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710

DOI: 10.1002/maco.200704052

Materials and Corrosion 2007, 58, No. 9

Application of Taguchi method for the


characterization of calcareous deposits formed
by pulse cathodic protection
M. Zamanzade, T. Shahrabi* and
E. A. Gharacheh

In this study, the Taguchi method, a powerful tool to design


optimization for quality, is used to find the optimal process
parameters of pulse cathodic protection system for the calcareous
deposits formation. An orthogonal array, main effect and the
signal-to-noise (S/N) ratio are employed to investigate the process
parameters in order to achieve optimum final current density.
Through this study also the main process parameters that affect
the calcareous deposits formation can be found. Experiments were
carried out to confirm the effectiveness of this approach. From the
results, chronoamperometric measurements have been used to

evaluate the influence of pulse cathodic protection on decreasing


the required cathodic current for protection and also decreasing the
surface coverage. The morphology of the formed deposits has been
evaluated through scanning electron microscopy (SEM) and chemical analysis of the formed deposits has been performed using X-ray
diffraction (XRD). It is found that the different environmental
conditions, i.e., Ca2 concentration, Mg2 concentration, rotation
speed, and temperature significantly affect the final required current
density of the pulse cathodic protection. The optimum levels of
parameters at different frequencies are also presented.

1 Introduction

and chloride and this facilitates the calcareous deposits


formation [4].
In this study, the Taguchi method was used to investigate
the effect order of factors on the final current density of
calcareous deposits on mild steel. This method is a
well-known technique that provides a systematic and
efficient methodology for design optimization and it has
been widely used for product design and process optimization worldwide [57].
The Taguchi method can minimize the number of
experiments to a practical level for optimization purposes
through the use of a statistical design of experiments at a
relatively low cost [8,9]. Four factors with three levels,
including the concentrations of calcium ion and magnesium
ion, rotation speed, and temperature were studied. Finally, a
confirmation experiment is conducted to verify the optimal
process parameters obtained from the process parameter
design.

There is a need for an improvement and modification of


cathodic protection systems, to be capable of adequately
protecting submerged structures. For steel structures in
seawater, the usual applied protection potential varies from
0.8 to 1.2 V/SCE (where SCE stands for saturated
calomel electrode), resulting in the reduction of dissolved
oxygen onto the metallic surface, and is accompanied for the
more cathodic potentials by hydrogen evolution. Both
reactions produce hydroxyl ions, which permit the magnesium hydroxide precipitation, provided that the interfacial
pH reaches the critical value of 9.3 [1]. Moreover, these
reactions lead to changes in the inorganic carbonic
equilibrium at the metallic interface, favor carbonate ion
over hydrogen carbonate and allow calcium carbonate
precipitation. Scale deposition on the metallic surface, the
so-called calcareous deposits, acts as a physical barrier
against oxygen diffusion and thus decreases the required
current density to keep efficient protection [2,3]. Furthermore, it has been shown that the pulse CP system requires at
least 10% less current than conventional CP for the same
level of surface potential because, first, the current has
uniform distribution over the structure and, second, perfect
calcareous deposits are formed at shorter times and lower
potentials. Other studies also confirmed that the intense
decrease in surface potential toward negative values causes
repulsion of the aggressive anions such as sulfate, phosphate,


M. Zamanzade, T. Shahrabi
Department of Materials Science and Engineering, Faculty of
Engineering, Tarbiat Modares University, Tehran (Iran)
E-mail: tshahrabi34@modares.ac.ir
E. A. Gharacheh
Department of Industrial Engineering, Faculty of Engineering,
Tarbiat Modares University, Tehran (Iran)

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2 Experimental work
Experiments were performed in an artificial solution
containing the main species present in natural seawater, as
described by the ASTM D1141. Four parameters, each at
three levels as presented in Table 1, were taken into
consideration in the study. A concentration of 25% means
that the bulk concentration is one quarter of the standard
concentration. To select an appropriate orthogonal array for
the experiments, the total degrees of freedom need to be
determined. The degrees of freedom are defined as the
number of comparisons between process parameters that
need to be made to determine which level is better and
specifically how much better it is. For example, a three-level
process parameter counts for two degrees of freedom. The
total degrees of freedom are obtained by multiplying the
degrees of freedom of each process parameter to the number

2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Materials and Corrosion 2007, 58, No. 9

Taguchi method for calcareous deposits

711

Table 1. Values of the parameters at different levels


Symbol

Parameter
Ca2 concentration
Mg2 concentration
Rotation
Temperature

A
B
C
D

Unit

Level 1

Level 2

Level 3

%
%
rpm (revolutions per min)
8C

25
0
120
0

50
50
600
20

100
100
1200
40

*)

*% bulk concentration/standard concentration.

