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Desalination 183 (2005) 227234

Erosioncorrosion of duplex stainless steel under Kuwait


marine condition
Essam Hussaina, A. Husainb*
a

Kuwait College of Technological Studies, Automotive and Marine Engineering Department


P.O. Box 23167, Safat 13092, Kuwait
b
Kuwait Institute for Scientific Research, Department of Building and Energy Technologies,
P.O. Box 24885, Safat 13109, Kuwait
Tel. 965 483 6100 Ext. 4522; Fax 965 484 5763; email: xhusain@yahoo.com, ematouq@hotmail.com
Received 22 November 2004; accepted 21 February 2005

Abstract
Erosioncorrosion of stable passive metals like Duplex Stainless Steels (DSS) proceeds by the repeated
removal and repair of the oxide film. When sand particles are entrained it can be a problem in marine pumps,
piping systems, heat exchangers, and units handling seawater in the Arabian Gulf for use as part of desalination
plants. More specifically, sand particles in the presence of seawater enhanced the erosion corrosion problem. If
the passive film structure is stable, it will reform spontaneously when it becomes damaged. The erosioncorrosion study is concerned with the application of a jet impingement apparatus to study the behavior of
DSS steel of Cr/Ni/Mo/N grade in simulated Arabian Gulf seawater. An interference color imaging technique
(ICI) for thickness measurement of the oxide film passivity, pitting, and transpassivity of the surface of DSS has
been developed under the effect of well defined hydrodynamic condition and potentiodynamic polarization
technique. Electrochemical imaging technique of surface corrosion potential mapping (SCM) was also introduced to measure the rate of repair of the passive film combined poteniodynamic polarization under flowing
conditions, both with and without the addition of sand particles. The main aim is to obtain a better understanding of the electrochemistry of DSS alloys in marine erosioncorrosion condition and to examine the
viability of SCM and ICI to be used as a diagnostic tool for DSS material evaluation. The results indicated that
both techniques gave optimum imaging analysis of DSS steel. Water jet impingement showed higher current
densities at the ferrite dissolution potential and austenite pitting potential during the introduction of sand
particles.

*Corresponding author.
Presented at the Conference on Desalination and the Environment, Santa Margherita, Italy, 2226 May 2005.
European Desalination Society.
0011-9164/05/$ See front matter 2005 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2005.02.051

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E. Hussain, A. Husain / Desalination 183 (2005) 227234

Keywords: Erosioncorrosion; Duplex stainless steel (DSS); Interference color imaging technique (ICI); Surface
corrosion potential mapping (SCM); Potentiodynamic

1. Introduction
Over the years, improvements in alloy
design were made for stainless steel. This
has been satisfied by the development of
DSS alloys. They were chosen to contain a
mixture of austenitic and ferritic phases,
usually in approximately equal proportions.
For example, the Cr/Ni balance was adjusted,
normally with the addition of ca. 0.10.17
nitrogen as an austenitiser. This effect vastly
improved weldability with high corrosion
resistance [1,2]. Current interest in high alloy
steels has centered on chloride media such as
handling chlorinated seawater in desalination
plants. Standard test and several studies have
usually employed acid with oxidizing condition according to ASTM G48 [3]. In the present work, the extent to which sand erosion
corrosion was likely to pose a problem in this
media has been studied using interference
color imaging technique (ICI) and surface
corrosion potential mapping (SCM). This
study is part of a larger experimental investigation on the effect of Kuwait Gulf seawater
on different grade of DSS steels.
The aim of the study described in this
paper was to measure the effects of flowing
seawater containing sand particles on the
thickness of the passive oxide films developed
on the surface of duplex stainless steel.
The developed oxide film was assessed from
its optical interference images by ICI. The
technique has been correlated with surface
electrochemical imaging SCM technique
developed earlier by Husain [4].
According to Evans [5] interference colors
occurs between light reflected from the surface of the oxide film and light retrieved from
reflection at the oxide/metal interface when

