Professional Documents
Culture Documents
Abu 2005
Abu 2005
Electroanalytical
Chemistry
Journal of Electroanalytical Chemistry 583 (2005) 133–139
www.elsevier.com/locate/jelechem
Department of Applied Physics, University of Fukui, 3-9-1 Bunkyo, Fukui-shi 910-8507, Japan
Received 18 April 2005; received in revised form 24 May 2005; accepted 24 May 2005
Available online 7 July 2005
Abstract
The iron plate covered with films of polyaniline-coated polystyrene latex (PANI–PS) microspheres were protected against cor-
rosion in 0.01 mol dm3 HCl and 3% (w/v) NaCl aqueous solution. PANI–PS particles 1.85 ± 0.06 lm in diameter were synthesized
by polymerizing chemically aniline on polystyrene (PS) latex in the suspension. The conducting state (emeraldine salt) of PANI film
shifted the corrosion potential of the underlying iron toward a positive from the insulating state of PANI (leucoemeraldine form).
The film from which core-polystyrene was removed by dissolution in tetrahydrofuran had the similar anti-corrosive properties. Tafel
plots, open circuit potential–time diagrams were used to examine the corrosion properties of PANI–PS coated and uncoated
electrodes.
2005 Published by Elsevier B.V.
contrast with using m-cresol or NMP for the organic was used for the next coating process. Features of the
solvents-aid coating. suspension of the PS latex particles were observed by
The PANI–PS has a core-shell structure, that is, a PS using a video microscope, VH-Z450 (Keyence, Osaka).
core and a PANI shell [42]. This structure is ascribed to
the immiscibility of the hydrophobic PS and the hydro-
philic PANI. Since the PANI–PS is stable in a suspen- 2.3. Coating the latex particle with PANI
sion form, it has been applied to voltammetry of
colloidal suspensions [41–44]. The suspensions have About 1.11 g aniline hydrochloride was dissolved in
shown diffusion-controlled voltammetric responses 100 cm3 of the PVP-stabilized 3% (w/v) PS latex suspen-
[41,42], and sometimes associated with periodic current sion. The mixture was stirred and cooled to 0 C in an
[43,44]. Self-standing PANI film of mono-particle-layer ice bath for 2 h in order to adsorb aniline on the surface
has been generated from the PANI–PS. The electro- of latex prior to polymerization. The polymerization
chemical properties are similar to those of the electro- was made at 0 C for 12 h after adding 2.45 g
chemically polymerized films [45,46] if the PANI–PS is (NH4)2S2O8 as the oxidant. The solution was kept at
purified at low temperature. This film may be helpful room temperature for further 24 h during stirring the
for corrosion inhibition as for conventional polyaniline mixture to complete the polymerization. Centrifugation
films. In this article, we report the protection properties of the suspension at 4 C yielded three layers. The sec-
of the PANI–PS-coated iron electrode in chloride-con- ond layer contained fragments of PANI. The bottom
taining solutions. layer, which contained a high portion of the PANI-
coated latex, was redispersed in 0.l M H2SO4 solution.
This suspension was centrifuged several times until the
H2SO4 solution layer became transparent. Then we ob-
2. Experimental tained the purified PANI–PS latexes and stored in 0.1 M
H2SO4 and 1% PVP solution.
2.1. Chemicals The particle under the reduced state was made by
adding hydrazine monohydrate to the suspension from
Styrene (Wako) was purified by distillation under which H2SO4 and PVP had been removed by centrifuga-
vacuum at 60 C. Poly(n-vinyl pyrrolidone) (PVP) tion and redispersion. After being kept for few hours,
(Wako) of 360 kg mol1 was used as a stabilizer or a the particle was washed by distilled water and stored
surfactant during the dispersion polymerization of sty- in 1% PVP solution. Both oxidized and reduced
rene. Ammonium peroxydisulfate (Wako), aniline PANI–PS particles were used for making films on
hydrochloride (Kanto), a-azoisobutyronitrile (AIBN) electrodes.
