Corrosion Science 47 (2005) 649662 www.elsevier.

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Corrosion performance of conducting polymer coatings applied on mild steel

P. Ocon *, A.B. Cristobal, P. Herrasti, E. Fatas
Departamento de Qu mica F sica Aplicada, Facultad de Ciencias, Universidad Autonoma de Madrid, 28049 Madrid, Spain Available online 13 August 2004

Abstract Conducting polypyrrole electrodes were obtained by galvanostatic electropolymerisation on mild steel electrodes from an aqueous solution. The electrochemical response of the coated electrodes in doped and in undoped state was compared with bare mild steel electrodes. The undoped polypyrrole coated electrode oered a noticeable enhancement of protection against corrosion processes. 2004 Elsevier Ltd. All rights reserved.
Keywords: A. Mild steel corrosion; C. Polymer coatings; C. Polypyrrole; B. Impedance

1. Introduction The development of conducting polymer lms has given rise to many advantages which will continue to encourage researchers to nd improved properties [15]. The use of barrier coatings on metal substrates is common in corrosion protection. With steel substrates, surface treatments such as the application of a zinc layer and rinsing with chromate-containing agents are often performed before applying the barrier coating in order to ensure long-lasting protection and self-healing

Corresponding author. Tel.: +34 91 497 4831; fax: +34 91 497 4785. E-mail address: pilar.ocon@uam.es (P. Ocon).

0010-938X/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2004.07.005

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properties. Unfortunately these techniques involve heavy metals which are preferably kept out of the environment. Interest has recently been focused on the possible use of conducting polymers as either lm-forming corrosion inhibitors or in protective coatings [511]. Polypyrrole (PPy) is one of the most promising conducting polymers in view of its high conductivity, stability and ease of synthesis. Beck et al. [12] showed that it is possible to obtain strongly adherent, smooth PPy lms on iron by the electrodeposition of pyrrole and oxalic acid from aqueous solutions. PPy lms on iron constitute a physical barrier to aggressive chemical reagents and can act as polymeric inhibitors and shift the potential of the coated material to values where the corrosion rate is lower. Hence the degree of corrosion protection aorded by a conducting polymer coating depends on both its structural and electronic properties [1316]. The advantage of electrochemical synthesis is that it achieves the direct synthesis of a polymer on the metal surface without any organic additives. The aim of this study is to investigate the electrosynthesis of an adherent polymer coating on mild steel, determining the conditions in which synthesis takes place and the protective properties that are achieved. Polypyrrole coatings are compared in doped and undoped states using open circuit, potentiodynamic and impedance techniques to study their protective eect.

2. Experimental Measurements were performed in a standard one-compartment three-electrode cell, synthesising the coatings on mild steel samples. The counter electrode was a graphite foil and the reference electrode was Ag/AgCl/ (3 mol dm3 KCl). All the potentials cited in this work refer to this reference electrode. The working electrode consisted of 2 cm2 of mild steel sheet. The steel samples were polished using 600 grit emery paper, washed with bidistilled water and placed in acetone in an ultrasonic bath for 5 min before use. Chemical treatment was performed prior to electrosynthesis. The electrode was immersed in 13.8% HNO3 for dierent times and rinsed with bidistilled water. This treatment produces a passivated area, allowing the polypyrrole to oxidise in similar conditions to those measured when using a Pt electrode. Polypyrrole electrodeposition on a mild steel electrode was performed in 0.1 mol dm3 Na2SO4 and 0.5 mol dm3 pyrrole (Merck product). The pyrrole was freshly distilled and stored in a nitrogen atmosphere until its use. The reagents were stored at 0 C in the dark. The electrolytes were dissolved in bidistilled water. PPy electropolymerisation experiments were conducted at room temperature in an aerated atmosphere and a non-stirred solution. Electrochemical growth was performed by the galvanostatic method. Electropolymerisation and electrochemical characterisations were carried out using the computerised Autolab Mod. PGSTAT 30 electrochemical instrument

