Corrosion Science 50 (2008) 2094–2100

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Electrochemical characterization and CFD simulation of flow-assisted corrosion

of aluminum alloy in ethylene glycol–water solution
L.Y. Xu, Y.F. Cheng *
Department of Mechanical and Manufacturing Engineering, University of Calgary, Calgary, AB, Canada T2N 1N4

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

Article history: An impingement jet system was used to study flow-assisted corrosion (FAC) of 3003 aluminum (Al) alloy
Received 13 January 2008 in ethylene glycol–water solutions that simulates the automotive coolant by corrosion potential and elec-
Accepted 6 May 2008 trochemical impedance spectroscopy (EIS) measurements as well as computational fluid dynamics (CFD)
Available online 13 May 2008
simulation. The effects of solution pH and fluid impact angle on Al FAC were determined. An increase of
solution pH enhances the activity of Al due to dissolution of Al oxide film in alkaline environment. More-
Keywords: over, Al activity decreases with the increasing fluid impact angle to the specimen. A CFD simulation
A. Aluminum
shows that, with the increase of impact angle, the electrode area under high-velocity flow field decreases
B. EIS
C. Flow-assisted corrosion
and that under low-velocity flow field increases. Consequently, the shear stress generated on electrode
surface and the resultant mechanical effect on electrode activity decreases. Therefore, the electrode is
more stable than that impacted at a smaller impact angle. There is an essential role of fluid hydrodynam-
ics in corrosion of Al electrode, which is confirmed by corrosion potential and EIS measurements as well
as CFD analysis.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction
Aluminum (Al) alloys, due to their good thermal conductivity
and favorable strength-to-weight ratio, have been commonly used
in a variety of industry fields, including the automotive industry. In
particular, aluminum alloys have been broadly integrated into
vehicular heat exchange systems, replacing more traditional mate-
rials like steels and copper alloys. However, aluminum alloys are
prone to flow-assisted corrosion (FAC) and erosion–corrosion (E–
C) in automotive cooling system [1,2].
In the previous work [3], the synergistic effects of fluid flow and
sand particles on corrosion of 3003 Al alloy in ethylene glycol–
water solution were studied through a rotating disk electrode
(RDE). It was found that, in the absence of sand particles, an en-
hanced electrode oxidation is achieved due to accelerated oxygen
diffusion and reduction upon electrode rotation. With the addition
of sand particles, the de-stabilization of electrode is predominant
and the anodic current density of Al increases with the electrode
rotation speed, which is attributed to the enhanced impact damage
to electrode by sand particles.
It has been known [4–7] that rotating electrode techniques, includ-
ing RDE and rotating cylinder electrode, are capable of simulating the
mass-transfer process by controlling the electrode rotating rate, and
investigating the corrosion of metals in a fluid flow system. However,
its ability to study the effects of fluid impingement and the resultant
shear stress on metal corrosion is very limited. In particular, the role
of sand impact in E–C cannot be quantified. For example, it was ob-
served [8] that most sand particles still deposit in the bottom of cell
when RDE was rotated as high as 8000 rpm.
Impingement jet system has been used extensively to investi-
gate the effects of sands on erosion–corrosion of metals in the var-
ious systems [9–14]. However, to date, there have been few works
to study the fundamentals of Al FAC and E–C in the automotive
cooling system.
In this work, an impingement jet system was used to study FAC
of 3003 Al alloy in ethylene glycol–water solution that simulated
the automotive coolant by measurements of corrosion potential
and electrochemical impedance spectroscopy (EIS). The effects of
solution pH and fluid impact angle on Al FAC were investigated.
Furthermore, computational fluid dynamics (CFD) software was
used to simulate the hydrodynamic conditions established on
specimen, determining the role of fluid hydrodynamics in FAC of
Al alloy. It is anticipated that this work provides an essential in-
sight into the correlation of Al FAC with the fluid hydrodynamic
conditions in the automotive cooling system.
2. Experimental
2.1. Electrode and solutions

The working electrode for electrochemical tests was made of

* Corresponding author. Tel.: +1 403 220 3693; fax: +1 403 282 8406.
E-mail address: fcheng@ucalgary.ca (Y.F. Cheng). 3003 Al alloy with the chemical composition (wt.%): Cu 0.20, Fe,