(Kanto), 2-propanol (Wako), tetrahydrofuran (THF)
(Wako), hydrazine monohydrate (Kanto) and sulfuric
acid and PVP were used as received. All aqueous solu- 2.4. Coating of iron electrode surface
tions were prepared with deionized water made by an
Advantec ultra pure water system (CPW – 100). A certain amount of 0.5% (w/v) PANI–PS suspension
including 0.05% (w/v) PVP was spread on the iron elec-
trode surface. Upon drying it at slow evaporation rate in
2.2. Synthesis of PVP-stabilized polystyrene latex an open atmosphere with 70% humidity at 25 C, a uni-
form multi-particle film was obtained on the electrode
A mixture of 120 cm3 2-propanol and 2.1 g PVP was surface. The PANI–PS coated-iron (PANI–PS–Fe) elec-
heated to 70 C with bubbling nitrogen during mechan- trode was inserted into THF for 45 min to remove the
ical stirring for 24 h in a three-necked round-bottomed soluble PS-core. It was washed carefully by distilled
flask to remove trace of oxygen. To this solution was water for several times and was dried. Then a thin PANI
added styrene (15 g) containing AIBN (0.15 g) drop-wise film without PS was obtained on the electrode surface.
for 40 min. The solution was maintained at 70 C for 24 The electropolymerization of aniline on the Fe elec-
h, during which the polymerization occurred. The result- trodes was carried out in 0.1 M aniline including 0.3
ing milky-white mixture was centrifuged with a centri- M oxalic acid, as described by Tüken et al. [47]. Firstly,
fuge, SRX – 201 (TOMY, Tokyo) equipped with a the electrode surface was passivated by applying a single
cooling system. The supernatant was decanted and re- forward scan from 0.5 to 0.3 V at scan rate of 4
placed by deionized water to yield white sediment of mV s1. Then one potential cycle was taken in the range
PS latex particles. This centrifugation–redispersion cycle from 0.0 to 1.6 V at a scan rate of 10 mV s1 and then
was repeated several times in order to remove residual 150 cycles were applied between 0.2 and 0.95 V at 50
reactants. Finally the particles were kept in aqueous mV s1. The coated electrodes were used as the working
medium with 3% (w/v) PVP. Then this latex suspension electrode for the measurement of corrosion.
Y.M. Abu, K. Aoki / Journal of Electroanalytical Chemistry 583 (2005) 133–139 135
2.5. Electrodes observed for the film on the epoxy resin and glass coated
area. PANI–PS particles coated at the iron electrode
The disk electrodes were made of an iron rod 1.2 mm were found to be reduced by the corrosion as evidenced
in diameter. The cylindrical wall of the rod was covered from the color change. The corrosion started near at the
with glass tube. A space between the inner wall of the interface of Fe and the shielding material, as shown as a
glass tube and the iron rod was insulated by epoxy resin. white product in Fig. 1(b), and the whole film turned red-
After curing the resin the surface of the electrode was brown finally. This behavior was observed also for the
polished with 500, 1000, 1500 and 2000 mesh sand pa- electropolymerized PANI coated iron (PANI–Fe) elec-
pers successively and washed with distilled water several trode, as shown in Fig. 1(c).
times in an ultrasonic bath before each use. A platinum Open circuit potential, Eoc of coated and uncoated
coil and saturated calomel electrode (SCE) were em- samples were measured, and plotted against the immer-
ployed as a counter and a reference electrode, respec- sion time in 0.01 M HCl solution in Fig. 2. The PANI-
tively. The potentiodynamic experiments were carried coated electrodes (b)–(d) showed more positive poten-
out with the coated and uncoated electrodes using the tials than the potential at the bare electrode (a), where
AutoLab potentiostat in 3% (w/v) NaCl solutions apply- the coating materials are (b) the reduced PANI–PS, (c)
ing a sweep rate of 1 mV s1 at room temperature. the electrochemically polymerized PANI, and (d) the
oxidized PANI–PS. Consequently, the PANI film works
as protection of the corrosion [48–53]. The oxidized
3. Results and discussion PANI is more effective for the corrosion protection than
the reduced form.