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equipped with an FRA module (Ecochemie, Utrecht, Netherlands). All measurements were made at room temperature. Potentiodynamic polarisation curves were obtained in a 3% NaCl dissolution by rstly locating the EOCP and from that value polarising the electrode in the cathodic direction to obtain the cathodic branch. With another new electrode, grown in the same conditions, the EOCP was once again located and polarisation performed in the anodic direction to obtain the anodic branch. The galvanostatically grown PPy was obtained in oxidised state, and therefore in the doped state. The backbone had a delocalised p-system and the polymer lm incorporated SO anions, stabilising the load on the polymers backbone. In order 4 to obtain more compact structures the PPy was subjected to a reduction process in a 0.1 mol dm3 Na2SO4 dissolution, imposing a cathodic potential of 1200 mV for 1200 s. In this way the polymer lm was partially reduced, expelling part of the anions in the chain from the polymer lm, which gave rise to the compaction of the lm due to the reduction in its volume. The coating thus obtained was less conductive, being termed as undoped. The perturbation voltage for EIS measurements was 5 mV and the frequency range went from 105 to 102 Hz. The electrodes were held for 500 s at the open circuit potential (EOCP) before starting the measurements. Scanning electron microscopy and EDX analysis were performed using a Philips instrument.

3. Results and discussion 3.1. Galvanostatic deposition of PPy on mild steel In the case of mild steel or iron, anodic or chemical oxidation is accompanied by dissolution of the metal. The oxidation potential of most monomers is in the region of metal dissolution. The metal is able to retard or to inhibit the oxidation of the monomer and thus the formation of an adherent polymer lm. Therefore the mild steel surface must be pretreated in order to avoid strong corrosion parallel to the lm formation. Homogeneous and adherent PPy lm have been obtained when treating a mild steel surface with HNO3 [17]. Nitric acid signicantly changes the electrochemical behaviour of the mild steel surface and produces a considerable shift in the oxidation barrier. When mild steel is immersed for 4 min in 13.8% HNO3 acid and polarised in 0.1 mol dm3 Na2SO4 (Fig. 1), the treatment is seen to cause considerable passivation of the electrode. The electropolymerisation of pyrrole can be obtained at current density values close to those measured when using a Pt electrode. Galvanostatic deposition has been performed using weak current densities in order to keep the mild steel electrode in the passivation region. From an industrial point of view, galvanostatic deposition produces turn out in a one-step process, which is a key criterion for most electrochemical deposition processes.

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60 50 40 30

i (A m-2)

20 10 0 -10 -1.0 -0.5 0.0 0.5 1.0 1.5

E(mV/Ag/AgCl)
Fig. 1. Cyclic voltammogram obtained for chemically passivated mild steel electrode in 0.1 mol dm3 Na2SO4. Scan rate 50 mV s1.

Under these conditions, a very adhesive PPy lm has been obtained for current densities reaching 5, 10, 15 and 20 mA cm2 and dierent deposition times. PPy electropolymerisation is characterised by a sharp rise to a maximum positive value, after which the potential quickly decreases to a steady value where a black PPy coating starts to form. An increase in the current density leads to a positive shift in the poten-

Fig. 2. Potential transients obtained in 0.5 mol dm3 Pyrrole and 0.1 mol dm3 Na2SO4 for dierent current densities: (a, b) 15 mA cm2, (c) 12 mA cm2 and (d) 10 mA cm2.

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Fig. 3. SEM surface micrograph of a PPydoped lm obtained on mild steel in 0.1 mol dm3 Na2SO4, 0.5 mol dm3 Pyrrole in galvanostatic conditions i = 15 mA cm2 and deposition time 500 s.

tial of the plateau. There is no inducting period for any of the experiments (Fig. 2). The result is a strongly adherent PPy lm. Fig. 3 shows a grained texture and an open structure typical of these polymer lms. However, when i = 20 mA cm2, mild steel dissolution becomes signicant, as is indicated by the rapid colouring of the solution. The best result in terms of the protective eect is obtained with i = 15 mA cm2. The coating thickness (dn) has been calculated using Faradays law, assuming a two-electron mechanism based on the monomer molecule involved in the process and a current eciency of 100%. The PPy density (q) is 1500 kg m3 and the pyrrole molar mass (M) is 67 103 kg mol1: d n QM=2F q where Q is the overall specic charge for electropolymerisation (C m2). 3.2. Corrosion test The open circuit potential has been monitored in an aerated corrosive solution (3% NaCl) for PPy lms obtained at dierent current densities for an electrodeposition time of 500 s (i.e. of dierent thicknesses). Monitoring the open circuit potential (EOCP) of the system allows the corrosion protection of mild steel by PPy lms to be assessed. In the rst step, the aim was to nd whether there is an optimum thickness value for a good protection time. As an example, Fig. 4 shows the evolution of the EOCP for PPy lms of the indicated thicknesses and for mild steel and mild steel coated with the chemically grown oxide layer. The curves for the latter two surfaces display