their paths differ by an odd number of half


wavelengths. Owing to the high refractive
index of the oxide film, the light inside the
film is almost normal to the surface for a
wide range of angles of incidence. The imaging colors were reproduced under stagnant
condition and whilst under the effect of the
different hydrodynamic conditions beneath
the jet apparatus.
2. Experimental methods
2.1. Erosion corrosion ICI and SCM tests
A close flow loop for the jet impingement
apparatus was designed with test specimen
mounted directly beneath the orifice of the
jet nozzle as illustrated in Fig. 1a. The loop
contained approximately 3 l of artificial seawater and capable of producing a velocity of
8.5 ms1 at the 5 mm diameter orifice. A 1.5-l
capacity glass cell contained the samples,
together with a platinum counter electrode
and standard calomel reference electrode.
The seawater temperature was controlled at
24 C using an electrical heater and thermostat
together with a water-cooled heat exchanger.
The sand particles were introduced to the
flow and were 250300 m in diameter,
varying in shape from rounded to angular.
Corrosion experiments were performed on a
test specimen consisting of cylindrical electrodes machined with the dimensions shown in
Fig. 1b.
An electrical connection was attached to
each electrode and it was then arranged concentrically and mounted in epoxy resin. The
surfaces were ground and polished down to
1 m diamond paste and then degreased and
ultrasonically cleaned and air dried. The

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E. Hussain, A. Husain / Desalination 183 (2005) 227234

passive current density at 0 mV (SCE) was


7.5 Acm2. The mean impact crater was
measured by scanning electron microscopy
to be 11.8 m in diameter. It follows that
for a total number of particle impacts, N, of
2400 per second, the mean number of impacts
on each point of the surface, n, was 0.013 per
second. Therefore, the mean interval between
these impacts would have been in the order of
76 seconds.
2.2. Materials Specification
Fig. 1. Schematic diagram of the test set up (a) closed
loop impingement apparatus and (b) the cylindrical
electrodes specimens.

The tests were performed on duplex stainless steel (UNS31803) with the composition
shown in Table 1.
2.3. Hydrodynamic conditions

electrode surface was polarized by holding it


at a potential of 400, 700 or 900 mV (SCE)
for six hours. Meanwhile, the specimen film
thickness and surface topography was analyzed with an interference color imaging technique (ICI) and surface corrosion potential
mapping (SCM). The SCM technique has
been used for the measurement of surface
equipotential lines emerging on the specimen
surface using the same set of sample under
potentiodynamic polariztion. These scanned
surface of equipotential lines represent partial
anodic and cathodic electrochemical current.
Details about the experimental setup of SCM
technique is given in reference [4]. The specimen was then tested at the same potential
under flowing seawater with the addition of
sand particles.
It was assumed that the passive current
density measured during erosioncorrosion
of the duplex stainless steel in seawater containing sand particles was due to disruption
and repair of the oxide film. The total kinetic
energy of particles impacting the surface has
been considered. Therefore, with 3 g sand
and an orifice velocity of 8.5 ms1, the

The hydrodynamic flow characteristic due


to jet impingement on a flat plate was established according to that proposed by Efird
[6]. The shear stress on the DSS surface of
the sample,  w, was calculated from the following formula
 
r
w 0:179w U0 Re  0:182
r0

where:  w is the density of the fluid, U0 is the


jet velocity, Re is the Reynolds number at the
orifice and;


2r0 U0
Re


r is the radial distance from the centre of the


jet, r0 is the orifice radius and  is the kinematics viscosity.
Table 1
Composition of Duplex Stainless Steel Material
Cr

Ni

Mo N

21.9 5.4 3.1

Si

Mn P

0.18 0.02 0.49 1.5

0.025 0.003

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E. Hussain, A. Husain / Desalination 183 (2005) 227234

2.4. Interference Color Imaging Technique


(ICI) for film thickness measurement
Topographical images in terms of interference colors of the specimens surface were
taken at a range of radial distances and compared with those in the Michel-Levy chart [7].
The path difference was identified for each
color, enabling the film thickness to be calculated for each region using Eq. 3. The values
of refractive index for each wavelength were
assumed to be those for oxides on iron, as
shown in Table 2.

