424 DOI: 10.1002/maco.200805141
Influence of turbulent flow on the corrosion of
Al-Zn-Mg galvanic anode in artificial
seawater media
The effect of hydrodynamics on the corrosion of Al(14 wt%)-
Zn(8 wt%)-Mg alloy in artificial seawater media at room tempera-
ture was studied in a rotating cylinder electrode (RCE) system under
turbulent flow conditions. Five different rotation rates were studied: 100,
1000, 3000, 5000, and 7000 rpm. The corrosion rates were measured by
electrochemical impedance spectroscopy (EIS). For the system studied,
the steady-state corrosion potential increased with increase in rotation
1 Introduction
Aluminum anodes have long been used in the fight against
corrosion. Applications for aluminum anodes include ship
hulls, tank interiors, offshore structures, submerged pipe-
lines, piers, pilings, etc. Aluminum alloy is the only anode
material that is safe for use in all types of water. It is lighter
and protects better than zinc. Some other advantages of
aluminum are:

Due to the fact that the capacity of aluminum (2700 A-h/
Kg) is almost 3.5 times higher than zinc (780 A-h/kg) total
amount of required anode material is less. This results in a
cheaper cathodic protection (CP) system to that given by
Zn with an equal protection level.

As a total weight of anode material for a system using
aluminum is less compared to a system using zinc anodes,
the installation costs for a system using aluminum anodes
will also be less.

In brackish water, aluminum anodes work more efficiently
than zinc, due to the higher driving voltage of aluminum.
Recently the Al-Zn-Mg alloy has been pointed out as a
promising alloy system to be studied due to its low electrode
potential and high current capacity to be used as galvanic
anode [1,2].
Understanding how CP works on ships involves con-
sideration of the ship as an electrochemical system. Cathodes
(hull/propeller) are protected regions, and anodes are either
discrete small pieces of sacrificial metal or electron source
points dispersed along the underwater hull at various
intervals. For a ship at sea, the wetted surface area of the
hull and the appendages (like bilge keel, rudder, and
propeller) are the cathodes that require CP. In a new hull

J. Genesca, M. C. Quevedo
Departamento Ingenieria Metalurgica, Facultad Quimica,
UNAM, Ciudad Universitaria, 04510 México D.F. (Mexico)
E-mail: genesca@servidor.unam.mx
www.wiley-vch.de/home/wuk ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Materials and Corrosion 2009, 60, No.
M. C. Quevedo and J. Genesca*
rate. The effect of increasing the rotation rate is to increase the avail-
ability of oxygen at the surface, which in turn will polarize the corrosion
reaction in the more noble direction. The corrosion rate also increases
with increase in RCE rotation rate. This reflects the fact that the rate of
corrosion is controlled, at least in part, by the rate of mass transfer. In this
case, the effect of increase in the rotation rate on the corrosion rate is to
increase the interfacial concentration of the reactant (oxygen).
state, typically only the propellers and small regions on the
hull where the coatings may not be adequate (including small
breaks in the paint, which are referred to as paint holidays)
require protection.
Whereas ships propellers are normally very well
protected, the hull near propellers is not fully protected.
Additionally, in typical propellers operating in ships in
service, the Reynolds number is ordinarily of sufficient
magnitude so that turbulent flow occurs about the propeller
services. Then it seems necessary to perform corrosion
research under turbulent flow conditions. Accordingly,
hydrodynamic factors are to be taken into account in the
analysis of the kinetics of galvanic anodes degradation. Mass
transfer and surface shear effects may have a profound effect
on the rate of anode degradation, either by modifying the rate
of transport of chemical species to or from the surface or by
shear-stripping protective films from the alloy/solution
interface. As a result, an accurate simulation of corrosion
phenomena that occur in the propeller environments can be
made in the laboratory only if the hydrodynamic effects are
taken into account.
The effect of fluid velocity on the corrosion rate of metals
in condensed media is a very well-known issue. The
corrosion of metals and alloys in condensed media involves
at least three fundamental steps:
1. Transport of the reactant to the metal surface.
2. Electron exchange resulting in metal loss.
3. Transport of the corrosion products from the surface to the
bulk solution.
Because the three steps occur in series, any one of them
can control the rate of the overall process. Accordingly, it is
necessary to take into account both charge transfer and mass
transfer phenomena when describing the corrosion of metals
in aqueous solutions.
In this context, we present in this paper the first results
obtained concerning the effect that turbulent flow has on the
corrosion kinetics and mechanism of Al-Zn-Mg galvanic
anodes recently developed for marine applications.
Materials and Corrosion 2009, 60, No. 6 Influence of turbulent flow on the corrosion of Al-Zn-Mg galvanic anode 425

