Electrochimica Acta 56 (2011) 37903798

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Electrochemical impedance spectroscopic investigation of the role of alkaline

pre-treatment in corrosion resistance of a silane coating on magnesium alloy,
ZE41
P. Chakraborty Banerjee a,b , R.K. Singh Raman a,c,
a

Department of Chemical Engineering, Monash University, Clayton, VIC-3800, Australia

CAST Cooperative Research Centre, Hawthorn,VIC-3122, Australia
c
Department of Mechanical and Aerospace Engineering, Monash University, Clayton, VIC-3800, Australia
b

a r t i c l e

i n f o

Article history:
Received 6 November 2010
Received in revised form 7 February 2011
Accepted 10 February 2011
Available online 17 February 2011
Keywords:
Silane coating
Electrochemical impedance spectroscopy
Magnesium alloys

a b s t r a c t
The protective performance of the coatings of bis-1,2-(triethoxysilyl) ethane (BTSE) on ZE41 magnesium
alloy with different surface pre-treatments were evaluated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 0.1 M sodium chloride solution. Electrical equivalent circuits
were developed based upon hypothetical corrosion mechanisms and simulated to correspond to the
experimental data. The morphology and cross section of the alloy subjected to different pre-treatments
and coatings were characterized using scanning electron microscope. A specic alkaline pre-treatment
of the substrate prior to the coating has been found to improve the corrosion resistance of the alloy.
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Magnesium alloys are the lightest metallic material with excellent physical and mechanical properties [1]. High strength to
weight ratio makes them very attractive to the automobile and
aerospace industries. But the use of magnesium alloys is restricted
due to their poor corrosion resistance. The surface lm formed upon
immersion of magnesium in aqueous solution consists of a noncompact duplex layer comprising of an inner MgO layer next to
the metal and an external porous layer of Mg(OH)2 [2]. The protection offered by this lm is highly dependent on the conditions
of exposure [3]. Moreover, the presence of several anions such as,
chloride, sulphate and nitrate in the aqueous solution hinder the
formation of the surface lm and also disrupts the existing lm,
which in turn accelerate the corrosion rate [3]. The partially protective surface lm, low standard reduction potential, presence
of certain impurities (viz., Fe, Cu, Ni) and microgalvanic coupling
between the secondary phases and the -solid solution, as well as
galvanic coupling with other metals accelerate the corrosion problems of magnesium and its alloys. Thus magnesium alloys undergo
different types of corrosion, such as, general, galvanic, pitting and
granular corrosion [3]. It is believed that desired corrosion resis-

Corresponding author at: Department of Mechanical and Aerospace Engineering, Monash University, Clayton, VIC-3800, Australia. Tel.: +61 3 9905 3671;
fax: +61 3 9905 1825.
E-mail address: raman.singh@eng.monash.edu.au (R.K. Singh Raman).
0013-4686/$ see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.02.050

tance of magnesium alloys will necessitate application of suitable

surface barrier, such as chemical treatments and/or coatings.
Silanes are emerging as an attractive environmentally friendly
alternative for improving the corrosion resistance of the metallic substrates as well as for enhancing the compatibility of the
metal surface with the paint systems [48]. The coupling ability of silanes is attributed to their unique chemical structure,
which is given by, R(CH2 )n SiX3 , where R is any organofunctional group, CH2 is the linker and X is the hydrolysable group.
When a silane is used for modication of a polymericinorganic
interface, the organofunctional group as well as the hydrolysable
groups of silane independently bond with the polymer and inorganic surfaces. Silanes form oxane bonds with the hydroxyl groups
of inorganic substrates as well as can form covalent bonds with
suitable functional groups of different polymers.
On the basis of the number of the hydrolysable groups, silanes
are of two types, viz., monosilane, having three hydrolysable
groups and bis-silane, having six hydrolysable groups. Though
monosilanes have been widely used on different metal substrates,
bis-silanes are reported to provide superior corrosion protection
[9]. As bis-silanes can form more silanol groups, in the reticulation stage, these silanol groups can react with each other to form
siloxane bonds, and thus can build robust hydrophobic polysiloxane layers (SiOSi linkages), which, in turn, enhances durability
of silane coatings in aqueous media [10].
The interaction of silanes with metal substrates also depends
on the nature of the inorganic surfaces [9]. Plueddamann [11] suggested that oxide surfaces with a higher number density of hydroxyl

P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

Table 1
Nominal composition of ZE41.