0010-938X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.05.004
 L.Y. Xu, Y.F. Cheng / Corrosion Science 50 (2008) 2094–2100
0.70, Si 0.60, Mn 1.50, Mg 0.05, Cr 0.05, Zn 0.10, Ti 0.05, and Al bal-
ance. The specimens were embedded in epoxy resin manufactured
by LECO Epoxy Cartridge System, leaving a circular working area of
0.68 cm2. The working surface was subsequently polished with
800, 1000 and 1200 grit emery papers, cleaned by distilled water
and methanol.
The basic test solution was a mixture of 50% (v/v) ethylene gly-
col + 50% distilled water + 100 ppm Cl solution, simulating the
automotive coolant, with an average pH of 6.8. To investigate the
effect of solution pH on Al corrosion, a controlled amount of
0.01 M NaOH solution was added to the solution to obtain solution
pH of 7.5, 8.0 and 8.5, which was measured by OAKTON Acorn pH
Meter Kit with an accuracy of ±0.01.
2.2. Impingement jet system
The impingement jet system, as shown in Fig. 1, was developed
to conduct FAC tests. The system, based on a design by Burstein
et al. [9], consisted of a large plastic tank used as a reservoir, a high
pressure pump, flow velocity controller, sand concentration con-
troller, stirrer and valves. When the fluid entered the ejector at
high speed, it produced a partial vacuum due to the venturing ef-
fect. The sands underneath the valve could be mixed with the flow-
ing fluid by means of suction. A speed-adjustable mechanical
stirrer was used to ensure the homogeneity of the slurry. The ejec-
tor, made of stainless steel with 7.6 mm in diameter, was 10 mm
away from the test specimen. The detailed installation of specimen
in the test chamber is shown in Fig. 2.
An electrochemical cell was incorporated into the test rig to en-
able in situ electrochemical measurements. The Al specimen was
used as working electrode (WE), a saturated calomel electrode
(SCE), which was held inside the test chamber, as reference elec-
trode, and a platinum ring as counter electrode. The impact angle
of the flowing fluid to WE, defined as the angle between the surface
of the specimen and the flow direction of fluid, was adjusted by
rotating the Al electrode.
The basic FAC tests were performed at a fluid flow velocity of
3 m/s with an impact angle of 90° for 10 h.
Fig. 1. Schematic diagram of impingement jet loop system (RE – reference electrode; WE – working electrode; CE – counter electrode).
2095
2.3. Electrochemical measurements
Electrochemical measurements were performed through a
Gamry Reference 600 system. Corrosion potential as a function of
time was recorded. During EIS measurements, a AC disturbance
signal of 10 mV was applied at open-circuit potential, with the
measurement frequency ranging from 100,000 Hz to 0.01 Hz.
2.4. CFD simulation
CFD is a numerical analysis technique based on solving the
well-known Navier–Stokes equations, which are formulations of
mass, momentum and energy conservation laws for fluid flows
[15–17]. The CFD simulations were conducted using a commercial
CFD software package COSMOSfloworks 2007 Service Pack, where
the Favre-averaged Navier–Stokes equations were solved. The ini-
tial and boundary conditions as well as input parameters for CFD
simulation included:
(1) Inlet: A flow of ethylene glycol–water (1:1) solution at the
velocity of 3 m/s, with a dynamic viscosity of about
2.9  103 Pa s and a density of 1.05  103 kg/m3. The test
temperature was 27 °C. Turbulence intensity was set at
10%. In particular, j–e turbulence model was used, where
the turbulent kinetic energy, j, was set as 1 J/kg and the tur-
bulent dissipation, e, was 1 W/kg for simulation.
(2) Outlet: Environment pressure was 101,325 Pa.
(3) Solid wall: The wall could be approximately considered as
an adiabatic wall with roughness of 10 lm, and the surface
of Al electrode was also set at 10 lm.
(4) Flow type: Turbulent flow as calculated, which was shown
later.
Fig. 3 shows the element points selected of finite element calcu-
lation of the average shear stress developed on the electrode. The
grid resolution was 0.769 mm. The calculation was finished once
one of the following conditions was satisfied: (a) minimum refine-
ment number of 0; and (b) maximum travels of 4.
2096 L.Y. Xu, Y.F. Cheng / Corrosion Science 50 (2008) 2094–2100

Holder
X=10 mm

d=7.6 mm
V=3 m/s θ
Angle of
Ejector Specimen
impact

Fig. 2. Detail of impacting test parameters in the specimen chamber.

