Electrochimica Acta 52 (2007) 4554–4559

Electrochemical and DFT studies of ␤-amino-alcohols

as corrosion inhibitors for brass
Guo Gao a,∗ , Chenghao Liang a,b
a State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China
b Electromechanics & Materials Engineering College, Dalian Maritime University, Dalian 116026, China

Received 9 October 2006; received in revised form 11 December 2006; accepted 15 December 2006
Available online 21 January 2007

Abstract
The electrochemical performance of 1-diethylamino-propan-2-ol (EAP) and 1,3-bis-diethylamino-propan-2-ol (DEAP) for brass in simulated
atmospheric water is evaluated by potentiodynamic curves and electrochemical impedance spectroscopy (EIS). The experimental results show that
the investigated compounds, which can effectively retard the anodic dissolution of brass, are anodic inhibitors. Furthermore, the inhibition efficiency
of DEAP is higher than that of EAP at the same concentration. This observation is supported by density functional theoretical (DFT) parameters
such as the highest occupied molecule energy level (EHOMO ), the lowest unoccupied molecule energy level (ELUMO ), the energy difference (E)
between EHOMO and ELUMO , Mulliken charges and the HOMO orbital.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Brass; Corrosion inhibitor; ␤-Amino alcohol; EIS; DFT calculation

1. Introduction cupied molecule orbital (LUMO), energy difference between

Nowadays the corrosion inhibitor of brass is an important
industrial and academic topic. A variety of organic compounds
containing heteroatoms (N, O, S) which can donate electron
pairs are used to inhibit brass corrosion in various aggressive
electrolyte [1–6]. The primary step in the action of organic
corrosion inhibitors in the solution is usually attributed to the
adsorption process [7]. Studies [8,9] report that the adsorption
process depends on the physico-chemical properties of inhibitor
molecule, related to the electronic density of donor atoms and
on the possible steric effects. The adsorption also depends on
the nature of metal surface, the chemical composition of the
solution, temperature of the reaction and on the electrochemical
potential at the metal/solution interface [10,11].
Recently, the density functional theory (DFT) is success-
fully applied to describe the structural importance of corrosion
inhibitors and its adsorption efficiency on the metal surface
[12,13]. The electronic properties of corrosion inhibitors such as
the highest occupied molecule orbital (HOMO), the lowest unoc-
EHOMO and ELUMO , atomic charges and dipole moments have
been achieved the appropriate correlation. So, we can understand
the reactivity behavior of hard and soft acid–base theory which
can provide a systematic analysis for the interaction between the
inhibitor and metal surface.
The aim of this work is to correlate the molecule structures
of ␤-amino-alcohols namely 1-diethylamino-propan-2-ol (EAP)
and 1,3-bis-diethylamino-propan-2-ol (DEAP) and their inhibi-
tion properties for brass in simulated atmospheric water. The
electrochemical performance of these compounds for brass is
investigated through potentiodynamic curves and EIS. The inhi-
bition efficiency of DEAP (92.9%) is higher than that of EAP
(90.7%), so that DEAP could be considered an effective cor-
rosion inhibitor to conserve metal surface from atmospheric
corrosion. This observation is supported by the DFT calcula-
tion which can provide an interpretation between the electronic
and structural properties of the investigated compounds and their
experimental results as corrosion inhibitors.
2. Experimental procedure

∗ Corresponding author. The potentiodynamic curves measurement was carried out

E-mail address: gaogaoguoguo@yahoo.com.cn (G. Gao). on a PAR M173 potentiostat/galvanostat. The EIS test was per-

0013-4686/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.12.058
 G. Gao, C. Liang / Electrochimica Acta 52 (2007) 4554–4559 4555

Fig. 1. Molecular structure of amino-alcohols.