2.3. Hydrolysis of silane and coating

Elements present in ZE41

wt%

3791

Mg

Zn

Ce

La

Nd

Pr

Zr

Fe

Cu

Ni

94.4

3.82

0.64

0.27

0.14

0.06

0.69

0.002

0.002

<0.001

groups facilitate silane deposition. Franquet et al. [12] studied

the effect of surface pre-treatment on an aluminium alloy. They
demonstrated that the variation in the number density of surface
hydroxyl groups provided by different pre-treatments can strongly
inuence the initiation and the formation of silane lms. The facilitating role of hydroxyl group is also suggested by van Ooij et al.
[9], who has reported that the acid or neutral pre-treatments to
be less desirable compared to the alkaline pre-treatments. To the
best of authors knowledge little has been reported in the open
literature on the mechanistic understanding of the inuence of
alkaline pre-treatment on corrosion resistance due to silane coating
on magnesium alloys.
In the present study, the inuence of different alkaline pretreatments on the corrosion resistance of silane coated ZE41 alloy
was investigated. Also for comparison, alloy substrates that were
coated without alkaline pre-treatments were investigated. The bis1,2-(triethoxysilyl) ethane (BTSE) silane was selected for this study,
for the following reasons:
1. It is a non-functional silane, which can form up to six
hydrolysable silanol groups, as a consequence, facilitating the
reaction of the silanol groups with the metallic substrates.
2. Use of non-functional silanes avoids the complications that could
arise due to the directionality of functional groups, such as possibility of upside-down bonding.

Conditions for hydrolysis of bis-1,2-(triethoxysilyl) ethane

(BTSE) are well established [1216]. In the present study, the
established conditions were employed for the hydrolysis, i.e., the
4/6/89.4 (v/v/v) ratio of silane, water and methanol were used as the
base solution for hydrolysis and subsequent condensation. Since
the presence of methanol retards the kinetics of hydrolysis, so 0.6%
acetic acid was added for increasing the kinetics. The silane solution
was then stirred for 24 h at room temperature to ensure complete
hydrolysis of the silane. The pH of the hydrolysed solution was
determined to be 4.5.
The substrates with different surface pre-treatments were
immersed in the silane solution for 5 min and drip dried in air
for 15 min. Curing was carried out at 120 C for 1 h to enhance the
cross linking of the silane lms. The dense network thus produced
may retard the electrolyte transport through the silane layer. For
investigation of the inuence of different pre-treatments alone, a
few specimens without any BTSE coating were subjected to electrochemical testing (potentiodynamic polarization and EIS) and
scanning electron microscopy.

2.4. Characterizations of morphology and cross section

The morphology and cross-section analysis of the coated
specimens (with and without alkaline pre-treatments) and only
pre-treated specimens (without any coating) were examined using
JEOL 840A scanning electron microscope (SEM). For examination of
the cross sections, the specimens were cold mounted and polished,
which enabled the measurements of the thickness of the hydroxide layers formed upon the pre-treatments as well as the coating
layers. All the specimens were required to be gold coated prior to
SEM to avoid charging of the less conductive silane and hydroxide
layers.

2. Experimental
2.1. Test material

2.5. Electrochemical tests

5 cm 10 cm coupons were cut from sand-cast rectangular

plates of ZE41A in T5 condition. The nominal alloy composition
(in wt%) is given in Table 1. The coupons were ground from 320
to 2500 grit on SiC paper. They were rinsed with deionized water,
degreased in acetone and nally dried with compressed air.