Fig. 3. Element points selected for finite element calculation to measure the shear stress on electrode surface.

-0.6 -0.6

-0.7
Corrosion potential (V, SCE)

-0.7
Corrosion potential (V, SCE)

-0.8

-0.8
-0.9
pH=6.8
30° pH=7.5
-0.9 -1
45° pH=8.0
60° pH=8.5
90° -1.1
-1
-1.2
0 500 1000 1500 2000 2500
-1.1
t(s)
0 400 800 1200 1600 2000
t(s) Fig. 5. Corrosion potential of Al electrode impacted at 900 in the test solutions with
the different pH.
Fig. 4. Corrosion potential of Al electrode at different impact angles in ethylene
glycol–water solution. then performed. Fig. 4 shows the corrosion potential as a function
of time under different impact angles in the basic test solution (pH
6.8). It is seen that corrosion potential of Al electrode increased
3. Results rapidly first, and then reached a relatively steady value. Further-
more, with the increase of impact angle, corrosion potential in-
3.1. Corrosion potential measurements creased (shifted positively).
Fig. 5 shows the time dependence of corrosion potential of Al
To ensure a fresh Al electrode surface with an identical state for electrode impinged at 90° in the solutions with the various pH val-
all tests, a cathodic potential of 1.1 V (SCE) was applied on elec- ues. It is seen that corrosion potentials were shifted negatively
trode for 2000 s, and measurements of corrosion potential were with the increasing solution pH.
 L.Y. Xu, Y.F. Cheng / Corrosion Science 50 (2008) 2094–2100
3.2. Electrochemical impedance spectroscopy measurements
Fig. 6 shows the EIS plots measured at the different impact an-
gles in solutions with the various pH values. It is seen that there
was an identical feature for all EIS plots, i.e., a semicircle over the
whole test frequency range. Furthermore, with the increase of
solution pH, the diameter of semicircle decreased apparently. At
each pH, the size of the semicircle increased with the decrease of
impact angle.
3.3. CFD simulation
Fig. 7 shows the simulated fluid flow field developed on Al elec-
trode at different impact angles. It is seen clearly that the fluid
fields established at the different impact angles were quite differ-
ent. In particular, at the impact angle of 30°, most of the electrode
surface was under a fluid flow field of 3 m/s. When the impact an-
gle increased to 45° and 60°, the electrode area experiencing low-
velocity flow field of about 1.5 m/s increased. Moreover, the re-
verse flow field enlarged. At the impact angle of 90°, the whole
electrode surface was under a very low flow field of about 1.2–
1.5 m/s, and the flow field was separated into two symmetrical,
opposite directions.
Fig. 8 shows the 3D views of flow field developed on electrode
surface at the different impact angles. The sunken area represented
the low-velocity field like a basin. It is clear that, with the increas-
ing impact angle, the peak area representing the high-velocity flow
field became smaller, and the sunken area enlarged.
Fig. 9 shows the shear stress distribution on the electrode sur-
face at different impact angles. At 30°, a uniform shear stress field
with the amplitude of 50–60 Pa was distributed over almost all the
electrode surface. When the impact angle increased to 45° and 60°,
a zero-shear stress region developed at the edge of electrode sur-
face, and the area increased with the increasing impact angle.
When the impact angle was 90°, the zero-shear stress region fur-
ther increased and concentrated on the center of electrode, with
a low shear stress of about 40 Pa surrounding the central area. Fur-
thermore, a rectangular pattern of shear stress was generated at
impact angle of 90°. It is mainly due to the special geometries of
the specimen holder and test chamber. The cylindrical specimen
was installed in a rectangular platform with a flange above the