2 Experimental 3 Results and discussion

Al, Zn, and Mg elements of commercial purity (99.5%), 3.1 Microstructure

previously weighed, were placed into a SiC crucible and
melted into a resistance furnace under an argon protective The microstructure observed in chill-cast ingots consisted
atmosphere. The liquid melt was gravity cast into a steel chill mainly of a-Al dendrites and the eutectic a þ t in
mold. The selected alloy composition was chosen in such interdendritic regions, following the dendritic arms [1], as
way that it lies between the maximum concentration of solute shown in Fig. 1. The microstructure was revealed by etching
at equilibrium (Ceeqmax ) and in the a þ t field, as indicated in the samples in a solution containing 10 g of NaOH in 90 mL
the phase diagram [3]. The alloy composition of as-cast of distilled water. Figure 1 shows the microstructure
ingots was determined by emission spectroscopy analysis, observed in the optical microscope corresponding to the
and the results are shown in Table 1. The resulting ingots, as-cast condition. The eutectic was identified by micro-
2 kg of weight approximately, were cut out in sections analysis. Figures 2 and 3 show the microstructure and
parallel to the heat flow. The samples were observed under energy-dispersive X-ray (EDX) microanalysis of the as-cast
optical (Zeiss-Olympus) and scanning electron (Jeol JSM and heat-treated ingots, respectively.
5900 LB) microscopes. Finally, a heat treatment at 400 8C
during 5 h under an argon protective atmosphere was
realized. 3.2 Electrochemical behavior
EIS measurements were conducted by using a Gill AC
potentiostat from ACM Instruments over a frequency range The RCE has been used extensively in corrosion research
of 10 kHz to 10 mHz (10 points per decade) superimposing a because of the fact that the flow is essentially turbulent even
10 mV AC signal. Potentiodynamic polarization curves were at very low rotational velocities [7,8]. The critical Reynolds
carried out with a Gill AC potentiostat at a sweep rate of number, Re, for the transition from laminar to turbulent flow
60 mV/min. lies within the range 50–300 for a smooth laboratory RCE
The aqueous solution was synthetic seawater prepared [9]. The RCE provides a relatively large surface area and is
according to ASTM D1141 standard [4]. All experiments well suited to turbulent flow laboratory studies of corrosion.
were performed at atmospheric pressure (Mexico City) and In the laminar flow regime (Re < 50), the Sherwood number,
room temperature, 20 8C. All the experiments were carried Sh, was found to be constant (Sh ¼ 37) and was independent
out in triplicate to check the reproducibility of the results. of Re. For turbulent flow (Re > 300), the mass transfer rate
Because the experimental error of the series was minimum, was correlated as
we only presented a plot of the three similar plots obtained.
The conventional three-electrode system was used. The
RCE, Pine Instrument model AFMSRX was used to simulate Sh ¼ 0:97Re0:64 (1)
turbulent flow conditions. Different rotation speeds such as
100, 1000, 3000, 5000, and 7000 rpm were tested. The open
circuit potential, Ecorr, was measured for 45 min approxi- In the present work, the range from 100 to 7000 rpm was
mately before each polarization run. selected as the peripheral velocity of the rotating electrode
Potentiodynamic polarization curves were obtained by giving a Re number between 754 and 52 800. Eisenberg et al.
first sweeping the voltage at a scan rate of 1 mV/s from the [10] showed that in the range of 103 < Re > 105 equation (2)
corrosion potential into the cathodic region. This sweep rate is a straight-line approximation over a more-limited Re
was selected as the fastest possible so that any further number range.
decrease in the sweep rate does not significantly change the
current measured. All electrochemical tests were carried out
on clean samples and in freshly prepared solutions.
An airtight three-electrode electrochemical cell was used,
as described previously [5]. The working electrode (WE) was
machined from the parent material, the as-cast Al alloy ingot
and had a diameter of 1.2 cm and an exposure area of
3.071 cm2. The counter electrode was a rod of sintered
graphite, while a saturated calomel electrode (SCE), was
used as the reference electrode. The Al alloy surface was first
polished with 600 grit SiC paper then was cleaned and
degreased with acetone and finally washed with distilled
water. Following these preparations, the polarization tests
were initiated.
Anode electrochemical efficiency, e, was in the order 50–
60%, for both the as-cast and heat-treated Al-alloy, as Fig. 1. Microstructure observed in optical microscope of the chill-
determined following NACE TM 0190-98 standard [6]. cast ingots of Al(13.8%)-Zn(8.8%)-Mg alloy