Potentiodynamic polarization and electrochemical impedance

spectroscopy (EIS) were performed in 0.1 M sodium chloride solution using a Princeton Applied Research potentiostat (Model 2273)
and an electrochemical cell with three electrodes (specimens with
an exposed area of 0.785 cm2 acted as the working electrode, platinum mesh as counter electrode and saturated calomel electrode
as the reference electrode). All the experiments were performed at
room temperature. Open circuit potential was monitored for 1 h to
conrm its stability with time. Any uctuation of the open circuit
potential less than 10 mV in a period of 1000 s was considered as
a stable potential for carrying out the corrosion tests. Potentiodynamic polarization tests were carried out starting at 250 mV more
negative potential to Ecorr at a scan rate of 0.5 mV/s.
Electrochemical impedance spectroscopy was performed on all
the specimens at 1 h of immersion in 0.1 M sodium chloride solution. The impedance tests were carried out by applying a sinusoidal
potential wave at Ecorr with an amplitude of 10 mV. Impedance
response was measured over frequencies between 1 MHz and
10 mHz, recording 10 points per decade of frequency using Princeton Applied Research (PAR) PowerSuite Electrochemistry package.
Impedance analysis was carried out using PAR ZSimpWin package
for Windows for frequencies between 100 kHz and 50 mHz to prevent misinterpretation of any artefacts that may be present in high
frequency region or the scatter in low frequency region.
All the electrochemical tests were duplicated to examine the
reproducibility of the results. All the plots and tabulated results in
this paper are normalised with respect to the surface area.

2.2. Surface pre-treatments

Three different surface pre-treatments were applied to investigate the inuence of each pre-treatment on the protective
performance of the formed silane coating:
Treatment 1: Substrate was ground to 2500 grit nish, rinsed with
deionized water, degreased with acetone and dried with compressed air. It was then stored in a desiccator for 24 h.
Treatment 2: Substrate was ground to 2500 grit nish, rinsed with
deionized water, degreased with acetone and dried with compressed air. It was then immersed in 3 M NaOH (pH 12) solution
for 48 h to produce a uniform hydroxide layer on the substrate.
Treatment 3: Substrate was ground to 2500 grit nish, rinsed with
deionized water, degreased with acetone and dried with compressed air. It was then subjected to potentiostatic polarization in
3 M NaOH (pH 12) for 600 s at 100 mVSCE to increase the number of
active hydroxyl groups on the substrate. The polarization potential
(100 mVSCE ) was determined upon potentiodynamic polarization
of pure magnesium in 3 M NaOH.

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P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

-1.1
-1.2

E vs SCE/V

3.2. Alloy with different pre-treatments: surface characterization

Tested after keeping in desiccator for 24 h

Tested after polarizing in hydroxide for 600 s
Tested after dipping in hydroxide for 48 h
Untreated ZE41

-1.3
-1.4
-1.5
-1.6
-1.7
-1.8
-8

-7

-6

-5

-4

-3

-2

log (j/A cm-2)

Fig. 1. Potentiodynamic polarization plots of the alloy with different pre-treatments
and untreated alloy.

Since the structure of the hydroxide lm determines the bonding of silane with the metal as well as the performance of silane
coatings in corrosive media, it became essential to develop a broad
understanding of the hydroxide lm formed on the metal surface
upon different pre-treatments. SEM of the surface and cross section
of the alloy after different pre-treatments provided some useful
information. Fig. 3 shows a thick (average thickness 20 m) and
uniform hydroxide layer on the specimen that was pre-dipped in
hydroxide for 48 h. The surface hydroxide lms formed on the other
two specimens (polarized in hydroxide and held in desiccator for
24 h) were too thin to be observed by SEM. Surface topography
of the polarized specimen (Fig. 4(b)) conrmed that the surface
hydroxide layer was indeed very thin, which allowed imaging of
the intermetallics at the grain boundaries of the underlying alloy
microstructure. The topographic features of the specimen that was
held in desiccator for 24 h were similar to those shown in Fig. 4(b).
However, the very thick hydroxide layer that developed over the
specimen dipped in hydroxide for 48 h (Fig. 3) did not allow observation of the underlying microstructure (Fig. 4(c)).

