erosion resistance could not match those of the duplex stainless
steels. The response to erosioncorrosion comparison between the
austenitic UNS S30403 and duplex alloys still follows the same
argument since the total weight loss under the corrosive 3.5% NaCl
solution is dominated by erosion. Therefore, higher hardness and
higher yield strength of the duplex stainless steels seem to be one
reason the alloys are having better resistance to erosion and
erosioncorrosion.
3.2. Anodic polarisation
Anodic polarisation shows that all the alloys are passive over a
very narrow range of potential when exposed to the impinging
jet. This is in contrast to their passive behaviour which has been
shown by many authors in static conditions. Active dissolution
due to the mechanical removal of the passive lm led to a steady
current increase for all the alloys tested. Tafel plots derived from
anodic polarisation were used to determine the corrosion current
density (i
corr
) as shown in Fig. 5.
3.3. Component of erosion-enhanced corrosion and corrosion-
enhanced erosion
The erosionenhanced corrosion component (dC
E
) was deter-
mined from the anodic polarisation measurement by calculating
the corrosion rate of the alloys under impinging 3.5%
NaCl 500 ppm sand at 15 m/s. The corrosion current density
was determined from the Tafel plots derived from the anodic
polarisation plots as shown in Fig. 5. This was used to calculate
Fig. 2. Recirculating jet impingement rig (a) pure erosion (b) erosion-enhanced corrosion.
0
2
4
6
8
10
12
14
16
18
0 200 400 600 800 1000
V
o
l
u
m
e

(
%
)
Particle size (m)
Fig. 3. (a) Silica sand particle shape and (b) size distribution.
Fig. 4. Weight loss measurements from the submerged impingement jet tests at
201C and 501C in N
2
sparged solution , 500 mg/l sand and erosioncorrosion in
aerated 3.5% NaCl solution, 500 mg/l sand both at 15 m/s.
S. Aribo et al. / Wear 302 (2013) 16021608 1604
the erosion-enhanced corrosion rate, where
Mass loss g dC
E

i
corr
W A T
nF
1
where i
corr
is the corrosion current density in A/cm
2
,W is the
atomic weight in g/mol, A is the surface area of the specimen in
cm
2
, T is time in seconds, n is the number of electrons involved in
the dissolution process, F is Faradays constant, 96,485 C/mol.
It has been reported [10,13] that the static corrosion compo-
nent (C
o
) is negligible for passive alloy. It is therefore assumed
that the total material degradation due to corrosion in this study
is approximately equal to the erosion-enhanced corrosion com-
ponent (dC
E
). Therefore the formula for total weight loss (TWL)
can be written as
TWL E
o
dE
C
dC
E
2
instead of
TWL E
o
C
o
dE
C
dC
E
3
where TWL is the total weight loss, E
o
pure erosion component,
C
o
static corrosion component (in this case negligible),
dE
C
corrosion-assisted erosion (synergy), and dC
E
erosion-
assisted corrosion (additive).
Fig. 6 depicts the trend of erosion-enhanced corrosion and
corrosion-enhanced erosion. Corrosion-enhanced erosion is gen-
erally higher than erosion-enhanced corrosion as expected. All
the duplex stainless steels exhibit an equivalent material degra-
dation due to erosion-enhanced corrosion (Fig. 6). UNS S30403
seems to have the highest susceptibility to material degradation
by erosion-enhanced corrosion. The higher material loss due to
corrosion-enhanced erosion (dE
C
) is clearly due to the fact that
erosion is the dominating factor and it is highly dependent on
mechanical properties of the alloys. On the other hand, erosion-
enhanced corrosion is dependent on the passive behaviour of the
alloys as well as the phase transformation induced by the
impacting slurry on the near surface of the alloys. After the
materials have been deformed by the impacting slurry, there will
be phase transformation from austenite to martensite as being
conrmed by XRD in Figs. 9 and 10. Because martensite phase is
less corrosion resistant than the austenite phase, there could be
an increase in the corrosion rate. This could be one reason why
the austenitic stainless steel is having a fairly high material loss
under erosion-enhanced corrosion compared to the lean duplex
stainless steels. One other reason could be that because the
austenite phase is softer than the duplex phase. There is a
likelihood of higher sand embedment [3234] within the near
surface of the austenite phase which could turn this area into a
composite (metalsand-oxide) of inferior corrosion resistance
compared to the duplex phase.
3.4. Properties of eroded surfaces
3.4.1. Erosion and total weight loss of an eroded surface
All the alloys show a decrease in weight loss after they have
been pre-eroded at 20 1C for 4 h in a nitrogen sparged slurry
(Fig. 7a and b). The weight loss is lower for both erosion and
erosioncorrosion at 50 1C as compared with alloys that were not
pre-eroded. The decrease in weight loss is most probably due to
work-hardening that led to an increase in hardness (Fig. 8).
Enough kinetic energy has been transferred from the erodent to
the surface of the alloys causing subsurface deformation in the
eroded surface. Induced stress as result of this deformation led to
phase change (Figs. 9 and 10) and grain renement (Fig. 11)
within the subsurface of all the alloys tested. Since an increase in
hardness is one parameter that enhances a materials resistance
0
0.5
1
1.5
2
2.5
3
3.5
S30403 S32304 S32101 S32205
M
a
t
e
r
i
a
l

l
o
s
s

(
m
g
)
Alloys
Erosion-enhanced corrosion Corrosion-enhanced erosion
Fig. 6. Erosioncorrosion synergy.
-500
-450
-400
-350
-300
-250
-200
-150
-100
-50
0
0.1 1 10 100
P
o
t
e
n
t
i
a
l