Table 2. Experimental plan using L9 orthogonal array


Experiment no.

1
2
3
4
5
6
7
8
9

1
1
1
2
2
2
3
3
3

1
2
3
1
2
3
1
2
3

1
2
3
2
3
1
3
1
2

1
2
3
3
1
2
2
3
1

Table 3. The average of I/I0 at various frequencies


Experiment no.
1
2
3
4
5
6
7
8
9

10 Hz

100 Hz

1000 Hz

0.7
0.4
0.35
0.4
0.3
0.31
0.4
0.3
0.25

0.62
0.25
0.4
0.3
0.3
0.23
0.2
0.18
0.15

0.6
0.25
0.5
0.125
0.35
0.25
0.05
0.1
0.15

of parameters. Therefore, in this study, four parameters,


each with three levels count for eight degrees of freedom.
Basically, the degrees of freedom for the orthogonal array
should be greater than or at least equal to those for the
process parameters. Obviously, the appropriate orthogonal
array in this case was the standard L9, with four columns and
nine rows. The L9 orthogonal array for this study is shown in
Table 2.

The pH of seawater, fixed by the buffering reaction of


carbonates, was adjusted in all cases to be at 8.2 with a 0.1 M
sodium hydroxide solution. Therefore, even if solutions
having different magnesium and calcium ion concentrations
were prepared, the pH was the same. An electrochemical cell
with a double glass wall for the control of temperature was
used.
The working electrodes were steel rotating disk electrodes
with 2 cm2 area. The electrode material was carbon steel,
with approximate composition (in wt%) of: 97.8% Fe, 0.33%
C, 0.35% Si, 0.67% Mn, 0.042% P, 0.029% S, 0.118% Cr,
0.02% Mo, 0.155% Ni, and 0.401% Cu. The steel surfaces
were polished with silicon carbide (particle size 25 mm),
rinsed thoroughly with distilled water and dried carefully.
Platinum gauze and an SCE were used as the counter and
reference electrode, respectively. A Luggin capillary was
used to position the reference electrode in the desired point of
the cell. After the formation of deposits, the samples were
rinsed with distilled water so as to avoid the crystallization of
sodium chloride.
The pulsed CP apparatus was connected to a Wavetek
model 172B programmable signal source which generated a
pulsed sawtooth potential signal to the specimen surface. The
signal source was triggered by an ATO F-44 sweep generator.
This arrangement allowed both the period and frequency of
the signal to be set independently of each other. The applied
potential signal profile was monitored on a Tektronix model
485 oscilloscope. Similarly, the response current was also
monitored on the oscilloscope using a Pearson electronics
model 411 wide bond pulse current transformer.
Ex situ characterization of the deposits was performed by
scanning electron microscopy (SEM) with elemental
analysis of the formed deposits being performed using
X-ray diffraction (XRD). SEM pictures were obtained on a
JEOL 5410 Low Vacuum.
Electrochemical experiments were driven under potentiostatic conditions using an EG&G Model 273. The formation
kinetic of calcareous deposits reaction has been studied with

Table 4. The factor response at different frequencies


1000 Hz

100 Hz

10 Hz

Parameters
Levels

Average I/I0
1
2
3

0.45
0.24
0.1

0.26
0.23
0.3

0.32
0.17
0.3

0.37
0.18
0.24

0.42
0.28
0.18

0.37
0.24
0.26

0.34
0.23
0.3

0.36
0.23
0.29

0.48
0.34
0.31

0.5
0.33
0.3

0.44
0.35
0.35

0.42
0.37
0.35

Difference

0.35

0.07

0.15

0.19

0.24

0.13

0.11

0.13

0.17

0.2

0.09

0.07

Rank

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712

Zamanzade, Shahrabi and Gharacheh

Materials and Corrosion 2007, 58, No. 9

Fig. 1. Main effect chart at 1000 Hz frequency

Fig. 2. Main effect chart at 100 Hz frequency

the aid of a chronoamperometric technique. Applied pulse


currents were initially interrupted after 80 h, and then the
surface potential was set at E 1.00 V/SCE to implement
the chronoamperometric techniques.

