Synthetic Metals 132 (2002) 35–41

Electrochemical synthesis and corrosion behavior

of poly(N-ethyl aniline) coatings on Al-2024 alloy
Kunal Shah, Jude Iroh*
Department of Material Science and Engineering, University of Cincinnati,
498 Rhodes Hall, Cincinnati, OH 45221 0012, USA
Received 20 August 2001; received in revised form 25 July 2002; accepted 28 August 2002

Abstract

Poly(N-ethyl aniline) coating was electrodeposited onto Al-2024 by using cyclic voltammetry. The coating was characterized by infrared
spectroscopy, cyclic voltammetry and UV-Vis spectroscopy. The corrosion resistance of the film was evaluated by dc polarization studies.
These coatings were formed in aqueous solution of oxalic acid. The concentration of monomer and oxalic acid were kept constant at 0.1 and
0.3 M, respectively. The formation of the polymer coating was monitored by cyclic voltammetry and infrared spectroscopy. Preliminary dc
polarization results show that poly(N-ethyl aniline) has a corrosion rate of about 0.004 mmpy, which is significantly lower (about one order of
magnitude) than that for the non-coated Al-2024.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Electrochemical synthesis; Substituted polyaniline; Corrosion resistant coatings; Conducting polymer coatings; dc Polarization studies;
Al-2024 alloy

1. Introduction nitrogen lone pair; as a result reducing the degree of con-

Intrinsically conductive polymers, have received consid-
erable attention in the past decade, in particular aromatic
polymers like polyaniline, polypyrrole and polythiophene
[1,2]. Among these polymers, polyaniline has been inten-
sively investigated due to its good chemical and environ-
mental stability. Excellent optical and electrochemical
properties of conducting polymers, have led to applications
in various areas such as display devices [3,4], microelec-
tronics [5], gas sensors [6] and corrosion protection [7,8].
However, it is a challenge to synthesis a highly conductive
and processable conducting polymer. Their rigid planar
backbone, which is necessary for electrical conductivity,
also leads to a material, which is insoluble in most common
solvents. The presence of a substituent on a conducting
polymer such as polyaniline may result in a material, which
is more soluble and readily processable while retaining the
appealing characteristics of polyaniline. However, these
substituted polyanilines possess lower conductivity than
polyanilines. It has been suggested that the increased tor-
sional angle induced by the presence of the substituent leads
to decreased orbital overlap of the p-electrons and the
*
Corresponding author. Tel.: þ1-513-556-3096; fax: þ1-513-556-2569.
E-mail address: jiroh@uceng.uc.edu (J. Iroh).
jugation and thus lowering the electrical conductivity.
Ring substituted polyanilines have been studied exten-
sively [9–11], however, less attention has been paid to the
N-substituted polyanilines [12–15]. Hence, a full understand-
ing of the mechanism of formation of these polymers and
the ability to control their physical and chemical structure is
necessary before utilizing them for large scale applications.
In the present work, poly(N-ethyl aniline) coating was
electrodeposited onto aluminum alloy (Al-2024). The coating
was characterized by using cyclic voltammetry (CV), reflec-
tion–absorption infrared spectroscopy (RAIR) and UV-Vis
spectroscopy (UV). The corrosion resistance of the coatings
was evaluated by using dc polarization (TAFEL) analysis.
2. Experimental
The monomer (N-ethyl aniline) and the electrolyte (oxalic
acid) were bought from Aldrich. The Al-2024 panels were
purchased from Q-Panel Inc. The reference electrode, satu-
rated calomel electrode (SCE) was supplied from Corning
Company.
An aqueous solution of the monomer (0.1 M) and the
electrolyte (0.3 M) was prepared by using deionized water.
About 200 ml of the solution was used for each experimental