formed on a potentiostat/galvanostat PAR M283 and a PAR

M1025 frequency response detector. The employed amplitude
of the sinusoidal signal was ±10 mV, frequency ranging from
10 kHz to 10 mHz. A saturated calomel electrode (SCE) was
used as the reference electrode and a platinum sheet as the
counter electrode, the working electrode was brass (composi-
tion, wt.%: 63.5–68.0 Cu, 0.10 Fe, 0.03 Pb, 0.005 Sb, 0.002 Bi,
0.01 P, and balance Zn) with exposed area of 1 cm2 . The EIS
parameters were determined with the software of ZSimpWin.
All the electrochemical tests of brass were done with the thick-
ness of 100 ␮m electrolyte layer, simulating the atmospheric Fig. 2. Polarization curves of brass with EAP at different concentrations.
corrosion. The equipment was similar to that reported by Vera
Cruz [14].
the investigated compounds were anodic inhibitors. The addi-
The electrolyte was simulated atmospheric water accord-
tion of inhibitors leads to a greater tendency towards passivity
ing to ASTM 1384, which was prepared by distilled water
than without the inhibitor, and the corresponding passive cur-
and 0.1 g/L NaCl, 0.1 g/L NaHCO3 and 0.1 g/L Na2 SO4 . The
rent density for EAP and DEAP is around 18 and 10 ␮A/cm2 ,
specimens were polished with grit emery paper to 2000 grade,
respectively. Furthermore, the passive trend is more evident in
degreased by ethanol, rinsed by distilled water and dried in air.
the presence of DEAP as suggested by the desorption potential
All the investigated amino-alcohols were synthesized in
(Edes ) which increased with increasing inhibitor concentration.
the laboratory through diethylamine with appropriate epoxide
The good inhibition performance shown by DEAP compared
(2-methyl-oxirane and 2-chloromethyl-oxirane) in the suitable
to EAP may be attributed to the free electron pair of DEAP
solvent at room temperature according to the reported proce-
molecule is easily for a reactant complex to be obtained by
dure. They were fully characterized by MS, IR, 1 H NMR and
13 C NMR by comparison with the known compounds [15–18]. means of collision, thus formation a stable adsorbed film on
the electrode surface.
Structure of the investigated compounds in this work was given
Figs. 2 and 3 also reveal that the inhibitor molecules were
in Fig. 1.
able to induce some corrosion activity of brass during the initial
anodic process, probably due to the inhibitor molecules displace
3. Computational details some hydrated layers of brass oxides/hydroxides film in order
to create more favorable sites for the formation of stable pro-
Calculations were carried out with the Gaussian 98 program tective layer. In the case of DEAP the heteroatoms such as N
[19]. Exchange and correlation calculations were performed
with the functional hybrid B3LYP [20] and the 6–311G** orbital
basis sets for all atoms. The structure optimization and the vibra-
tional analysis of the optimized structures were performed in
order to determine whether they corresponded to a maximum
of a minimum in the potential energy curve. For the molecule
structures of EAP and DEAP, the possible electrophilic sites
reactions with metal surface have been traced out by applying
frontier molecule orbital theory and Mulliken charges.

4. Results and discussion

4.1. Potentiodynamic measurements

The polarization curves were used to find the interac-

tion between the organic inhibitor and the electrode surface.
Figs. 2 and 3 show the polarization curves for brass under thin
electrolyte layer containing different concentration of EAP and
DEAP. It is clearly that the cathodic effect is approximate con-
stant whereas the anodic effect is more pronounced, suggesting Fig. 3. Polarization curves of brass with DEAP at different concentrations.
4556 G. Gao, C. Liang / Electrochimica Acta 52 (2007) 4554–4559
Fig. 4. Impedance diagram obtained for brass in the presence different concen-
trations of EAP in simulated atmospheric water.
and O atoms with lone pair electrons are firstly chemisorbed on
the electrode surface, displacing the SO4 2− and Cl− ions and
the positive charge part of the ethyl group is fixing by physical
adsorption. Then the anodic active sites vulnerable for corro-
sion attack gradually decreases with increasing the inhibitor
concentration.
4.2. EIS tests
The inhibition process of amino-alcohols on brass is also
studied by EIS tests at different concentrations. Figs. 4 and 5
present the Nyquist complex plane plots of brass in simulated
atmospheric water containing different concentrations of EAP
and DEAP. It is seen that the semicircles whose diameters
increase for both inhibitors whereas the extent is much higher
for DEAP than for EAP. This observation is consistent with the
polarization curves measurements revealing that DEAP is a good
inhibitor.
Fig. 5. Impedance diagram obtained for brass in the presence different concen-
trations of DEAP in simulated atmospheric water.
Fig. 6. Equivalent circuit model for brass under thin electrolyte layer.
It is also found that the impedance spectra display a depressed
semicircle which can be modeled as an electric equivalent circuit
(see Fig. 6) that has been previously used to evaluate the inhi-
bition mechanism of organic inhibitors in aggressive medium
[21]. This model considers the charge transfer resistance (Rct ),
the double layer capacitance (Qdl ), the adsorption resistance (Ra )
relating to the diffusion processes of brass and hydrogen cations
through the adsorbed film, the adsorption capacitance (Qa ) and
the solution resistance (Rsol ). The equivalent circuit represents
the corrosion process and the constant phase element (CPE), Qi ,
may be expressed as [22]:
(iw)−n
ZQ = (1)
Y0
where ZQ is the impedance of CPE, Y0 the part of the CPE
independent of the frequency, i the imaginary number (i2 = 1),
w the angular frequency and n is the surface irregularity.
The CPE is attributed to the non-homogeneity of the electrode
surface as well as due to the mass transport process [23]. If the
electrode surface is homogeneous and plane, the exponential
value (n) is equal to 1 and the electrode surface can be treated
as an ideal capacitance. The interface time constant (τ) and the
double layer capacitance value (Cdl ) of the CPE can be calculated
by the following equations [24,25]:
1/n
Cdl = (Y0 R1−n
ct ) (2)
τn
Y0 = (3)
Rct
The inhibition efficiencies of the inhibitors are determined
by EIS measurements using the following equation [26]:
 