3. Results and discussion

3.3. Coated alloy with different pre-treatments: surface
characterization

3.1. Alloy with different pre-treatments: electrochemical

characterization
The potentiodynamic polarization plots of the alloy with different pre-treatments and the untreated alloy are shown in Fig. 1.
Both cathodic and anodic current densities of all the pre-treated and
untreated specimens were respectively similar. The similar shapes
of the anodic plots as well as the similar magnitudes infer that
the dissolution rate and the dissolution mechanism are analogous.
However, EIS were conducted to further assess the protection, if
any offered by different pre-treatments. The Nyquist plots (Fig. 2)
of the alloy with different pre-treatments and the untreated alloy
are characterized by two capacitive semicircles. The high frequency
semi circles correspond to the charge transfer processes whereas
the medium/low frequency semicircles correspond to the mass
transport relaxation (Mg+ ) in the solid phase, i.e., in an aggregating
layer [17]. The corrosion resistance is determined by the combined diameter of these two semicircles [18]. A marginal increase
in the corrosion resistance was observed in case of the pre-dipped
and pre-polarized specimens, whereas the specimen with naturally
developed hydroxide lm (upon storing in a desiccator for 24 h)
showed a similar corrosion resistance as that of the untreated alloy
(scatter in the data was 500  cm2 ).

3000

Tested after keeping in desiccator for 24 h

Tested after polarizing in hydroxide for 600 s
Tested after dipping in hydroxide for 48 h
untreated ZE41

Z"/ cm

2500

3.4. Polarization and electrochemical impedance spectroscopy

tests: uncoated and different coated specimens

2000
1500
1000
500
0
0

500

1000

1500

2000

As shown in Fig. 5, the silane coated specimens with different pre-treatments have different surface morphologies. Thickness
of the coatings that are developed upon the silane treatments is
expected to be limited to a few hundreds of nanometres [19], which
allows the features underneath the coating to be observed. Therefore, it was possible to observe intermetallic precipitates present at
the surface of the coated specimens without alkaline pre-treatment
(Fig. 5(a)) and, to some degree, even in the case of the alloy with
presumably very thin hydroxide layer as developed upon polarization (Fig. 5(b)). In this context, it is interesting to observe a few
precipitates on the alloy pre-dipped in hydroxide for 48 h and then
BTSE coated (Fig. 5(c)), in spite of the considerably thicker hydroxide layer developed upon this pre-treatment (Figs. 3 and 4(c)).
However, a careful observation of the cross section of the specimen pre-dipped in sodium hydroxide (Fig. 3(a)) would suggest
that though the alloy matrix had reacted with sodium hydroxide
to produce a thick hydroxide layer, the intermetallic particles had
not reacted and were embedded into the hydroxide layer. In fact,
some of these particles extend right up to the surface of the hydroxide layer, which explains the observed particles under the silane
coated specimens (Fig. 5(c)). Examination of the cross section of this
specimen (Fig. 6) conrms the silane coating to be thinner in comparison with the thickness of the hydroxide layer and it is barely
distinguishable.

2500

3000

Z'/ cm

Fig. 2. Nyquist plots of the alloy with different pre-treatments and untreated alloy.

Fig. 7 depicts the potentiodynamic polarization plots for the

uncoated, only hydroxide pre-dipped (without any coating) and
BTSE coated (with and without different alkaline pre-treatments)
specimens. The anodic current densities of the BTSE coated alloy
with prior alkaline pre-treatments (both pre-dipped and prepolarized) were higher than others up to 1.2 VSCE , which conrms
that the alkaline pre-treatments and then BTSE coating were effective in impeding the anodic dissolution reaction for these coated
specimens. Beyond this potential, anodic current densities of all
the specimens were similar, implying that the protective coatings
formed on the alkaline pre-treated and then BTSE coated specimens
disintegrate at these high anodic over potentials. The effectiveness
of the combined role of alkaline pre-treatment and BTSE coating is