0379-6779/02/$ – see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 7 9 - 6 7 7 9 ( 0 2 ) 0 0 2 1 3 - 8
36 K. Shah, J. Iroh / Synthetic Metals 132 (2002) 35–41
run. A single compartment polypropylene cell was used for
electrodepositing the polymer coatings onto the substrate.
Al-2024 panel (1 in:  4 in.) was used as the working elec-
trode, two stainless steel sheets (1:4 in:  5:750 in.) were
used as counter electrodes and saturated calomel electrode
(SCE) was used as the reference electrode.
Cyclic voltammetry was used to electrodeposit the coat-
ings onto the substrate. An EG&G Princeton Applied
Research model no. 363 potentiostat/galvanostat was used
as the source of power supply. The scan range used was 1.0
to 3.0 V versus SCE. The number of cycles was varied from
1 to 25. The EG&G PARC model no. 270/250 software was
used to analyze the results and perform the experiment.
An FTS-BioRad reflection absorption infrared spectro-
scopy (RAIR) instrument was used to obtain the infrared
spectra of the polymer coatings. All the RAIR spectra were
taken at a resolution 8 cm1 and the scan range was 400–
4000 cm1. A total of 256 scans were taken for each spectrum.
Ultrasonically cleaned bare Al-2024 was used to obtain the
background spectrum. The background was subtracted from
the sample spectrum to obtain the spectrum for the coatings.
The UV spectra were taken using a U-3000 UV-Vis
spectrometer. The coatings were dissolved in NMP and
placed in a sample holder. Pure NMP solvent was used as
the reference. The spectra were taken in wavelength scan
mode in the region 190–1100 nm. The UV spectra for the
monomers were taken by mixing monomer:NMP (1:10).
The dc polarization studies were done to evaluate the
corrosion resistance offered by the coatings. The experi-
ments were carried out by using an EG&G flat cell. Al-2024
coupon was used as the working electrode; AgCl was used as
the reference electrode and a stainless steel panel as the
counter electrode. An aqueous solution containing 3.5 wt. %
of NaCl was used as the electrolyte. Four points were taken
on each sample (two on each side) and an average value is
reported.
The corrosion potential (Ecorr) and the corrosion current
(Icorr) were obtained from the TAFEL plots. EG&G 273A
potentiostat equipped with a 352 SOFT CORR III corrosion
software was used to analyze the TAFEL plots. A potential
of 250 mV was applied in both positive and negative direc-
tion from the open circuit potential. A TAFEL plot consists
of an anodic and a cathodic branch, the intersection of these
branches gives the Icorr and the Ecorr. The equilibrium open
circuit potential (OCP) of the polymer-coated electrode can
be considered as the corrosion potential. It can give an
indication about the nature of the protection, which is
offered by the coating (anodic or cathodic). The corrosion
current is used to calculate the corrosion rate of the metal.
The corrosion current was calculated using the Stern–
Geary equation [18]:
IðEÞ ¼ Icorr ½10ðEEcorr Þ=ba  10ðEcorr EÞ=bc (1)
where I is the total current at a potential E, Ecorr the open
circuit potential and ba and bc the TAFEL proportionality
constants for the anodic and cathodic reactions, respectively.
The corrosion rate was calculated using the following
equation [18]:
  
EW Icorr
corrosion rate ¼ C (2)
d A
where C is the conversion constant (C ¼ 3:268  103 , when
Icorr is in ampere and the corrosion rate in mmpy), EW the
equivalent weight of the sample in gm/eq., A the sample area
in cm2 and d the density of the sample in g/cm3.
3. Results and discussion
Poly(N-ethyl aniline) was electrodeposited onto Al-2024 in
aqueous solution containing the monomer and oxalic acid, by
using cyclic voltammetry. The analysis of CV data provided
information about the kinetics and the mechanism of electro-
deposition of PNEA. The chemical structure of the coating
was analyzed using RAIR. UV-Vis spectroscopy was used to
obtain information about the nature and extent of conjugation
in the polymer coatings. The corrosion resistance offered by
the coatings was evaluated by dc polarization studies.
3.1. Infrared analysis
Fig. 1 shows the infrared spectrum for poly(N-ethyl aniline)
(PNEA). As shown in the Fig. 1 characteristic PNEA peaks
occur at 2850, 1600, 1500, 1350 and 1120 cm1 in agree-
ment with the literature [16]. The peak at 830 cm1 is due
the 1,4-para-substituted benzene ring, which is expected in
the poly(N-ethyl aniline) structure. The two strong peaks at
1120 and 620 cm1, are due to in plane and out of plane C–H
bending motion of quinoid and benzenoid rings, respec-
tively. The peaks at 1250 and 1350 cm1 are characteristic
of aromatic amines. The peaks at 2950 and 2850 cm1 are
due to the symmetric C–H stretch, which arises due to
C2H5 substitution in the polymer backbone. The peaks at
1500 and 1600 cm1 are due to the benzenoid and quinoid
groups, respectively. There are also two strong peaks at 1680
and 1720 cm1, which are due to the dopant and carbonyl
groups, respectively. The dopant used here is oxalate ion,
which comes from the dissociation of oxalic acid (the
electrolyte). The carbonyl groups are due to the overoxida-
tion of the polymer. The characteristic peaks of poly(N-ethyl
aniline) are summarized in Table 1.
Table 1
Characteristic peaks of poly(N-ethyl aniline)
Peak (cm1) Comments
2830–2800 N–CH3 (aromatic)—symmetric CH3 stretch
1500 Benzenoid groups
1600 Quinoid groups
1350, 1250 N–H defined for amines
820 1,4-para-substituted benzene
1120, 620 In plane and out of plane C–H bends of benzenoid
and quinoid groups
 K. Shah, J. Iroh / Synthetic Metals 132 (2002) 35–41 37