Figures 13 depict the graphs for the output characteristic of the prototypes when they were bent at 10, 100, and
1000 Hz, respectively. It can be seen from Fig. 1 that on the
basis of average I/I0 value, the best combination of
parameters and their levels for the optimum performance
current requirement for 1000 Hz is A3B2C2D2. The
parameters and their levels, i.e., A3B2C2D2 once again
appear to be the best combination for 100 Hz, as it is evident
from Fig. 2. Finally, it can be observed from Fig. 3 that the
best combination of parameters and their levels for 10 Hz
is A3B3C3D3.

3 Results and discussion


The results were obtained by testing all the nine prototypes
for different pulse frequencies, i.e., 10, 100, and 1000 Hz. In
order to normalize the final required current for protection, I/
I0 value was used, in which, I and I0 are the final and initial
current values needed for protection, respectively. Each
prototype represented each experiment of the orthogonal
array (Table 2). The average I/I0 values at different frequencies are summarized in Table 3. In the latter, the results
were analyzed by employing main effects and the signalto-noise ratio (S/N) analyses. Finally, a confirmation test was
carried out to compare the experimental results with the
estimated results and the effects of different parameters were
determined.
3.1 Main effects
For performing the main effect, the average I/I0 value from
the prototypes, which were produced according to the
experimental plan of the orthogonal array (Table 2), at each
frequency was calculated and the results are shown in
Table 3. The factor response on the final current of deposits is
shown in Table 4, which was synthesized by calculating the
mean final I/I0 of all deposits at each level for the various
factors. The maximum difference between the average I/I0 at
two levels of each factor indicated the general effect of that
factor. Based on the value of the differences, the effect order
of factors on the final I/I0 of deposits can be found.

3.2 S/N
The S/N ratio measures the sensitivity of the quality
investigated to those uncontrollable factors (error) in the
experiment. A higher value of S/N ratio is desirable because
a greater S/N ratio will result in smaller product variance
around the target value. The quality characteristic used in this
study was the-lower-the-better.
In order to perform S/N ratio analysis, mean square
deviation (MSD) for the-lower-the-better quality characteristic and S/N ratio were calculated from the following
equations [9]:
MSD

n
1X
1
n i1 y2i

(1)

S=N 10 log10 MSD

(2)

where n is the number of levels in which each parameter


was investigated and yi is the I/I0 value for the ith experiment.
The S/N ratio obtained for each applied frequency is

Table 5. S/N value for different frequencies


Experiment no.

1
2
3
4
5
6
7
8
9

1000 Hz

100 Hz

10 Hz

I/I0

MSD

jS/Nj

I/I0

MSD

jS/Nj

I/I0

MSD

jS/Nj

0.6
0.25
0.5
0.125
0.35
0.25
0.05
0.1
0.15

0.36
0.06
0.25
0.02
0.12
0.06
0.00
0.01
0.02

4.44
12.04
6.02
18.06
9.12
12.04
26.02
20
16.48

0.62
0.25
0.4
0.3
0.3
0.23
0.2
0.18
0.15

0.38
0.06
0.16
0.09
0.09
0.5
0.04
0.03
0.02

4.15
12.04
7.96
10.46
10.46
12.77
13.98
14.89
16.48

0.7
0.4
0.35
0.4
0.3
0.31
0.4
0.3
0.25

0.49
0.16
0.12
0.16
0.09
0.10
0.16
0.09
0.06

3.1
7.96
9.12
7.96
10.46
10.17
7.96
10.46
12.04

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Materials and Corrosion 2007, 58, No. 9

Taguchi method for calcareous deposits

713

3.3 The effects of different parameters

Fig. 3. Main effect chart at 10 Hz frequency

presented in Table 5. It can be seen from this table that the


average value of the S/N ratio increased on increasing the
frequency. For 10 and 100 Hz frequency, the combination of
the parameters and their levels, A3B3C2D1 has consistently
resulted in the maximum value of the S/N ratio. This shows
that in the present case study, the parameters and their
levels, A3B3C2D1 yields the optimum quality characteristic
with minimum variance around the target value for each
frequency. But for 1000 Hz frequency, optimum quality
characteristic with minimum variance is obtained for
A3B1C3D2.