P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

3793

Fig. 3. Back scattered electron (BSE) image of the cross section of the alloy pre-dipped in hydroxide.

evidenced from the observation that the anodic current densities

of the BTSE coated specimen (without alkaline pre-treatment) and
the only hydroxide pre-dipped specimen (without BTSE coating)
were similar to that of the uncoated specimen at all anodic over
potentials. Cathodic current densities for all the specimens were
similar. The corrosion potentials (Ecorr ) of the BTSE coated specimen
(without alkaline pre-treatment) and the specimen polarized in
hydroxide and then BTSE coated are more active than the uncoated
alloy, whereas, Ecorr of the specimen dipped in hydroxide and BTSE
coated is about 90 mV more positive than the untreated alloy. It

may be interesting to note that the Ecorr of the BTSE coated (with
and without alkaline pre-treatment) specimens varied over a wide
range (maximum variation is about 200 mV). However, this kind
of difference in Ecorr between different coated magnesium alloys
has been observed in several other studies [10,2026]. It is quite
plausible to assume that the nature (uniformity and thickness) of
the silane lms formed after different pre-treatments will be dissimilar. In the present study, the observed variation in Ecorr (which
is a measure of the corrosion susceptibility [27]) of the different
BTSE coated specimens, may be attributed to the different corro-

Fig. 4. SEM images of the surface morphology of the alloy: (a) untreated, (b) polarized in hydroxide and (c) dipped in hydroxide for 48 h.

3794

P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

Fig. 5. SEM images of the surface morphology of silane coated alloy: (a) without alkaline pre-treatment, (b) polarized in hydroxide for 600 s and (c) pre-dipped in hydroxide
for 48 h (arrows show the intermetallic particles underneath the coatings).

sion susceptibility, arising due to dissimilar nature of the silane

coatings formed on these specimens.
The Nyquist plots (Fig. 8) of all the specimens show that while
slight improvement in impedance was observed in the case of the
only hydroxide pre-treated and only BTSE coated specimens, the
highest improvement in impedance was observed in case of the
BTSE coated specimens with alkaline pre-treatments. A comparison of the plots would suggest that the total impedances, which
are the measure of the corrosion resistances, offered by the alkaline
pre-treated specimens to be 56 times superior to that of uncoated
alloy. The total impedance of the specimen pre-dipped in hydroxide
and then BTSE coated is 6 k, and that of the specimen prepolarized in hydroxide and then BTSE coated is 5 k, whereas
the total impedance of the uncoated alloy is in the range of 1 k.
From the polarization and EIS results, it can be concluded that
the improvement in corrosion resistance was not only due to the
alkaline pre-treatment or BTSE coating alone, but due to the combined effect of both. Electrical equivalent circuits (EEC) can be
employed to obtain a mechanistic insight into the inuence of the
different surface pre-treatments on the corrosion behaviour of the
BTSE coated specimens. In the present study, impedances of the
interfaces of substrate/surface hydroxide/NaCl solution and substrate/surface hydroxide/silane lm/NaCl solution were analysed
on the basis of identication of appropriate EEC. In corrosion processes, each of these interfaces can be represented as a parallel
combination of a capacitance and a resistance. This concept forms
the basis of EECs that have been employed here. EECs were developed for different interfacial scenarios based upon hypothetical
corrosion mechanisms, and the simulation data were generated for

each EEC. The experimental data sets were compared with the corresponding simulated data sets, in order to arrive at an appropriate
corrosion mechanism for each scenario. It was possible to calculate interfacial resistances and capacitances that can be related to
the homogeneity of the lms and can describe the corrosion mechanisms. The relative magnitudes of these components provide an
estimation of the protection provided by a given coating.
In the present study, complex nonlinear least squares tting
(CNLS) was used to analyse the impedance data. In this method, all
the data are simultaneously tted to a given EEC containing a set of
unknown parameters (for example, circuit elements), which may
enter nonlinearly in the formula for the measured function of frequency and impedance. It also provides uncertainty estimates for
all the estimated parameters in a given EEC. Unlike the other methods (KronigKramers relations, ordinary nonlinear least squares,
etc. [28]) it allows to t a very complicated model with large number of circuit elements. CNLS procedure implies minimization of
the sum of square functions [28],