The PANI–PS was dark green, very similar to the col- Fig. 3 shows the Tafel lines (a), (b), (c) and (d) for un-
or of electropolymerized PANI films. The aqueous sus- coated-Fe, reduced PANI–PS–Fe, PANI–Fe and oxi-
pension through a video microscope showed that most dized PANI–PS–Fe electrodes, respectively, in 3% (w/
particles were so well isolated each other that no lump v) NaCl medium at the scan rate of 1 mV s1. The films
of particles was generated and that each was subject to were not removed from the Fe surface even at 1.2 V by
the Brownian motion. The acidic suspension was stable hydrogen gas evolution. Indeed no gas evolution was
for a few days without gravitational sedimentation. The observed. The corrosion potentials, Ecorr for all the three
sedimented particles could be easily redispersed by sim- coated electrodes are more positive than that observed
ply mixing. The PANI–PS was nearly mono-dispersed in the uncoated-Fe. The most anodic value of Ecorr indi-
and spherical with 1.85 ± 0.06 lm in diameter. Since cates that the oxidized PANI–PS–Fe electrode should
the PS latex particle before loading PANI had have the highest corrosion protection.
1.80 ± 0.05 lm, the thickness of PANI layer is ca. The polarization resistances, Rp were evaluated from
0.025 lm [=(1.85 1.80)/2]. the Tafel plots, according to the Stearn–Geary equation
Fig. 1(a) and (b) are optical microscope photographs [54],
of the bare iron and PANI–PS–Fe electrodes after 7 days
Rp ¼ ba bc =2.303ðba þ bc ÞI corr . ð1Þ
immersion in 3% (w/v) NaCl solutions, respectively. The
coated electrode (b) was more anti-corrosive than the Here, Icorr is the corrosion current determined by an
bare iron (a). The color of the PANI–PS film on the iron intersection of the linear portions of the anodic and
changed from dark green of the emeraldine salt to pale cathodic curves, and ba and bc are anodic and cathodic
green of leucoemeraldine, whereas no color change was Tafel slopes (DE/Dlog I), respectively. The protection
Fig. 1. Photographs of: (a) Fe electrode, (b) PANI–PS–Fe electrode, (c) PANI–Fe electrode, after 7 days immersed in 3% (w/v) NaCl aqueous
solutions. The curve in (b) was drawn in order to display the location of the interface between the iron electrode and the shielding material (epoxy
resin). White lumps in (b) and (c) are corroded products after 7 days of immersion.
136 Y.M. Abu, K. Aoki / Journal of Electroanalytical Chemistry 583 (2005) 133–139
-0.5
-0.5
-0.6
(d)
EOC / V vs.SCE
-0.6
(b) -0.7
(e) -0.8
-0.7
(a)
Table 1
Some corrosion parameters obtained in 3% (w/v) NaCl solutions, varying with the amount ratio of the oxidized PANI–PS to the reduced PANI–PS
at a common value of the total loaded amount of PANI–PS
Samples W(ox):W(rd) Ecorr/V vs. SCE Icorr/lA cm2 Rp/kX PEF %
Uncoated-Fe – 0.880 15.3 22 –
PANI–PS/Fe 0:1 0.865 17.0 76 70
PANI–PS/Fe 1:4 0.812 8.2 180 87
PANI–PS/Fe 2:3 0.755 7.4 372 94
PANI–PS/Fe 1:1 0.723 6.3 552 96
PANI–PS/Fe 3:2 0.698 5.3 694 96
PANI–PS/Fe 4:1 0.645 3.4 833 97
PANI–PS/Fe 1:0 0.614 1.9 1120 98
Y.M. Abu, K. Aoki / Journal of Electroanalytical Chemistry 583 (2005) 133–139 137
Ecorr / V vs.SCE
-0.7
þ
jPANI ¼ k PANI ½PANI exp½bnFE=RT ; ð5Þ
where a and b are transfer coefficients. Since the anodic
current is compensated with cathodic one in corrosion, -0.8
summation of cathodic and anodic current densities
yield,
jFe þ jPANI ¼ 0. ð6Þ
-0.9
From Eqs. (4)–(6) we can write, -13 -12 -11
RT ln( Io / A)
Ecorr ¼ fln½PANIþ þ const.g ð7Þ
F ðam þ bnÞ Fig. 6. Variation of corrosion potential with logarithm of the
corrosion current at PANI–PS–Fe electrodes.