Rct
η% = 1 −  × 100 (4)
Rct
where Rct and Rct represented, respectively, the charge transfer
resistance in the absence and presence of inhibitors.
The values of associated electrochemical parameters are
given in Table 1. An increase in the Rct value is observed
with increasing the inhibitor concentration, suggesting that
the charge transfer process is retarded due to the diminish-
ing of uncovered area available for corrosion reaction. In this
case, the higher inhibitor concentration, the lower is the asso-
ciated corrosion rate. It shows that the Rct value increase
to 89.3 k cm2 when the DEAP concentration is at 10−2 M,
however, at the same concentration for EAP, the Rct value is
68.1 k cm2 , revealing that DEAP can effectively inhibits the
 G. Gao, C. Liang / Electrochimica Acta 52 (2007) 4554–4559 4557

Table 1
Values of the equivalent circuit used for the best fit to Nyquist complex plane plots of brass with different concentrations of EAP and DEAP

Cinhibitor Ya (×10−4 k−1 cm−2 sn ) na Ra Ydl (×10−4 k−1 cm−2 sn ) ndl Rct Cdl τ (×10−2 s) η (%)
(mol/L M) (k cm2 ) (k cm2 ) (␮F cm−2 )

Blank 0.40 0.93 4.3 0.14 0.60 6.3 2.77 1.75 –

EAP
10−3 0.18 0.94 6.5 0.41 0.52 36.7 59.8 219.40 82.8
2.5 × 10−3 0.15 0.96 5.3 0.29 0.51 47.6 39.5 188.17 86.8
5 × 10−3 0.14 0.95 6.4 0.26 0.50 52.9 35.8 189.17 88.1
7.5 × 10−3 0.16 0.96 5.8 0.27 0.52 63.2 44.2 279.44 90.0
10−2 0.12 0.97 4.5 0.19 0.53 68.1 23.8 162.6 90.7
DEAP
10−3 0.19 0.95 9.8 0.24 0.54 50.4 28.20 142.25 87.5
2.5 × 10−3 0.14 0.96 8.9 0.12 0.51 65.9 9.57 63.11 90.4
5 × 10−3 0.20 0.96 13.1 0.24 0.60 72.8 37.74 253.50 91.3
7.5 × 10−3 0.24 0.91 29.9 0.20 0.56 84.0 30.01 252.58 92.5
10−2 0.23 0.90 39.4 0.19 0.58 89.3 27.89 223.42 92.9