S=

k


{wia [feia fta (; p)] + wib [feib ftb (; p)] }

(1)

i=1

where ft ( ; p) is a function of both the angular frequency () and

a set of EEC parameters p. i = 1,. . ., k represents the data points
associated with i . ft ( ; p) can be divided into two parts, fta (; p)
and ftb (; p), (both depend on the same set of parameters). fta (; p)
and ftb (; p) can either represent Zreal and Zimaginary or |Z| and 
(phase angle of impedance), respectively. wia and wib are the weights

P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

3795

Fig. 6. SEM images of the cross section of the pre-dipped in hydroxide and then BTSE coated specimen: (a) secondary electron image, (b) back scattered electron image and
(c) secondary electron image (higher magnication).

obtained data values. When ftb (; p) = 0, CNLS reduces to ordinary

non linear least squares [28]. In the present study, since feia and

feib values do not vary over several orders of magnitude, the t-

ting procedure was chosen to be unity weighted (i.e., wia = wib = 1).
The circuit description code (CDC) used by Boukamp [29], has been
followed in the present study.
For the uncoated alloy, a simple EEC was used to simulate
the data corresponding to a hypothetical corrosion mechanism,
where electrical double layer and naturally formed surface hydroxide lm behave as a set of capacitance and resistance in parallel
(as shown in Fig. 9). Theoretical simulation was conducted using
a Rs (Cf [Rf (Cdl Rc )]) electrical equivalent circuit (Fig. 9), where the
solution resistance is represented by Rs . The surface lm, which is
represented by a parallel combination of a capacitance (Cf ) and the
surface lm resistance (Rf ), is in parallel with the electrical double layer (represented by the parallel combination of the electrical
double layer capacitance (Cdl ) and charge transfer resistance (Rc )).
A comparison with the simulated results based upon other EECs
suggested that Rs (Cf [Rf (Cdl Rc )]) was the closest t to the experimental impedance data for the uncoated alloy with a relatively low
chi square value (2 103 ) as well as a low error (4%) in impedance
measurement. The calculated parameters for the proposed EEC are
shown in Table 2.
The simulated results and the observed Bode impedance plots
for the uncoated ZE41 alloy are shown in Fig. 10. Error plots (Fig. 11)

for the uncoated alloy show that the maximum error in simulated
data is less than 7% for both |Z| and angle. Though the coated specimens were found to conform to a different EEC, the trend of error
plots for all of them was similar to that shown in Fig. 11.

-1.1

Uncoated
BTSE coated (without alkaline pre-treatment)
Dipped in hydroxide and BTSE coated
Polarized in hydroxide and BTSE coated
Only hydroxide pre-treated (dipped)

-1.2

E vs SCE/V

related to the ith data point. feia and feib are the experimentally

-1.3

-1.4

-1.5

-1.6

-1.7
-8

-7

-6

-5

-4

-3

-2

log (j/A cm-2)

Fig. 7. Potentiodynamic polarization plots of BTSE coated (with and without alkaline
pre-treatment), hydroxide pre-treated (without any coating) and uncoated ZE41
alloy.

3796

P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

6000

BTSE coated (without alkaline pre-treatment)

Polarised in hydroxide and BTSE coated
Dipped in hydroxide and BTSE coated
Uncoated
Only hydroxide pre-treated (dipped)

Z"/ cm2

5000
4000
3000
2000
1000
0
0

1000

2000

3000

4000

5000

6000
Fig. 11. Error plots for measured and calculated values of uncoated ZE41 alloy.

Z'/ cm

Fig. 8. Nyquist plots of the BTSE coated (with and without alkaline pre-treatment),
hydroxide pre-treated (without any coating) and uncoated ZE41 alloy.