Values of am and bn were obtained from the Tafel slopes
in Fig. 3(a). The value of RT/F(am+bn) is 0.052 V, When the PS-core was dissolved in THF from the
which is close to the value of the slope in Fig. 4. There- PANI–PS–Fe electrode [41,42] the resulting film exhib-
fore the linearity in Fig. 4 is based on the simple combi- ited the linear variation of Ecorr with ln W, as shown in
nation of Eqs. (4)–(6). Fig. 4 (triangles). We succeeded in fabricating a large
Fig. 5 shows the variation of Ecorr against the loga- PANI film (5 · 4 cm2) by removing PS-core from the
rithm of the ratio of the amount of the oxidized PANI–PS film in THF. This film was uniform on the
PANI–PS to the reduced one, where the amounts of scale of 0.5 mm, as is shown in Fig. 7. However, it
loaded PANI–PS were common. A Nernst-like variation
is found, showing the slope of 0.060 V. If the linear rela-
tion were to be regarded as the Nernst equation, the va-
lue of n is 0.4. This is within the conventional domain of
n from 0.2 to 0.5 [57,58]. Therefore, Ecorr at the PANI–
PS–Fe electrode is strongly controlled by the redox reac-
tion of PANI.
Values of Ecorr for several values of W(ox)/W(rd)
showed a linear variation of the logarithm of the corro-
sion current, as shown in Fig. 6. The slope was 0.13 V,
which is equivalent to bn = 0.21. Since n = 0.4, we got
b = 0.5. This belongs to the conventional charge transfer
process.
-0.6
Ecorr / V vs.SCE
-0.7
-0.8
-1 0 1
ln[ W(ox) / W(rd) ]
Fig. 5. Dependence of corrosion potential on the logarithm of the Fig. 7. Photograph of large (5 · 4 cm2) PANI–PS film on Fe-plate
amount ratio of the oxidized PANI–PS to reduced PANI–PS at a after removing the PS-core by THF. White part is the uncovered Fe-
common value of the total loaded amount of PANI–PS. plate. The inset is a magnified photograph.
138 Y.M. Abu, K. Aoki / Journal of Electroanalytical Chemistry 583 (2005) 133–139
[17] W. Lu, R. Elsenbaumer, B. Wessling, Synth. Met. 71 (1995) 2163. [38] P. Beadle, S.P. Armes, S. Gottesfeld, C. Mombourquette, R.
[18] V. Brusic, M. Angelopoulos, T. Graham, J. Electrochem. Soc. Houlton, W.D. Andrews, S.F. Agnew, Macromolecules 27 (1992)
144 (1997) 436. 2526.
[19] R. Gašparac, C.R. Martin, J. Electrochem. Soc. 149 (2002) [39] H.Q. Xie, H. Liu, Z.H. Liu, J.S. Guo, Angew. Makromol. Chem.
B409. 246 (1996) 117.
[20] R. Gašparac, C.R. Martin, J. Electrochem. Soc. 148 (2001) [40] C. Barthet, S.P. Armes, S.F. Lascelles, S.Y. Luk, H.M.E. Stanley,
B138. Langmuir 14 (1998) 2032.
[21] P.J. Kinlen, V. Menod, Y. Ding, J. Electrochem. Soc. 148 (1999) [41] T. Lei, K. Aoki, J. Electroanal. Chem. 482 (2000) 149.
3690. [42] K. Aoki, J. Chen, Q. Ke, S.P. Armes, D.P. Randall, Langmuir 19
[22] S. de Souza, J.E.P. da Silva, S.I.C. de Torresi, M.L.A. Temperini, (2003) 5511.