specimen. When fluid impacts the specimen at 90°, the fluid will
100000
pH=6.8
80000
Zimag (Ω cm )
2
60000
pH=7.5
40000
30°
20000
pH=8.0 60°
pH=8.5
0 ferent impact angles.
0 50000 100000 150000 200000
2 Reynolds number, Re, is described as the ratio of inertial forces
Zreal (Ω cm )
Fig. 6. EIS plots of Al electrode measured in ethylene glycol–water solutions with
different pH values under the various impact angles.
2097
be reversed back to affect the fluid flow field. Simultaneously,
the reversed fluid from the surrounding wall of the test chamber
can result in the same influence. When fluid impacts at other an-
gles, the fluid flow is not symmetrical on the specimen surface.
Thus, the rectangular pattern of shear stress is not obvious.
Table 1 summarizes the results of average shear stress vs. im-
pact angle. It is seen that the average shear stress of the electrode
increased with the decreasing impact angle.
4. Discussion
4.1. Corrosion electrochemistry of Al alloy in ethylene glycol–water
solution
Generally, the anodic and cathodic reactions of Al alloy in an
aerated, near-neutral aqueous solution are characterized by the
Al oxidation and reduction of oxygen:
Anodic reaction : 2Al þ 6OH ! Al2 O3 þ 3H2 O þ 6e ð1Þ
Cathodic reaction : 3=2O2 þ 3H2 O þ 6e ! 6OH ð2Þ
The dissolved oxygen diffuses towards the electrode surface for the
cathodic reaction which generates hydroxide ions used by the oxi-
dation of Al to form aluminum oxide film, leading to the positive
shift of corrosion potential of the electrode, approaching a relatively
steady-state value with time.
Upon the increase of solution alkalinity, Al oxide film experi-
ences dissolution by
Al2 O3 þ 2OH ! 2AlO2 þ H2 O ð3Þ
The increase of electrode activity with solution pH results in a more
negative, steady-state corrosion potential in the solution with a
higher pH, as shown in Fig. 5.
The enhanced electrode activity is also shown by the EIS results.
In general, the existence of only one semicircle over the whole fre-
quency range in impedance plot indicates a capacitive behavior of
the metal electrode. The size of semicircle corresponds to the
charge-transfer resistance, which is directly associated with the
interfacial electron-exchange reaction. For an impedance response
with a larger real impedance, i.e., a bigger semicircle, the electrode
will be more resistant to corrosion attack. Moreover, the imped-
ance feature also indicates the rate-controlling mechanism for cor-
rosion process. The presence of one semicircle is correspondent to
the activation-controlled corrosion, while a diffusive Warburg
impedance existing in the low-frequency range indicates that cor-
rosion process is controlled by mass-transfer step [18–20].
The present work shows that, with the increase of solution pH,
the diameter of the semicircle that represents the charge-transfer
resistance decreases significantly, indicating the enhanced dissolu-
tion of Al electrode at the alkaline solution. Furthermore, the
impedance feature of only one semicircle over the measured fre-
quency range indicates that the electrode process is controlled by
activation step, rather than the oxygen diffusion. It could be attrib-
uted to the accelerated mass-transfer process in the flowing fluid
system. The electrode process is thus controlled by activation step
at all impact angles.
45°
4.2. Hydrodynamic analysis of FAC of Al alloy
90°
Both corrosion potential and EIS measurements show that there
are quite different electrode activity and FAC rate of Al at the dif-
250000
to viscous forces and, consequently, it quantifies the relative
importance of these two types of forces for given flow conditions.
It is also used to identify and predict different flow regimes, such as
2098 L.Y. Xu, Y.F. Cheng / Corrosion Science 50 (2008) 2094–2100