anodic dissolution of brass than for EAP in simulated atmo- are all over 2.5 s. This observation suggests that the amount of
spheric water. accumulated charge per unit on electrode surface with DEAP is
Table 1 shows that the Ra value increases in all cases com- lower than EAP.
pared to the medium without inhibitors. This evolution exhibited
indicates that a modification of the adsorbed film occurring 4.3. Theoretical studies
on the brass surface originated from the adsorbed inhibitor
molecules. The smaller modification appears in the presence The corrosion inhibition of brass by EAP and DEAP was
of EAP, and the significant modification occurs with DEAP. For attributed to the adsorption of the molecule species. It was shown
example, the Ra value is markedly raised to 39.4 k cm2 when from experimental results that the investigated compounds were
the DEAP concentration is at 10−2 M, while for EAP at the same good inhibitors, but no giving further insight into the correlations
concentration the Ra value is moved only to 4.5 k cm2 . On the between corrosion inhibition and the molecule properties such as
other hand, the values of na were found in the 0.90–0.97 interval, frontier orbital energies, dipole moment, Mulliken charges and
revealing that the adsorbed film were relatively homogeneous. the HOMO orbital. Thus the density functional theory (DFT)
The variation na value is consistent with the modification of the was applied to study the geometrical and electronic structures
chemical composition of the adsorbed film in combination with of the inhibitors. The optimized molecule of EAP and DEAP
their thickness as suggested by the Ya value. as well as the bond parameters such as the bond distance, bond
The addition of inhibitors to the aggressive medium also angles and dihedral angles were given in Fig. 7 and Table 2.
modifies the Cdl value. The analysis of the electrochemical It is shown that the distance C6 –C7 is smaller for EAP with
parameters reveals that the Cdl value increases in the presence respect to DEAP due to the replacement of the H-atom (C7 )
of inhibitors whereas has a decrease trend with increasing the
inhibitor concentrations. For example, for EAP (10−3 M), the
Table 2
Cdl value (59.8 ␮F cm−2 ) declined to 23.8 ␮F cm−2 (10−2 M) Geometric parameters (bond length in Å, bond angles and dihedral in ◦ ) of EAP
while for DEAP (10−3 M), the Cdl value (28.20 ␮F cm−2 ) is and DEAP
reduced to 27.89 ␮F cm−2 (10−2 M). This shows that a higher
Bond EAP DEAP
concentration is needed for EAP to reduce the double layer
capacitance. However, for DEAP, the evolution of Cdl value Bond length (Å)
shows a slight decrease with increasing the inhibitor concen- C1 –C2 1.53 1.53
tration, stabilizing in values around 28 ␮F cm−2 . This indicates
C2 –N1 1.48 1.48
C6 –C7 1.52 1.54
that the adsorbed film by DEAP on electrode surface is more C6 –O8 1.46 1.46
stable than that by EAP.
Bond angle (◦ )
The interface time constant value (τ) against the amino- C5 –N1 –C3 113.34
alcohols at different concentrations, also shows that DEAP C7 –C6 –C5 113.08
behaves as a better corrosion inhibitor than EAP. In general, the C1 –C2 –N1 114.39
τ value will be as large as possible when the corrosion inhibitor C11 –C10 –N2 33.87
is added to an aggressive medium. Thus, the value of τ can be Dihedral angle (◦ )
used to evaluate the inhibitor adsorption process on the elec- C5 –N1 –C3 –C4 74.62
trode surface. For example, when the EAP concentration is only C7 –C6 –C5 –N1 165.20
−29.74
at 7.5 × 10−3 M, the τ value moves over 2.5 s, while for DEAP
C1 –C2 –N1 –C5
C11 –C10 –N2 –C8 −40.19
at the concentration range (5 × 10−3 to 10−2 M), the τ values
4558 G. Gao, C. Liang / Electrochimica Acta 52 (2007) 4554–4559

Table 3
Mulliken charge of EAP and DEAP
Atom EAP DEAP

C1 −0.520 −0.530
C2 −0.205 −0.204
N1 −0.451 −0.412
C3 −0.215 −0.218
C4 −0.509 −0.499
C5 −0.229 −0.243
C6 0.087 0.139
O8 −0.600 −0.614
C7 −0.503 −0.233
N2 −0.455
C8 −0.206
C9 −0.527
C10 −0.212
C11 −0.512

because these atoms have an larger negative charge, suggest-

ing that those active centers with excess charges could act as
a nucleophilic reagent. Generally, the larger negative charge of
heteroatom has, the better action is for the electron donor. Com-
pared with the net atomic charges of O8 , it is found that DEAP
has a stronger interaction with brass and has a better corrosion
inhibition effect on brass than EAP. When the HOMO orbital for
EAP and DEAP (Fig. 8) is analyzed, it is found that the highest
occupied molecule orbital (HOMO) is in the N1 and O8 for EAP,
this being the preferred zone for nucleophilic attack. For DEAP,
the HOMO is localized over the nitrogen atoms N1 and N2 , con-
sequently this is the favorite sites for interaction with the metal