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Fig. 4. Open circuit potential electrode EOCP (mV) as a function of immersion time (h) in 3% NaCl. (j) Mild steel, (n) passivated mild steel, (s) PPydoped 5.0 lm, ( ) PPydoped 10.4 lm, (s) PPydoped 17.5 lm and (m) PPyundoped 17.5 lm.

a decrease towards a pseudo-plateau around 650 mV. On this plateau some oscillations in the potential can be observed. These oscillations can be associated with the onset of pitting [18,19]. For all the studied PPy lms, the EOCP for zero time shows a less negative potential, but the evolution is not the same for all the lms. When the thickness is less than 17.3 lm the EOCP decreases towards the corrosion potential of uncoated mild steel and the metal is no longer protected as some blistering is detected. For the 17.3 lm thickness, PPy in the doped state shows EOCP = 300 mV at rst which evolves to EOCP = 550 mV after 72 h immersed in the corrosive solution. This value is obtained as a pseudo-plateau for a long time, approximately 24 days. This PPy lm was obtained in doped state. Furthermore the PPy (17.3 lm) was obtained and undoped in the Na2SO4 0.1 mol dm3 solutions with a potentiostatic method (E = 1200 mV, t = 1200 s). A SEM micrograph for this coated lm is shown in Fig. 5, in which the coatings structure is seen to be more compact. In this situation the EOCP reaches a less negative value and the prolonged pseudo-plateau at EOCP = 500 mV is obtained. Fluctuations in the potential may represent anionic exchanges of sulphate and chlorides and solvent exchanges between the polymer lm and the solution during equilibrating in 3% NaCl solution. This EOCP does not indicate the formation or maintenance of a passive layer on the mild steel. For the thicknesses of more than 17.3 lm the results are no better. Experiments were also carried out after drying the polymer lm at 80 C for two days, but the EOCP results were worse and after 48 h approached those of bare mild steel, revealing their unsuitability to protect the mild steel substrate. Cyclic voltammetry in 3% NaCl at a scan rate of 5 mV s1 was also performed with the electrodes described in the former paragraph, yielding the results indicated in Fig. 6. With mild steel and chemically passivated mild steel the current density has high values, indicating that the substrates are not protected in this aggressive medium (Fig. 6a and b). Compared with the PPydoped lm (Fig. 6c) the current density is somewhat lower, though its value continues to be high, since as well as the contri-

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Fig. 5. SEM surface micrograph of a PPyundoped lm (E = 1200 mV, t = 1200 s).

3500

a
3000 2500

b
i (A . m-2 )
2000

c
1500 1000 500 0 -500 -1000

d e

-500

500

1000

1500

E (mV/Ag/AgCl)
Fig. 6. Cyclic voltammogram in 3% NaCl, scan rate 50 mV s1. (a) Mild steel, (b) chemically passivated mild steel, (c) PPydoped, (d) PPydoped and polarised and (e) PPyundoped.

bution of the corroding substrate it is necessary to take into account that the polymer layer is active from the redox point of view, and therefore the oxidation current contributes to this density. When the PPydoped is subjected to a polarisation process (between EOCP and EOCP 1000 mV at v = 2 mV s1), the polymer lm presents good anti-corrosive properties as a protective lm. This process implies a partial reduction in the polymer layer. Better results are obtained when the PPy