(
m
V

v
s

A
g
/
A
g
C
l
)
Log i (A/cm
2
)
UNS S30403
UNS S32304
Fig. 5. Tafel plot for current density determination.
0
1
2
3
4
5
6
7
S30403 S32304 S32101 S32205
W
e
i
g
h
t

l
o
s
s

b
y

e
r
o
s
i
o
n

(
m
g
)
Erosion ( polished surface)
Erosion (pre-eroded surface)
0
1
2
3
4
5
6
7
8
9
10
S30403 S32304 S32101 S32205
T
W
L

(
m
g
)
TWL (polished surface)
TWL (pre-eroded surface)
Fig. 7. Effect of pre-erosion on (a) erosion and (b) TWL under erosioncorrosion conditions.
S. Aribo et al. / Wear 302 (2013) 16021608 1605
to pure erosion, a general reduction in weight loss can be seen to
have occurred for the alloys.
The same trend is also noticed on all the alloys after erosion
corrosion in 3.5% NaCl. As can be seen in Fig. 7b, there is a general
reduction in the total weight loss of all the alloys under erosion
corrosion for the pre-eroded surface as compared to the polished
surface. Mohammed and Luo [13] also reported a decrease in
erosioncorrosion rate with an increase in cold work on a UNS
S30403 austenitic stainless steel. This could be due to the fact that
erosion is still the dominating factor as compared to corrosion.
Invariably, effects of the increase in hardness as a result of work-
hardening caused by erosion is having a superior impact on the
material degradation by erosion as compared to the higher
corrosion susceptibility that will be expected from the transfor-
mation of austenite to martensite (Figs. 9 and 10) in the austenitic
and duplex stainless steels.
3.4.2. Hardness prole of the eroded surface
Fig. 8 shows the micro-hardness prole of the cross-section of
the alloys after erosion at 20 1C in nitrogen purged slurry for 4 h.
There is a general increase in hardness within the centre of the
specimen. Bargmann et al. [22] reported such hardness prole for
slurry containing 500 ppm sand at velocity of 16.8 m/s. The increase
in hardness is very pronounced in the austenitic stainless steel
compared to the duplex alloys. This is thought to be as a result of
the better response of the austenitic phase (high volume fraction of
austenite) in UNS S30403 to strain-hardening [27].
3.4.3. X-ray diffraction (XRD) pattern of the eroded surface
The XRD spectra for the as-polished and eroded UNS S30403
and UNS S32101 are shown in Figs. 9 and 10. Erosion by 500 mg/l
sand at 15 m/s has been able to induce enough stress to transform
some of the austenite volume fraction to an a-martensite. As can
be seen in Fig. 9a and b, all the austenite peaks (A) in the polished
samples of UNS S30403 have been drastically reduced and the few
martensite and ferrite peaks (MF) in Fig. 9a have increased after
the work-hardening (Fig. 9b). It is assumed that some martensite
peaks in Fig. 9a could be as a result of induced strain during
mechanical grinding and polishing. The ferrite phase in the
polished sample is most likely due to the fact the austenitic
stainless steel would not have 100% austenite phase as produced.
Martensitic phase (body-centred tetragonal) and ferrite phase
(body-centred cubic) are difcult to distinguish by the XRD due to
their similar lattice parameters [35]. Hence, the two peaks are
assumed to overlap each other. Fig. 10 shows the XRD pattern for
the lean duplex stainless steel, UNS S32101. It is expected that
after work-hardening there will be a reduction in ferrite volume
fraction as a result of higher strain rate sensitivity of ferrite as
compared to austenite [27,35]. This can be seen from Fig. 10b as
the volume fraction of martensite and ferrite seems to be lower
than the initial ferrite peaks. There is however a general reduction
in the austenite peaks conrming that transformation to
a-martensite has occurred.
3.4.4. Scanning electron microscope (SEM) images of eroded surface
SEM images of the cross section of the alloys are shown in
Fig. 11. Outside the area not affected by the impact, the grain sizes
can be seen to be larger. Grain renement and twin formation are
noticed closer to the surface of the damaged layer. This is visible
within the etched layer of about 5 mm from the deformed surface.
This is clear evidence that enough energy has been transferred from
the erodent to the deformed surface to cause grain renement.
3.5. Discussion
The initial high hardness and yield strength of the lean duplex
stainless steels seem to be one of the reasons why pure erosion and
erosioncorrosion resistance of these alloys are better than the
austenitic stainless steel. Austenitic stainless steel, UNS S30403,
0
50
100
150
200
250
300
350
0 5 10 15 20
M
i
c
r
o