Fig. 1. Infrared spectra of poly(N-ethyl aniline), deposited by CV for 25 cycles at a scan rate of 20 mV/s.

Fig. 2. CVs of (a) 1st to 15th cycles and (b) 15th to 25th cycles. Poly(N-ethyl aniline) coated at 30 mV/s.
38 K. Shah, J. Iroh / Synthetic Metals 132 (2002) 35–41

Fig. 3. Formation of NEA at shorter reaction times: 30 mV/s for fifth cycle. (a) CV and (b) IR spectra.

3.2. Cyclic voltammetry analysis
Fig. 2a shows the cyclic voltammograms of 1st, 5th, 10th
and 15th cycles of CV at a scan rate of 30 mV/s. It is shown
that the PNEA coating increases proportionally with the
number of cycles. A sharp peak is observed at 0.5 V and a
broad peak occurred at 1 V in the first few cycles. Fig. 2b
shows the formation of the polymer at longer reaction time.
As shown in Fig. 2b, the peak at 0.5 V disappeared leaving
only one peak at 1 V. This suggests the formation of the
oxidized form of the polymer. Analysis of these peaks is
shown in the successive figures.
Fig. 3 shows the formation of PNEA at shorter reaction
times (cycle 5). The cyclic voltammogram show a sharp
peak at 0.5 V versus SCE and a broad peak at 1 V versus
SCE. The IR spectrum of cycle 5 shows a prominent peak at
1500 cm1 (due to benzenoid groups) and peak at 1600 cm1
is absent. This suggests that the peak at 0.5 V in the cyclic
voltammogram is due to the formation of the leucoemer-
aldine form (the reduced state) of PNEA.
Fig. 4a shows the variation of the peak area (A1600/1500)
versus the shift in the potential for 5th to 25th cycles. Fig. 4b
shows the infrared spectra for different cycles. The shift in
potential is calculated by taking the potential for the third
cycle as the reference potential. The ratio of the areas of
1600–1500 cm1 peak in the infrared spectra’s can be used
to estimate the oxidation state of the polymer. The ratio is 0
for reduced form, 0.5–1 for the protoemeraldine form, 1 for
the partially oxidized form and >1 for the oxidized form of
the polymer. As the peak potential in CV shifts from 0.51 to
1.21 V versus SCE, the peak area ratio in infrared spectra
shifts from 0 to 0.55. This suggests that as the reaction time
is increased the polymer structure is changed from leucoe-
meraldine to protoemeraldine form of PNEA.
Fig. 5 shows the formation of PNEA as a function of
number of cycles. It is seen that as the number of cycles are

Fig. 4. (a) Variation of oxidation state of NEA with respect to number of cycles (E0 ¼ potential of third cycle). (b) Infrared spectra of different cycles.
 K. Shah, J. Iroh / Synthetic Metals 132 (2002) 35–41 39

Fig. 5. Formation of NEA at longer reaction times. Scan rate ¼ 30 mV/s. (a) CV and (b) IR spectra.