Rs

Surface film

Cf

Electrical
double layer

Rf

Cdl

Rc

Metal
Fig. 9. The electrical equivalent circuit tted to the experimentally obtained
impedance data of the uncoated alloy.
Table 2
Calculated parameters for the components in Rs (Cf [Rf (Cdl Rc )]).
Parameters

Estimated values

Rel. std. error/%

Rs / cm2
Cf /F cm2
Rf / cm2
Cdl /F cm2
Rc / cm2

157
1.1 105
364
1.3 105
523

1
5
17
18
11

Several EECs were employed to t the experimental impedance

data for the BTSE coated specimens with different pre-treatments.
However the lowest chi square values and the minimum overall errors in impedance measurements were obtained with
Rs (Qsi [Rsi (Cfdl Rc )]) (Fig. 12). In this EEC, the solution resistance is
represented by Rs . The silane lm is characterized by a constant
phase element (CPE) (Qsi ) and pore resistance (Rsi ). Other studies [4,7,20,30,31] suggest that it is typical to represent the silane
lm using a CPE, instead of a pure capacitor. The other time constant (represented by the parallel combination of a capacitance
Cfdl and a resistance Rc ) that is present in the EEC is assumed to
describe the combined responses of the electrical double layer and
the hydroxide lm. This aspect will be explained in more details in
the following sections. The calculated and the measured Bode plots
for the specimens with different coatings are shown in Fig. 13.
Table 3 presents the calculated values of the different parameters associated with the proposed EEC for different specimens. Both
Rsi and Rc for the specimen dipped in hydroxide and then BTSE
coated is higher than others. Also, the total impedance, which is a
measure of the corrosion resistance [18], has the highest value for
the pre-dipped specimen. Although Qsi for all specimens are similar,
Cfdl of different specimens varies over several orders of magnitude.
Also, Cfdl determined for different coated specimens are different
from the typical electrical double layer capacitance for metal electrodes, which in general ranges in F/cm2 [32]. Thus it is suggested
that the time constant, consisting of Cfdl and Rc did not arise due to
the sole response of the electrical double layer, but it did due to a
combined response of the surface hydroxide lm and the electrical
double layer. The Cfdl of the BTSE coated specimen pre-dipped in

Rs
Silane film

Qsi Rsi

Electrical
double layer

Cfdl Rc

Metal
Fig. 10. Bode plots for measured and calculated values of uncoated ZE41 alloy.

Fig. 12. The electrical equivalent circuit tted to the experimentally obtained
impedance data of the different BTSE coated specimens.

P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

3797

Fig. 13. Bode plots for measured and calculated values of the different coated specimens: (a) only BTSE coated, (b) pre-dipped in hydroxide and then BTSE coated and (c)
pre-polarized in hydroxide and then BTSE coated.

hydroxide was 34 orders of magnitude lower than the other two

specimens (Table 3). Since capacitance is directly proportional to
the area of the capacitor, the relatively lower capacitance indicates
a comparatively lower exposure of the metal/hydroxide interface to
the electrolyte. This can be attributed to the fact that after immersion of the specimen in 3 M sodium hydroxide (pH 12) for 48 h, a
considerably thicker and less defective surface hydroxide lm was
developed on this specimen (Fig. 3), which enhanced the cross linkage of silane with surface hydroxide during coating process, and
thus presumably produced a uniform and less defective coating.
Improvement in the corrosion resistance of the BTSE coated
specimens as a result of the alkali pre-treatments is understandable
if one considers the Pourbaix diagram for magnesium [33], shown
in Fig. 14. In aqueous environment, magnesium forms a surface lm
of magnesium hydroxide. The protection offered by Mg(OH)2 lm is
highly dependent on the pH and presence of different anions in the
solution [34]. From the Pourbaix diagram, it is evident that a passive
Mg(OH)2 lm will form at pH >11. The nature and protectiveness
of this hydroxide layer is reported to be profoundly inuenced by
the alloying constituents of different magnesium alloys [3436].
For example, in the case of MgAl alloys, the major alloying element, Al plays an important role in the surface lm formation [35].