Table 1. Chemical composition of Al alloy as determined by emission spectroscopy analysis.

Element Al Zn Mg Si Cu Fe Mn Ni Ti Sr

wt% Bal. 13.76 8.79 0.0803 0.3669 0.2832 0.1033 0.0018 0.0052 0.0001

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426 Quevedo and Genesca
Fig. 2. Microstructure and microanalysis of the as-cast Al(13.8%)-Zn(8.8%)-Mg alloy. SEM mapping of Al, Zn, Mg, Si, and Cu chemical
elements
Figure 4 shows the behavior of the corrosion potential,
Ecorr, as a function of the rotation rate of RCE. As can be
observed, the relationship between Ecorr and u0.7 is not as
good as can be expected, which constitutes possible evidence
that the corrosion process is not under total mass-transfer
control. But Ecorr values show a clear tendency to be more
anodic as RCE rotation rate increases. It is interesting to note
that the flow regime, laminar or turbulent, seems to be more
important that the effect of the rotation rate.
The measured Ecorr values are in the interval between
1269 and 955 mV (SCE) and are similar to the previously
obtained by other authors such as Barbucci et al. [1],
Orozco et al. [2], Foley and Trazskoma [11], and Talavera
et al. [12] working with Al-alloys of similar chemical
composition.
Materials and Corrosion 2009, 60, No. 6
The effect of flow on the anodic and cathodic polarization
curves of the studied Al-alloy is presented in Fig. 5 at
different RCE rotation rates. As can be observed the effect of
flow is especially significant on the cathodic polarization
mechanism and significant differences between laminar and
turbulent flow regime can be noted. Under quiescent
conditions, the anodic behavior shows an active–passive
transition, while the cathodic mechanism seems to be typical
of a charge transfer process. A Tafel region with a slope of
128 mV/decade, possibly related to the oxygen reduction
reaction (ORR) can be noticed, while at more cathodic
potentials H2O reduction could take place.
The effect of flow significantly affects both anodic and
cathodic polarization behavior. The anodic part of the
polarization curve shows a typical resistive behavior, which
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Materials and Corrosion 2009, 60, No. 6 Influence of turbulent flow on the corrosion of Al-Zn-Mg galvanic anode 427

Fig. 3. Microstructure and microanalysis of the heat-treated Al(13.8%)-Zn(8.8%)-Mg alloy. SEM mapping of Al, Zn, Mg, Si, and Cu
chemical elements

can be attributed to the formation of a corrosion products 3.3 Assessing mass transfer control
layer. Cathodic polarization curve shows a classical diffusion
conduct. Two limiting current density regions can clearly be To determine if mass transfer controls the cathodic process
observed before the water reduction reaction could take under the experimental conditions prevailing in this study,
place. one might measure the limiting current density at several
RCE rotation rates at the same potential in the cathodic
0 polarization curve. The hydrodynamics must be turbulent at
-200 0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 all times.
Figure 5 shows the potentiodynamic polarization curves
Ecorr , mV vs sce

-400
y = 3.6664x - 1156.2 corresponding to the ASTM seawater solution at 20 8C.
-600
R2 = 0.5651 Regarding the cathodic polarization curves the following
-800
features can be observed in Fig. 5. At all rotation rates two
-1000 well-defined cathodic limiting current density, ilim, regions
-1200 can be observed. These regions are clearly affected by the
-1400 rotation rate of the electrode and, in general terms, as the
(u, cm.s-1)0.7
rotation rate of the electrode increases the value of current
density at which ilim appear also increases. These facts can
Fig. 4. Corrosion potential, Ecorr as a function of RCE rotation rate suggest that a diffusion-controlled process taking place on
in synthetic seawater at room temperature the surface of the electrode is being measured.