increased the peak at 0.5 V is shifted more towards higher
potential and at the end of 20 cycles the peak had shifted to
1 V. The IR spectra for these cycles also show a similar trend.
As the numbers of cycles are increased the 1600 cm1 peak
became more prominent. This peak arises due to the formation
of the quinoid group. The intensity of the characteristic peaks
is also increased as a function of the number of cycles. This is
due the formation of a thick polymer film on the substrate.
Fig. 6 shows the increase in peak current (peak at 1 V in
CV) as a function of the number of cycles. The increase in
transition in the benzenoid structure,
peak current is associated with the increased deposition of
the polymer film on the substrate. As shown in the figure, the
peak current increases from 0.003 to 0.014 A as the number
of cycles was increased from 5 to 25. This suggests that as
the reaction time is increased the polymer is correspondingly
deposited on the substrate.
Fig. 7 shows the plot of ln(Ip) versus ln(time), where Ip is
the peak current (peak at 0.5 V) for the 1st, 5th, 10th and
15th cycles. As shown in the figure a slope of 0.7 was
obtained. This suggests that the growth of the polymer film is
controlled by the diffusion of the reactive species onto the
aluminum substrate.
3.3. UV-Vis spectroscopy analysis
Fig. 8a shows the UV-Vis spectra of N-ethyl aniline. Two
strong peaks at 270 and 320 nm are observed. These peaks
are due to the p–p
which are expected for the monomer (NEA).
Fig. 8b shows the UV-Vis spectra for the poly(N-ethyl
aniline). The peak at 270 nm disappeared and the peak at
320 nm has become broader. This suggests the formation of
the polymer film on the substrate. There is also another peak
at 620 nm; which is related to formation of the quinoid rings.
Thus, suggesting the presence of conjugation on the polymer
backbone.

Fig. 6. Variation of peak current at 1.0 V vs. SCE with number of cycles, during the deposition of PNEA.
40 K. Shah, J. Iroh / Synthetic Metals 132 (2002) 35–41

Fig. 7. The plot of ln(Ip) vs. ln(time). Poly(N-ethyl aniline) coated at 30 mV/s.

3.4. The dc polarization studies
Fig. 9 shows the TAFEL plots for the control and the
PNEA-coated Al-2024. As seen from the plot, the Icorr
decreases from 1.97 mA for the control to 0.325 mA for
the coated sample. The corrosion rate of the metal is redu-
ced by about one order of magnitude. The Ecorr increases
from 234 mV for the control to 125 mV for the PNEA-
coated sample. This positive shift of 109 mV in Ecorr
indicates that PNEA coatings ennoble the metal surface
[17]. Table 2 shows the variation of Icorr, Ecorr and corrosion
rate as a function of reaction time for the PNEA-coated
samples.
As shown in the Table 2, the corrosion rate of the coatings
is not significantly changed when the reaction time is varied
suggesting that the thickness of the coating may not
significantly influence the corrosion resistance offered by
the poly(N-ethyl aniline) coatings.

Fig. 8. UV-Vis spectra of (a) N-ethyl aniline and (b) poly(N-ethyl aniline). NEA coated at scan rate 20 mV/s for 25 cycles.
 K. Shah, J. Iroh / Synthetic Metals 132 (2002) 35–41 41

Fig. 9. TAFEL plot for (a) Al-2024 (control) and (b) PNEA-coated Al-2024.

Table 2 Acknowledgements
Comparison of Icorr, Ecorr and corrosion rate for PNEA-coated Al-2024

Control PNEA coated for The financial support for this research by National Science
5 cycles 10 cycles 15 cycles 25 cycles
Foundation, Division of Materials Research (DMR) is grate-
fully acknowledged.
Icorr (mA) 1.97 0.649 0.621 0.776 0.325
Ecorr (mV) 234.6 190.0 125.0 103.2 158.1
Corrosion 0.026 0.008 0.0084 0.0106 0.0044
rate (mmpy) References

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4. Conclusions
Poly(N-ethyl aniline) coatings were successfully electro-
deposited onto Al-2024. Infrared spectroscopy, cyclic vol-
tammetry and UV-Vis spectroscopy were used to characterize
the coatings. The corrosion protection offered by PNEA
coatings was evaluated using dc polarization studies.
Infrared and cyclic voltammetry analysis showed that at
shorter reaction time, the reduced state (leucoemeraldine
form) of the polymer is formed and as the reaction time is
increased the structure of the polymer changes to partially
oxidized (protoemeraldine) form of PNEA. Thus, the
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the polymer, suggesting the presence of conjugation on the
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The dc polarization studies showed that the corrosion rate
of the Al-2024 is reduced by about one order of magnitude.
The corrosion potential of the sample was shifted to more
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