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(17.3 lm) is in the undoped state (Fig. 6e). In this case E = 1200 mV was applied to the lm for 1200 s. The layer is compact and it seems that the partial reduction in the load on the polymers backbone contributes favourably to the protection process. As complementary experiments, potentiodynamic polarisation curves have been plotted (Fig. 7) for the dierent samples (mild steel, chemically passive mild steel, PPydoped coated mild steel and PPyundoped coated mild steel) in the corrosive solution. Corrosion rate information can be obtained by the Tafel extrapolation method, where the intersection point of a cathodic and anodic polarisation curve provides both the corrosion potential and the corrosion current. Tafel extrapolations show that the PPydoped and PPyundoped coatings cause a positive shift of around 200 mV in the corrosion potential compared with bare mild steel. The Tafel measurements also show that the i0 values for coated mild steel are higher than for bare mild steel (Table 1), but in this case i0 is the exchange current density for the complex process, where there are several electroactive species and surfaces with several structural and morphology exchanges. The polymer lm also contributes to the exchange current density and thus the value of i0 is not only the contribution of the corrosion rate. We propose a complex mechanism for the corrosion process according to the results obtained Anodic reactions Fe 2e ! Fe2 PPyundoped ne ! PPydoped
1000 800 600 400 200 0 -200 -400 -600 -800 -1000 -1200 -1400 -1600 -1800

E (mV/Ag/AgCl)

b a

c d

-2.0

-1.0

0.0

1.0
-2

2.0

3.0

log i ( i = A m )
Fig. 7. Potentiodynamic curves in 3% NaCl for: (a) mild steel, (b) chemically passivated mild steel, (c) PPydoped 17.5 lm and (d) PPyundoped 17.5 lm.

 P. Ocon et al. / Corrosion Science 47 (2005) 649662 Table 1 Interchange current densities System Mild steel Chemically passivated PPydoped (17.3 lm) PPyundoped (17.3 lm) Current density i0 (A m2) 3.8 2.8 24 5.2

657

Cathodic reactions PPydoped ne ! PPyundoped O2 H2 O 4e ! 4OH PPyundoped ne ! PPy0undoped Chemical reaction 2OH Fe2 ! FeOH2 ! FeOH3 ! Fe2 O3 This mechanism assumes that mild steel has oxidised by yielding electrons to PPydoped and that PPydoped has been reduced, as a result of which the SO anions 4 are ejected and the polymer lm is more compact. But the PPyundoped can be reoxidised by the oxygen from the solution (i.e. from the air), and the time of protection by the polymer lm coating will depend on the relative reaction rate, as well as the available amount of PPydoped. When the coating lm is undoped, its volume changes and the lm is more compact and the corrosion solution less accessible to the substrate. The depolarisation of mild steel may be modied depending on the quality of the chemically generated oxide lm. In order to study the protection of PPy lms the amount of free (Fe2+) in solution was determined. The reaction with ortho-phenantroline allows the quantication of these species by spectroscopy, which is indicative of the corrosion process. Their evolution with immersion time has been determined and Fig. 8 shows the amount of Fe2+ in parts per million (ppm). According to these experiments PPyundoped is the best coated lm in terms of anti-corrosive properties. If 1 ppm of (Fe2+) is established as the threshold for corrosion evaluation, it can be seen that PPyundoped with 17.3 lm, has protected the substrate for at least 120 h, but that PPydoped can only be considered protective for a time of less than 24 h; irrespective of the i0 values determined by the potentiodynamic curves. Electrochemical impedance spectroscopy (EIS) measurements conrm the potentiodynamic and OCP results. The corrosion of a PPy-coated mild steel electrode has been investigated for dierent immersion times in an aerated 3% NaCl solution. EIS, as a means of determining the eectiveness of corrosion inhibitors, provides valuable insight into corrosion mechanisms. The frequency by frequency response can be modelled by equivalent circuits [2025].

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Fig. 8. [Fe2+] in solution for dierent immersion times. ( ) Mild steel, (h) chemically passivated mild steel, ( ) PPydoped and (j) PPyundoped.