h
a
r
d
n
e
s
s

(
H
V
5
0
0
g
)
Distance across the specimen surface (mm)
UNS S30403 WH UNS S32101 WH UNS S32205 WH
Fig. 8. Micro-hardness prole of the cross-section (AA) of alloys after erosion by
sand in de-aerated tap water at 15 m/s and 500 ppm sand for 4 h. (Arrow showing
direction the hardness was taken.)
40 50 60 70 80 90 100 110
0
200
400
600
800
1000
1200
C
o
u
n
t
s
2-Theta (Degrees)
Counts
A
A
A
A
M+F
M+F
M+F
M+F
40 50 60 70 80 90 100 110
0
200
400
600
800
1000
1200
1400
1600
1800
c
o
u
n
t
s
2-Theta (degrees)
counts
M+F
A
A
M+F
A
M+F
A
M+F
Fig. 9. (a) XRD pattern of 304L/UNS S30403 as polished. (b) XRD pattern of 304L/UNS S30403 after erosion at 15 m/s and 500 ppm sand for 4 h in a nitrogen purged tap
water.
S. Aribo et al. / Wear 302 (2013) 16021608 1606
suffered the highest material degradation because of its inferior
mechanical properties as compared to the duplex stainless steels.
The hardness prole in Fig. 8 shows that UNS S30403 responded
better to strain-hardening which translated to a higher percentage
increase in hardness compared to the duplex stainless steels.
However, despite this, its resistance to pure erosion and erosion
corrosion is inferior to the duplex stainless steels. It seems the
inuence of mechanical properties is more dominant when both
erosion and corrosion occur simultaneously.
The higher material loss of UNS S30403 due to corrosion-
enhanced erosion (dE
C
) compared to the lean duplex stainless steels
could be attributed to its lower mechanical properties as earlier
explained. On the other hand, erosion-enhanced corrosion (dC
E
) is
dependent on the passive behaviour of the alloys as well as the phase
transformation induced by the impacting slurry on the near surface of
the alloys. Phase transformation from austenite to martensite
occurred as a result of the impacting sand making the alloys less
corrosion resistant. This could be one reason why UNS S30403 with
high volume fraction of austenite phase (and hence a higher volume
fraction of martensite after strain-hardening) has a fairly high
material loss under erosion-enhanced corrosion compared to the
lean duplex stainless steels (with almost equal proportion of austenite
and ferrite). Another possibility is the likelihood of higher sand
embedment [3234] within the near surface of the austenite phase
(austenite phase is softer than the duplex phase) which could turn
this area into a composite (metalsand-oxide) of inferior corrosion
resistance compared to the duplex phase.
4. Conclusions
1. Lean duplex stainless steels, UNS S32101 and UNS S32304,
seem to have better resistance to pure erosion and erosion
corrosion than UNS S30403 austenitic stainless steel from the
data presented. This is still subject to verications by
considering a wider experimental matrix.
2. Lean duplex stainless steels, UNS S32101 and UNS S32304,
have higher resistance to pure erosion and an equivalent
erosioncorrosion resistance to the duplex UNS S32205 at
both 20 1C and 50 1C.
3. Erosion at 20 1C with 500 mg/l silica sand at an impinging
velocity of 15 m/s is able to transfer enough kinetic energy
causing subsurface deformation, phase transformation and
increase in hardness on both austenitic and duplex stainless
steel alloys.
4. Increase in hardness as a result of pre-erosion at 20 1C resulted
in lower weight loss of the alloys after erosion and erosion
corrosion at 50 1C.
Acknowledgements
The Petroleum Technology Development Fund (PTDF) Nigeria
is appreciated for the Ph.D. scholarship awarded Sunday Aribo to
carry out this research. The Federal University of Technology,
40 50 60 70 80 90 100 110
0
200
400
600
800
1000
1200
1400
1600
1800
F+M
A
A
F+M
A
F+M A
c
o
u
n
t
s
2-Theta (Degrees)
counts
A
F+M
40 50 60 70 80 90 100 110
0
200
400
600
800
1000
1200
1400
1600
1800
F+M
A
A
F+M
A F+M
A
C
o
u
n
t
s
2-Theta (Degrees)
Counts
A
F+M
Fig. 10. (a) XRD pattern of UNS S32101 as polished. (b) XRD pattern of UNS S32101 after erosion at 15 m/s and 500 ppm sand for 4 h in a nitrogen purged tap water.
Fig. 11. SEM images of the cross section (etched in diluted aqua regia) showing the ne grains near the deformed surface.
S. Aribo et al. / Wear 302 (2013) 16021608 1607
Akure, Nigeria is also appreciated for granting Sunday Aribo a
study leave for his Ph.D.
The Authors will also like to appreciate Outokumpu Stainless
Research Foundation, Avesta, Sweden for supplying all the stain-
less steel alloys for this research.
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