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428 Quevedo and Genesca Materials and Corrosion 2009, 60, No. 6

-600
-5 -4 -3 -2 -1 0 1 2
0.9
-700
0.8 -1100 mV
0.7

i lim , mA.cm -2
-1400 mV
-800 0.6
0.5 O2 theoretical
-900
0.4 y = 0.0027x + 5E-06 Lineal (-1400 mV)
0.3 R2 = 1
E, mV vs sce

-1000 Lineal (O2 theoretical)

0 RPM 0.2
-1100
1000 RPM
3000 RPM 0.1 Lineal (-1100 mV)
5000 RPM
7000 RPM
0
-1200
0 20 40 60 80
-1 0.7
-1300
(u, cm.s )
-1400
Fig. 7. Theoretical limiting current density as a function of RCE
-1500 rotation rate for O2 reduction reaction
-1600

Log i, mA.cm-2
Fig. 5. Potentiodynamic polarization curves of Al(13.8%)-
Zn(8.8%)-Mg alloy in synthetic seawater at room temperature at
different RCE rotation rates
Two plateaus (diffusion-limited current) were observed in
the cathodic region at each RCE rotation rate for this
hydrodynamic system. These plateaus could be due to the
reduction of O2 diffusing through the diffusion boundary
layer only or to the reduction of O2 diffusing through the
diffusion boundary layer and an incompletely reduced
surface film, depending on the value of the RCE rotation rate.
In both the cases, the plateau is controlled by mass transfer.
According to the analysis proposed by Schmitt and
Rothmann [13] and Mendoza [14], it is possible to establish
the different cathodic reactions involved in a system
controlled by mass transfer and under flow turbulent
conditions.
As proposed by Eisenberg et al. [10], it is possible to
calculate the individual contributions to the cathodic current
using the equation:
0:30 0:344 0:644 0:7
ilim ¼ 0:0791nFCi dRCE y Di uRCE
plotted versus the rotation rate of the electrode to a power of
0.7, u0:7
RCE , to obtain Fig. 6. In this figure, the rotation rate of
the electrode is expressed as the peripheral velocity, uRCE.
To determine if the cathodic process is under mass transfer
control, an analysis of the cathodic branch of the polarization
curve could be realized, Fig. 6. In this figure the ilim
experimental data obtained at two different potentials, 1100
and 1400 mV (SCE) within the mass transfer region of the
polarization curve, Fig. 5, are represented by the rhombus
and square markers. Plotting those ilim values as a function of
the RCE rotation rate, Fig. 6, a linear relationship can be
observed. This analysis shows that the measured ilim is
affected by the rotation rate of the electrode and follows the
linear behavior predicted for the RCE equation proposed by
Eisenberg et al. [10], Equation (2), which can be expressed in
a simplified form by Equation (3):
ilim;i ¼ Ai u0:7 (3)
RCE
which constitutes an experimental confirmation that the
cathodic process is mass transfer controlled.
To demonstrate if the cathodic reaction corresponds to the
(2) proposed ORR

where the ilim are in A/m2, F the Faraday constant, n the O2 þ 2H2 O þ 4e ! 4OH (4)
number of electrons involved in the electrochemical
reaction, dRCE the diameter of the cylinder (m), y the it is necessary to calculate the theoretical limiting current
kinematic viscosity of the solution (m2/s), Ci the bulk density of ORR at the different RCE rotation rates using the
concentration of the chemical specie (mol  m3), Di the Eisenberg et al. [10] proposed equation.
diffusion coefficient (m2/s), and uRCE is the peripheral To determine the theoretical relationship between ilim and
velocity of the RCE. u0:7
RCE for O2 reduction, the values of density and kinematic
The above expression for the RCE proposed by Eisenberg viscosity were calculated according to the analysis proposed
et al. [10] is considered and the values of limiting current by Mendoza [14]. The other parameters, like the O2 diffusion
densities ilim are taken from Fig. 5 at each rotation rate and coefficients, were taken from reference [15]. Substituting
these parameters, the theoretical relationship for O2 reduc-
0.9
tion reaction can be obtained, as shown in Fig. 7.
0.8 y = 0.0104x + 0.0784 As can be seen in Fig. 7, good fitting is obtained for the ilim
0.7 R2 = 0.9433 values corresponding to 1100 mV (SCE), allowing then to
i lim, mA.cm -2