Fig. 7. Optimised structures of EAP and DEAF.

in EAP by diethyl-amine group decreases the electronic den-

sity of C6 –C7 bond. The weak bond was found for the C–N
bond with a bond length value equal to 1.48 Å, compared with
a strong C–O bond with a bond length value equal to 1.46 Å.
This could explain the importance of the N atom of ␤-amino-
alcohols as a stronger adsorption center compared with O8
atom. The bond and dihedral angle showed that EAP has a
unequilibrium configuration due to the asymmetric adsorption
centers (N1 , O8 ) were susceptible to undergoing configuration
change. However, for DEAP, the configuration, being planar,
can present an equilibrium configuration because the symmetri-
cal adsorption centers (N1 , N2 ) were less likely to change, thus
helping the interaction of inhibitor molecules with the metal
surface.
The Mulliken charge of EAP and DEAP was shown in
Table 3. It can be seen that the most favorable sites for the inter-
action with the metal surface were the following atoms: C1 , N1 ,
C4 , C7 and O8 for EAP, C1 , N1 , C4 , O8 , N2 and C9 for DEAP, Fig. 8. Molecular HOMO orbital for EAP and DEAF.
 G. Gao, C. Liang / Electrochimica Acta 52 (2007) 4554–4559
Table 4
Quantum chemical parameters calculated by DFT
Inhibitor EHOMO ELUMO Etotal Dipole moment
(a.u.) (a.u.) (a.u.) (Debye)
EAP −0.222 0.036 −406.93 2.95
DEAP −0.205 0.037 −619.50 2.32
surface. Furthermore, the DEAP presents a linear structure in
which the most reactive sites can effectively interact with the
metal surface. This could explain its stronger interaction with
the metal surface and having a better inhibition effect for brass
than EAP.
In order to obtain more information about the electronic inter-
action of the inhibitor molecules with the metal surface, the
frontier orbital energy such as EHOMO , ELUMO , energy differ-
ence (E) and dipole moment (μ) are used to rationalize the
reactivity of the inhibitor molecule and molecule orbital coef-
ficient. It is known that the value of EHOMO is often associated
with the electron donating ability of inhibitor molecule, higher
values of EHOMO is an indication of the greater ease of donat-
ing electrons to the unoccupied d orbital of metal. The value
of ELUMO is related to the ability of the molecule to accept
electrons, lower values of ELUMO shows the inhibitor molecule
would accept electrons. Consequently, the value of E provides
a measure for the stability of the formed complex on the metal
surface. The lower value of E has, the higher stability is for the
formed complex. The quantum chemical parameters calculated
by DFT were given in Table 4.
It was shown from our calculations that EHOMO of DEAP
(−0.205 a.u.) was greater higher than in the case of EAP
(−0.222 a.u.), suggesting that the interaction between the
inhibitor molecule and the metal surface has been strengthened
due to the replacement of the H-atom (C7 ) in EAP by diethyl-
amine group. The value of E for EAP and DEAP are −0.258
and −0.242 a.u., respectively. The decrease of the energy dif-
ference between the frontier molecule orbital means that the
quality of the formed film by DEAP is superior to EAP. It was
also found that the value of dipole moment (μ) relating to the
hydrophobic character of molecules for DEAP (2.32) is lower
than that for EAP (2.95), suggesting that DEAP molecules are
more favoring the accumulation of the inhibitor molecules on
the metal surface. From the theoretical calculations carried out
for EAP and DEAP, it can be concluded that the structural and
electronic properties of the inhibitors are correlated with their
inhibition performance.
5. Conclusions
(1) The inhibition process of EAP and DEAP were evaluated by
polarization curves and EIS. The results indicated that the
investigated compounds behave as good anodic inhibitors
for brass in simulated atmospheric water, and the inhi-
4559
bition efficiency is found to be in the following order:
DEAP > EAP.
(2) The structure of the inhibitors influences their inhibition
efficiency. The reason for DEAP was the better corrosion
inhibitor duo to its equilibrium configuration, thus favoring
formation a stable adsorbed film through its symmetrical
adsorption centers (N1 , N2 ).
(3) The application of DFT calculations have been very suc-
cessful and can be used to understand the inhibition process
of corrosion.
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