Therefore, it may be important to consider the role of Zn, the major

alloying element in ZE41 alloy. The surface lm formed on a Zn
electrode is stable in an aqueous solution at pH 8.212.1 [37]. Thus,
on immersion in the alkaline solution (3 M NaOH) with pH 12 for
48 h, a thick and uniform hydroxide lm was formed on ZE41 alloy
(Fig. 3). The protective performance of any silane coating primarily depends on the successful cross linkage between the silane lm
and the metal hydroxide. Plueddamann [11], Franquet et al. [12]
and van Ooij et al. [9] have earlier suggested that the alkaline pretreatment facilitates silane deposition, which is consistent with the
observation of the present study. Formation of a uniform hydroxide lm after alkaline pre-treatments indeed aids formation of a
protective coating on the metal surface (as is evidenced from the
electrochemical results).
Among the specimens that were alkaline pre-treated before
BTSE coating, the specimens pre-dipped in hydroxide and then
coated with BTSE showed a superior corrosion resistance to those
subjected to polarization in hydroxide and then coating (as evidenced from the Nyquist plots (Fig. 8)). This behaviour may be
attributed to the characteristics of the hydroxide lms developed
during the two pre-treatments. Also, Figs. 3 and 4 show formation of
a thicker and relatively uniform hydroxide lm upon prior dipping

Table 3
Calculated parameters of the proposed EEC for the coated specimens.
Specication

Only BTSE coated

Pre-polarized in NaOH + BTSE coated
Pre-dipped in NaOH + BTSE coated

Rsi / cm2

Rc / cm2

Qsi /F cm2

Value

Error/%

Value

Error/%

Value

3167
4620
4881

1
2
24

899
352
997

12
11
6

1.1 105 3
1.1 105 2
1.3 105 8

Cfdl /F cm2

Error/%

Value

Error/%

Value

0.9
0.9
0.7

1
1
2

2.1 103 12
7.5 104 6
9.7 107 18

Chi squared
value

Total
error/%

8.3 104
7.5 104
2.8 103

3
3
5

Error/%

3798

P. Chakraborty Banerjee, R.K. Singh Raman / Electrochimica Acta 56 (2011) 37903798

Acknowledgements
Authors would like to acknowledge DSTO for their nancial support for investigation of silane coating for ZE41 alloy. The kind
assistance of Abhishek Saxena is also gratefully acknowledged.
References

Fig. 14. Pourbaix diagram [33].

in hydroxide for 48 h. A cursory comparison may not provide any

convincing reason for the prior dipping (as opposed to polarization)
to produce a thicker and less defective hydroxide lm. However,
the thermodynamic and kinetic factors seem to provide a convincing explanation. As the Pourbaix diagram (Fig. 14) would suggest,
little thermodynamic preference for the two scenarios since magnesium will form a stable hydroxide lm at every potential when
immersed in an aqueous solution of pH 12. Thus, the lm deposition kinetics would be the only governing factor for the properties
of the hydroxide layer. The long dipping time (48 h) in hydroxide
solution, allowed development of a relatively uniform and thicker
lm (Figs. 3 and 4) under close to equilibrium condition. On the
other hand, the effective exposure time of the specimen subjected
to prior polarization was only 600 s and the deposition occurred
in a relatively forced condition, compromising the quality of the
hydroxide lm.
4. Conclusions
Inuence of alkali surface pre-treatment of BTSE coated ZE41
has been analysed using potentiodynamic polarization and electrochemical impedance spectroscopy. A comparative study of the
corrosion resistance offered by BTSE coated (with and without
alkali pre-treatment) and uncoated ZE41 suggests that alkaline
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resistance. However, the nature of the alkaline pre-treatments
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of a pre-treatment that results in the formation of a thick and
uniform hydroxide lm on the surface, which facilitates formation of a protective silane lm on the substrate. The EIS results
are in good agreement with the potentiodynamic polarization
results.

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