Path difference 2t 2n  1
2

Where n = 1, 2, 3 etc; t, thickness of the


oxide film; , wavelength most strongly
absorbed in the incident light; , refractive
index of the oxide at this wavelength.
Accordingly, when light is reflected at an
interface between media of different optical
density a phase change can occur, which is
equivalent to an additional film thickness C.
Consequently, the maximum interference
would occur at film thicknesses of t = /4C,
t = 3/4C, t = 5/4C etc. However, for
a transparent oxide film on a metal substrate
it is usual to assume that no phase change
takes place and that C = 0. The refractive
index of the film on stainless steel was as

assumed by Evans. However, refractive


index is dependant on wavelength and a correction can be made. The values shown in
Table 2, used in the present work, are for a
mixed iron oxide where;
104
 1:35 18:8  2 4


3. Results and Discussion


Samples of water/sand were collected
from the loop in order to measure the quantity of sand that was suspended in the flow
and to allow for any particle that had settled
out. From these measurements, the rates of
particle impacts were calculated. For the
addition of 3 g of sand, the rates were 2400
and 1400 impacts/second at velocities of 8.5
and 7.9 ms1, respectively. It follows that
the corresponding average times between
particle impacts over the electrode surface
were 0.42 and 0.71 m sec. The effect of adding sand was to erode the oxide film, particularly in the stagnation region beneath the
orifice.
The developed interference colors remaining after exposure at velocities of 8.5 and
7.9 ms1 are shown in Figs. 24, respectively. The original film was thin in the high

Table 2
Complementary colors displayed by destructive interference [7]
Wavelength (nm)

Color Absorbed

Complementary Color Observed

Refractive Index ()

417.5
457.5
485
495
530
570
577.5
589
700

Violet
Blue
Blue-green
Green-blue
Green
Yellow-green
Yellow
Orange
Red

Yellow-green
Yellow
Orange
Red
Purple
Violet
Blue
Blue-green
Green-blue

2.43
2.25
2.15
2.12
2.02
1.93
1.89
1.90
1.73

E. Hussain, A. Husain / Desalination 183 (2005) 227234

231

Fig. 2. Film thickness measurements for DSS in seawater containing 3 gm sand at 8.5 ms1 with potentials of
400, 700 & 900 mV (SCE) for 618 hours.

Fig. 3. Film thickness measurements for DSS exposed to seawater at 8.5 ms-1 with potentials of 400, 700 &
900 mV (SCE) with 3 gm of sand after 618 hours.

turbulence region and the sand particles


appeared to have little additional effect due
the low angle of the impacts on the surface.
Similarly, no film thinning was recorded in
the low turbulence region.

Short exposure times of 1060 minutes


removed the oxide film in the stagnation
region alone (Fig. 3), whereas longer exposure
(618 hr) progressively removed the oxide over
wider areas of the surface (Fig. 2). In the

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E. Hussain, A. Husain / Desalination 183 (2005) 227234

Fig. 4. Film thickness measurements for DSS in seawater containing 3 gm sand at 7.9 ms-1 with potentials of
400, 700 & 900 mV (SCE); for exposure of 1 hour.

stagnation region, the film was a first order


grey-blue color for all exposure times. This
film color corresponded to approximately
33 m in thickness and suggests that the film
being removed and immediately reforming.
3.1. SCM scan and the effect of potentiodynamic
polarization
An important feature of the polarization
behavior of the duplex stainless steel was the
existence of two discrete pitting potentials.
The steel was passive at the open circuit
potential and remained so up to 400 mV
(SCE). Above this potential pitting occurred
in the ferrite phase, while the austenite
remained passive until a potential close to
900 mV (SCE) has been reached and pitting
occurred in both phases. This has been confirmed by the SCM mapping of the surface
obtained at 400, 700, and 900 mV as shown
in Fig. 4. Metallographic examination also
confirmed that in the range 400900 mV
(SCE) pitting was in the ferrite alone (Fig. 5).