-1100 mV
0.6
0.5 -1400 mV
propose that the ORR occurs at the first plateau of the
0.4 y = 0.0022x + 0.0144 Lineal (-1100 mV)
cathodic polarization curve, in the potential range between
0.3
R2 = 0.9762 Lineal (-1400 mV)
1000 and 1200 mV (SCE).
0.2
0.1 3.4 Electrochemical impedance spectroscopy
0
0 20 40 60 80
(EIS) analysis
(u, cm.s-1)0.7
EIS was used as an alternative tool to get more information
Fig. 6. Limiting current density as a function of RCE rotation rates about the effect of flow on the corrosion mechanism. Figure 8
at two different potentials, 1100 and 1400 mV (SCE) within the shows the Nyquist and Bode diagrams for the Al-Zn-Mg
mass transfer region of the cathodic polarization curves shown in alloy immersed in synthetic seawater. Important differences
Fig. 5 can be noticed between laminar and turbulent flow regimes.

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Materials and Corrosion 2009, 60, No. 6
Fig. 8. Impedance diagrams of Al-Zn-Mg alloy in synthetic seawater at different RCE rotation rates
The Nyquist diagram reveals a single capacitive semicircle.
The diameter of this semicircle, that can be attributed to the
charge-transfer resistance, Rct, is higher in laminar than in
turbulent regime. Under laminar flow conditions, Rct reach
values of 1132 Vcm2, while under the turbulent conditions
Rct values decrease significantly, 99.39, 70.67, 67.15, and
59.7 Vcm2 for the different rotation rates 1000, 3000, 5000,
and 7000 rpm, respectively.
One useful method to characterize the mass transfer
influence on the corrosion process is the analysis proposed by
Silverman [16]. Plotting the inverse of Rct, 1/Rct, as a
measure of the estimate corrosion rate versus the logarithm
of the rotation rate as measured in rpm, as can be seen in
Fig. 9, a linear relationship can be observed. If the data points
or slope are similar to those expected from the literature-
derived relationship for the rotating cylinder, mass transfer
probably controls the corrosion rate.
Performing a linear regression of the data points, a
reasonable agreement between the measured and calculated
values of the regression can be observed, providing
experimental evidence that corrosion rate under turbulent
flow conditions could be diffusion controlled, with O2
transport being the most probable mass transfer process.
1 Technology, CONACYT (Mexico).
1 10 100 1000
0.1
1/Rct, Ohm -1.cm -2
y = 5E-05x 0.6926
R2 = 0.9166
0.01
0.001
0.0001
RCE rotation rate, rpm
Fig. 9. Corrosion rate, as 1/Rtc as a function of RCE rotation rates
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Influence of turbulent flow on the corrosion of Al-Zn-Mg galvanic anode 429
According to Silverman [16] if the slope of the regression,
0.69, lies between about 0.65 and 0.75, the corrosion rate is
likely to be significantly influenced or even controlled by
mass transfer, as this is the case.
4 Conclusions
Flow exerts a marked effect on the electrochemical
behavior of the studied Al-Zn-Mg alloy.
Experimental evidence was provided to support the
influence of turbulent flow conditions on the corrosion rate
and the mechanism of the cathodic reaction.
It has been demonstrated that under turbulent flow regime
the cathodic process, the ORR, is mass transfer control.
The corrosion rate of the studied Al-Zn-Mg alloy is
significantly influenced or even controlled by mass transfer.
Acknowledgements: This work was made on the frame of
the following projects: CONACYT NC-204 and CONACYT-
SEMAR 11513.
During this work, Marcela C. Quevedo was supported by
a PhD scholarship from Mexican Council for Science and
10000
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(Received: August 25, 2008) W5141
(Accepted: September 22, 2008)
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