R.M. Torresi, Electrochem. Solid-State Lett. 4 (2001) B27. [43] T. Lei, K. Aoki, K. Fujita, Electrochem. Commun. 2 (2000) 290.
[23] S. Pruneanu, E. Csahok, V. Kertesz, G. Inzelt, Electrochim. Acta [44] K. Aoki, T. Lei, Langmuir 16 (2000) 10069.
43 (1998) 2305. [45] Y.M. Abu, K. Aoki, J. Electroanal. Chem. 565 (2004) 219.
[24] R.J. Mortimer, Electrochim. Acta 44 (1999) 2971. [46] Y.M. Abu, K. Aoki, Electrochim. Acta 50 (2005) 3634.
[25] C.A. Ferreira, S. Aeiyach, J.I. Aaron, P.-C. Lacaze, Electrochim. [47] T. Tüken, A.T. Özyılmaz, B. Yazc, M. Erbil, Appl. Surf. Sci. 236
Acta 41 (1994) 1801. (2004) 292.
[26] C.A. Ferreira, S. Aeiyach, M. Delamer, P.-C. Lacaze, J. Electro- [48] A.A. Hermas, M. Nakayama, K. Ogura, Electrochim. Acta 50
anal. Chem. 284 (1990) 351. (2005) 2001.
[27] J.L. Camalet, J.C. Lacroix, S. Aeiyach, K. Chane-Ching, P.-C. [49] B.N. Grgur, N.V. Krstajic, M.V. Vojnovic, C. Lacnjevac, L.J.
Lacaze, Synth. Met. 93 (1998) 133. Gajic-Krstajic, Prog. Org. Coat. 33 (1998) 1.
[28] G. Troch-Nagels, R. Winand, A. Weymeersch, L. Renard, J. [50] T.L. Nguyen, B. Garcia, C. Deslouis, L.Q. Xuan, Electrochim.
Appl. Electrochem. 22 (1992) 756. Acta 16 (2001) 4259.
[29] G. Mengoli, M.M. Musiani, Electrochim. Acta 31 (1986) 201. [51] P. Li, T.C. Tan, J.Y. Lee, Synth. Met. 88 (1997) 237.
[30] F. Beck, M. Musiani, J. Coat. Tech. 64 (1992) 59. [52] K. Aramaki, Corros. Sci. 42 (2000) 1975.
[31] M. Shirmeisen, F. Beck, J. Appl. Electrochem. 19 (1989) [53] M. Kraljic, Z. Mandic, L. Duic, Corros. Sci. 45 (2003) 181.
401. [54] M. Stern, A.L. Geary, J. Electrochem. Soc. 104 (1957) 56.
[32] P. Hulser, F. Beck, J. Appl. Electrochem. 20 (1990) 596. [55] J. Bockris, K.N. Reddy, Modern Electrochemistry, New York,
[33] Y. Xia, B. Gates, Y. Yin, Y. Lu, Adv. Mater. 12 (2000) 693. 1976, p. 622.
[34] X.G. Li, M.R. Hung, J.F. Zeng, M.F. Zhu, Colloids Surf. A 248 [56] T.D. Nguyen, T.A. Nguyen, M.C. Pham, B. Piro, B. Normand,
(2004) 111. H. Takenouti, J. Electroanal. Chem. 572 (2004) 225.
[35] P. Banerjee, B.M. Mandal, Macromolecules 28 (1995) 3940. [57] K. Aoki, T. Edo, J. Cao, Electrochim. Acta 43 (1998) 285.
[36] H. Eisazadeh, K.J. Gilmore, A.J. Hodgson, Colloids Surf. A 103 [58] D.E. Stilwell, Su.-M. Park, J. Electrochem. Soc. 136 (1989) 427.
(1995) 281. [59] K. Aoki, J. Cao, J. Electroanal. Chem. 428 (1997) 97.
[37] B.D. Chin, O.O. Park, J. Colloid Interf. Sci. 234 (2001) 344. [60] K. Aoki, S. Tano, Electrochim. Acta 50 (2005) 1491.