The largest influence of flow and sand


erosion on the polarization behavior was
recorded on the central electrode (cylindrical 1),
positioned in the stagnation region directly
beneath the orifice. Fig. 3 shows the results
for a velocity of 8.5 ms1 both in flowing
seawater alone and with the addition of 3 g
of sand. Each of the polarization scans had
the same general features as in the low turbulence region on Ring 3, shown in the same
Figure, and exhibited a passive range and
separate pitting potentials for the ferrite and
austenite phases.
Without sand additions, the current density in the passive range was essentially the
same on the three cylindrical specimens.
However, the addition of sand particles
caused a systematic increase in the current
densities recorded on cylindrical 1, beneath
the orifice. This is the most pronounced effect
observed in the passive range, where an
increase of one order of magnitude occurred,
but a smaller increase also took place in the
ferrite pitting range. The increase in passive

E. Hussain, A. Husain / Desalination 183 (2005) 227234

233

Fig. 5. SCM scan of DSS surface at (a) passivity 400 mV, (b) pitting at 700 mV and (c) transpassivity at 900 mV.

current density with the addition of sand also


displaced the intersection of the anodic and
cathodic polarization curves and resulted in a
lowering of the open circuit potential. The
fact that a discernable color was present
directly beneath the orifice (Figs. 2 and 3)
indicates that the film was reforming rapidly
between particle impacts and that film
removal and repair were occurring simultaneously as competing processes.
In flowing seawater, without sand additions, the passive current density was close
to 0.8 Acm2 (Fig. 4) and the additional
current measured when sand was added
represented that required to repair the film.

However, the typical blue-grey color of the


film (33-m thickness) shows that there was
insufficient time between particle impacts for
it to grow to its steady state thickness. Other
researchers have investigated the charge
passed when the passive film on stainless
steels is mechanically damaged. In each case,
a large initial current occurs and gradually
decays.
Furthermore, it was anticipated that the
current density would be shown to be directly
related to the total kinetic energy of the
impacting sand particles. Clearly, in one second a total charge of 1.5 C would pass in
reforming the passive film, because of 2400

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E. Hussain, A. Husain / Desalination 183 (2005) 227234

impacts. Therefore, the charge passed per


impact may be estimated as 6.3  1010 C.
Similarly, as there is (0.013) impacts/sec on
each point of the surface, the mean charge
passed in one second on each point would
be in the range of 8.2  1012 C.
3.2. Interference and SCM imaging colors
Pronounced interference colors were visible on the electrode surfaces after exposure to
flowing seawater for six or more hours at the
anodic applied potentials.
The colors differed at each potential but
all displayed essentially three zones which
corresponded to the stagnation, high turbulence and low turbulence regions.
The thickness was similar in the stagnation
and low turbulence regions but considerably
thinner in the high turbulence region. This
effect might be attributed to the high surface
shear stress in that position. Similar trend
was observed at a jet velocity of 7.9 ms1.
The SCM maps in Fig. 5 clearly indicated
the viability of the technique to be used as a
diagnostic tool for DSS steel surface characterization. The reddish color images of the
surface indicated anodic areas which probably represent ferrite dissolution whereas the
blush color indicated cathodic areas and passivity of the surface. The transpassive region
of the surface has been clearly defined where
ferrite and austenite interlink at such high
polarization potential.
4. Conclusions
Interference color imaging analysis on
DSS stainless steel cylindrical specimens
showed a distinct series of zones with distance
from the concentric during damage and
growth of passive oxide film. Some of these
zones were correlated very well with thickness

of the oxide layer, metallographic and SEM


observations under controlled hydrodynamic
condition. The color images also show clearly
the incubation periods before the onset of any
visible passive oxide film on the DSS samples.
The SCM observation technique as a standalone test does however, show the potential
differences which correlate with film thicknesses and other zone or even a general visual
image of the three zones altogether specifically when a wider sample is being used.
Both techniques have offered considerable
contribution and strong evidence for the protective performance of DSS oxide film during
erosion corrosion in simulated seawater
environment.

References
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(2000) 514.
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London., 1984. pp. 240.
[3] A.S.T.M. Standard G4876, Standard test
method for pitting and crevice corrosion resistance for stainless steels and related alloys by the
use of Ferric Chloride Solution. Philadelphia,
PA, ASTM, 1980
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333340.
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seawater. Proc. Conf., Institute of Materials,
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