Fig. 7. Fluid flow field developed on Al electrode under different impact angles.

Fig. 8. 3D plots of velocity flow field developed on electrode surface: (a) panoramic view and (b) cropped front view.

laminar or turbulent flow. Laminar flow occurs at low Reynolds by smooth, constant fluid motion, while turbulent flow occurs at
numbers, where viscous forces are dominant, and is characterized high Reynolds numbers and is dominated by inertial forces, which
 L.Y. Xu, Y.F. Cheng / Corrosion Science 50 (2008) 2094–2100
Fig. 9. Shear stress generated on electrode surface at different impact angles.
Table 1
Average values of shear stress generated on electrode surface at different impact
angles
Impact angle 30° 45° 60° 90°
Average shear stress (Pa) 50.38 43.68 38.84 33.36
tend to produce random eddies, vortices and other flow fluctua-
tions. Typically it is given as
qu0 L u0 L
Re ¼ ¼ ð4Þ
l m
where u0 is the fluid velocity (m/s), L is the characteristic length
(m), l is the (absolute) dynamic fluid viscosity (Pa s), m is the kine-
matic fluid viscosity (m2/s), and q is the density of the fluid (kg/m3).
Replace the parameters and variables in Eq. (4) with the present
conditions, Re is calculated to be about 2  104 for the fluid flow
velocity of 3 m/s. The calculated Re value is much higher than the
threshold value of 2300 for laminar flow [21]. It is thus apparent
that the impingement jet system generates a turbulent flow.
The fluid impingement on electrode generates a mechanical
shear stress, s, on the surface, which is the measurement of viscous
energy loss within the turbulent boundary layer and related to the
turbulent intensity acting on the surface [22–24]. The shear stress
is expressed as
s  0:5fu2 q ð5Þ
where f is the friction factor which is a function of Re and the rough-
ness of the surface. Apparently, an increasing fluid velocity results
in the elevation of shear stress, which is confirmed by the present
CFD simulation shown in Fig. 9.
The CFD simulation results show clearly that there are different
flow fields and flow velocity on the electrode surface at the differ-
ent fluid impact angles. At a small impact angle such as 30°, the
whole electrode surface is under a uniform flow field with a high
flow velocity of about 3 m/s, as shown in Fig. 6. The resultant shear
stress is thus high and distributes uniformly over the electrode sur-
face (Fig. 9). Shear stress, representing a mechanical effect, would
thin and remove oxide film and corrosion product deposit, and
2099
even damage the electrode matrix, enhancing the electrode activ-
ity. For example, Hussain and Robinson [25] found that the thick-
ness of oxide film on stainless steel is thinned at high turbulent
flow range which is associated with high shear stress. Therefore,
the Al electrode impacted at 30° generates the highest shear stress
over the whole electrode surface (Table 1), resulting in the highest
corrosion activity, which is indicated by the most negative corro-
sion potential (Fig. 4) and the smallest charge-transfer resistance
(Fig. 6).
With the increase of impact angle, the electrode area under
high-velocity flow field (3 m/s) decreases, and the low-velocity
flow field with the value of about 1.2–1.5 m/s dominates the elec-
trode surface, which is clearly shown in Figs. 7 and 8. As a conse-
quence, the electrode area with a small shear stress (0–10 Pa)
increases and that with a large shear stress (up to 60 Pa) decreases
with the increasing impact angle, as shown in Fig. 9. Finite element
calculation of the average value of shear stress (Table 1) also indi-
cates that the average shear stress generated on electrode surface
decreases with the increase of impact angle, resulting in a more
stable electrode state, as shown in corrosion potential and EIS
measurements.
When the impact angle increases to 90°, the electrode is under
low-velocity flow field with the value of about 1.5 m/s (Fig. 7). The
resultant shear stress has the lowest value (Table 1). Therefore,
there is the smallest mechanical effect due to fluid impingement
on the electrode state. Consequently, there is the most positive cor-
rosion potential and the largest charge-transfer resistance in
impedance measurement.
5. Conclusions
An increase of solution pH enhances the activity of Al in ethyl-
ene glycol–water solution due to dissolution of Al oxide film in
alkaline environment.
Fluid hydrodynamics play an important role in Al FAC. The Al
electrode activity decreases with the increasing fluid impact angle
to the specimen. With the increase of impact angle, the electrode
area under high-velocity flow field decreases and that under low-
velocity flow field increases. Consequently, the shear stress gener-
ated on the electrode surface and the resultant mechanical effect
2100 L.Y. Xu, Y.F. Cheng / Corrosion Science 50 (2008) 2094–2100
on electrode activity decreases. Therefore, the electrode is more
stable than that impacted at a smaller impact angle.
Acknowledgements
This work was supported by Canada Research Chairs Program,
Natural Science and Engineering Research Council of Canada
(NSERC) and Dana Canada Corporation.
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