In Figs. 13, the final I/I0 decreased by increasing the Ca2


concentration. The first prominent characteristic of these
figures is the tangible increase in the range of the lines on
increasing the Ca2 concentration. This shows that at 25%
[Ca2]ref, the concentration was too small to allow the
formation of an aragonite layer. The curves obtained at 50%
[Ca2]ref and 100% [Ca2]ref show that the steel surface is
totally covered in each case. Furthermore, it is obvious that at
lower frequencies there will be less sensitivity to calcium ion
concentration. The reason is that at 100 and 1000 Hz, the
formation of Ca-rich deposits (aragonite) is preferred,
therefore, the formation rate of these precipitations can be
controlled by the concentration of this factor. But at lower
frequencies, ton (the duration of current applied) increased,
and this factor resulted in a water reduction reaction and also
buracite formation. Therefore at 10 Hz, the dominant phase
is buracite.
The low effectiveness of the magnesium ion concentration
in the high frequencies is because of the special potential at
which the experiments had been conducted. Normally, by
applying conventional cathodic protection, at potential E
1.0 V/SCE the possibility of buracite precipitations

Fig. 4. SEM micrograph and XRD analysis (l-Co_/Ka1 radiation) of the deposits formed by applying pulse potential at 600 rpm, 1.0 V/
SCE, T 0 8C after 80 h and different frequencies. A are the diffraction lines of aragonite, B those of brucite, and a-Fe are those of the
carbon steel substrate. (a and b) 1000 Hz, (c and d) 100 Hz, (e and f) 10 Hz
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714

Zamanzade, Shahrabi and Gharacheh

(magnesium hydroxide) decreases, and it is the reason for the


low effectiveness of this parameter at higher frequencies
because in this case the ton is too short to change the surface
potential significantly. But the effectiveness of this parameter
increased in the case of 10 Hz as the formation of buracite
favored. On the other hand, it is generally agreed that the
magnesium ions inhibited the formation of calcium carbonate precipitates but it has been shown that a uniform
magnesium-rich film is formed within the very short times of
polarization by pulse cathodic protection at high frequencies,
followed by nucleation and growth of CaCO3 precipitates. It
may be the reason for the observation of low I/I0 value in the
higher frequencies and 50% [Ca2]ref concentration.
The other examined parameter is the varying value of
rotation. Indeed there are different flow rates in the field
because of this; examination of different rotations can shed
light on the different field conditions for deposits formation.
It is obvious that the curve, corresponding to this parameter,
has an optimum point; thus there are factors with opposite
effect. One of these factors is the low penetration rate of
different ion species to the electrolytemetal interface in low
rotations. It is known that at V < 360 rpm, calcium carbonate
precipitation can be controlled by the ion penetration rate
[10], at high rotation speeds, the growth rate is only
controlled by the crystallization kinetics of calcium
carbonate. Otherwise, it has been proved that the calcareous
deposition proceeds by growth of isolated crystals. For less
rotation speeds, the crystals start to coalesce and a 3-D
porous layer builds up. At high rotation speeds, a 2-D type or
a partial blocking deposit was formed and the blocked area
deducted.
Then again, at the lower frequencies the effect of various
rotation speeds decreased. This phenomenon shows that
normally the buracite formation is not controlled by mass
transfer.
On increasing the temperature, oxygen and other ions
penetration rates increase continuously but the concentration
of oxygen solutes in the seawater decreases, this factor is a
critical parameter especially in V < 360 rpm, and the effect
of this parameter at the higher rotations will be lower.
Finally, it is obvious that the diagram corresponding to the
effect of temperature is due to an interactive effect in these
two factors. However, this curve illustrated that T can favor
aragonite at high frequencies (e.g., 100 and 1000 Hz), where
the formation of CaCO3 governs the dominant phenomenon.
Furthermore, it can favor brucite at low frequencies (e.g.,
10 Hz) where the interfacial pH which exists during the
hydrogen evolution, a thermally activated phenomenon,
mainly controls the deposition.

3.4 Confirmation test


Once the optimal combination and levels of the process
parameters at frequency had been obtained, the final step was
to verify the estimated result compared with experimental
values. Figure 4 shows the SEM and XRD analysis of the
calcareous deposits formed in A3B3C2D1 at all the frequencies.
Figure 4a presents a fine-grained flower-shaped structure,
which looks like aragonite deposits; this is because of a
homogeneous nucleation of deposits. These deposits appear
to be compact covering the entire surface. Also XRD analysis confirms that only aragonite deposits could be formed
(Fig. 4b). In this case, we have neither hydrogen evolution
nor deposits deterioration.

Materials and Corrosion 2007, 58, No. 9

As shown in Fig. 4c, on applying pulses with 100 Hz


frequency, calcareous deposits present a typical non-homogeneous layer, but it is clear that the dominant phase is
aragonite. This shows that, in this frequency, the water
reduction reaction is limited but also we have conical porous
structures which could be related to the local water reduction. XRD analyses confirmed that the deposits which are
formed in this case consist of a magnesium-rich layer
(buracite). This is because of hydrogen evolution by the
activation of water reduction reaction [4]. Given a fixed duty
cycle, an increase in frequency decreases ton. As may be
expected, the different ton magnitudes influence the water
reduction reaction and, subsequently, the buracite formation
on the steel surface.
The SEM micrograph and XRD analysis of the deposits
obtained with pulse CP after 80 h are illustrated in Figs. 4e
and 4f. As these figures show, at low frequencies (10 Hz), a
water reduction reaction is activated and then the porous
structure of a buracite layer is formed and also the calcite
islands on all deposits can be seen clearly.
These results consist of the main effect charts at different
frequencies. As seen before, the average amount of I/I0
increases on decreasing the frequency. Because at high
frequencies, the deposits dominantly consist of compact
aragonite deposits which can reduce the final required
current; but on decreasing the frequency formation of buracite is favored.

4 Conclusions
This work was aimed at providing a better understanding
of the competition between the different parameters during the formation of calcareous deposits on steel substrate
under pulse cathodic protection. On the basis of the results
obtained, the following can be concluded:

 The optimal parameters and their levels for 10, 100, and
1000 Hz are A3B3C3D3, A3B2C2D2, and A3B2C2D2,
respectively.
 For 10 Hz frequency, Mg2 concentration produces maximum contribution to the output performance of the
product (I/I0).
 For 100 and 1000 Hz frequencies, Ca2 concentration
demonstrates a maximum contribution to the output
performance of the product (I/I0).
 The parameters and their levels, i.e., A3B3C2D1 yield the
optimum quality characteristic by minimum variance for
100 and 1000 Hz frequencies considered in the study. But
for 1000 Hz, the optimum quality with minimum variance
is A3B1C3D2.

5 References
[1] C. Deslouis, D. Festy, O. Gil, V. Maillot, S. Touzain, B.
Tribollet, Electrochim. Acta 2000, 45, 1837.
[2] R. U. Lee, J. R. Ambrose, Corrosion 1988, 44, 887.
[3] S. Rossi, P. L. Bonora, R. Pasinetti, L. Benedetti, M.
Draghetti, E. Sacco, Corrosion 1998, 54, 1018.
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Materials and Corrosion 2007, 58, No. 9


[4] M. Zamanzade, T. Shahrabi, A. Yazdian, Anti-Corros. Methods
Mater. 2007, 54, 74.
[5] W. H. Wang, Y. S. Tarng, J. Mater. Proc. Technol. 1998, 84,
122.
[6] T. Chung-Chen, H. Hong, J. Mater. Proc. Technol. 2002. 123, 1.
[7] C. Y. Nian, W. H. Yang, Y. S. Tarng, J. Mater. Proc. Technol.
1999, 95, 90.

Taguchi method for calcareous deposits

[8] R. K. Roy, A Primer on the Taguchi Method, Competitive


Manufacturing Series, Van Nostrand Reinhold, New York,
1990.
[9] M. S. Phadke, Quality Engineering Using Robust Design,
Prentice Hall International Inc., Englewood Cliffs NJ, 1989.
[10] D. Deslous, D. Festy, O. Gil, G. Rius, S. Touzain, B.
Tribollet, Electrochim. Acta 1998, 43, 1891.

(Received: December 22, 2006)


(Accepted: January 22, 2007)

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