EIS data was recorded after immersing the electrode in the aggressive medium for 500 s. Nyquist plots were constructed and an appropriate equivalent circuit model was used to correlate the impedance with the capacitance and the resistance of the lm. Figs. 911 show Nyquist plots for mild steel, PPydoped and PPyundoped respectively for dierent immersion times. Equivalent circuit models for these substrates are assumed and the values are given in Table 2. It can be seen that the models t the experimental data reasonably well, considering in all cases e 6 5% for all the

350

300

250

mild steel
-Z "/ ohm
200

150

0h 10 Hz

100

50

10 Hz

24 h

0.5 Hz

0.5 Hz

0 0 50 100 150 200 250 300 350

Z'/ ohm

Fig. 9. The Nyquist diagrams for the mild steel in 3% NaCl for dierent immersion times.

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60

659

50

40

PPydoped

-Z "/ ohm

30

0.1 Hz
20

10 Hz 120 h 0h 0.1 Hz
20 30 40 50 60

216 h 10 Hz

10

0.1 Hz

0 0 10

Z'/ ohm

Fig. 10. The Nyquist diagrams for PPydoped in 3% NaCl for dierent immersion times.

120

100

PPyundoped

80

-Z "/ ohm

60

72 h 0.1 Hz 10 Hz

40

192 h 0.1 Hz 0.1 Hz

60 80 100 120

20

10 Hz 10 Hz
0 20 40

oh

Z'/ ohm

Fig. 11. The Nyquist diagrams for PPyundoped in 3% NaCl for dierent immersion times.

parameters of the corresponding equivalent circuits. From these EIS results it can be seen that immersion time has a signicant eect on the impedance of the samples. For mild steel and timmersion = 0 the Rp is 500 X and the CPE 4.5 107 and n = 0.55. With an immersion time of 24 h the corrosion rate rises and the parameters are as shown in Table 2. Furthermore the value of n = 0.64 indicates a greater degree of roughness of the substrate compatible with the formation of iron oxide and hydroxide type corrosion products. In the case of coated samples and short immersion times the impedance plots present a linear region in the low frequency region, which means that the lm behaves like a blocked electrode. The corrosion reaction is inhibited by mass transfer limitation and a redox reaction may be taking place

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Table 2 The values obtained from the equivalent circuit for dierent samples System immersion time (h) Fe, t = 0 Rs (X) 2.00 Rct (X) 500 QCPE (F) 4.5 107 n 0.55 W (X1 s1/2) Equivalent circuit
Rs Q Rct

Fe, t = 24

6.74

321

8.3 104

0.64

Rs

Q Rct

Fe/PPydoped, t = 0

6.89

5.50

8.4 104

0.44

0.20

Rs

Q R ct
W

Fe/PPydoped, t = 120

9.25

46.4

6.7 105

0.66

0.03

Rs

Q R ct
W

Fe/PPydoped, t = 216

2.16

32.6

7.7 105

0.73

0.02

Rs

Q R ct
W

Fe/PPyundoped, t = 0

5.96

75.3

1.2 105

0.37

Rs

Q Rct

Fe/PPyundoped, t = 72

11.55

3500

3.6 107

0.35

Rs

Q Rct

Fe/PPyundoped, t = 192

8.79

73.2

6.0 105

0.68

0.03

Rs

Q R ct
W

n indicate the capacitive like behaviour of the constant phase element Q. The impedance of the constant phase element is ZQ = A(jx)n, where 0 < n < 1, A is the frequency independent constant, and x is the angular frequency.

within the coating. When the immersion time is short the chemically passive lm constructed in the initial process before the PPy is grown can continue to prevent the corrosion of mild steel. When the immersion time is longer, the linear region is transformed into a capacitative loop and the resistance is decreased. The capacitative behaviour can be attributed to the interface inside the polymer layer. In summary, Table 2 shows the circuit that correspond to the bare mild steel electrode. The parallel net RQ is in series with the ohmic resistance. Where R represents the charge transfer resistance and Q is related with the double layer capacity. In Fe/ PPydoped electrode, Warburg impedance appears which is related with anionic exchange between the solution and inside of the polymer layer. This impedance parameter W decreases when the immersion time increases, because of the saturation

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of the polymer layers with the arrival of Cl anions. In the Fe/PPyundoped we can see that there is no impedance associated with mass transfer which indicates that there is no ionic exchange with the solution until a time longer than 192 h. Above this considerations, explain the observed protective behaviour of this polymer coating against corrosion in that strongly corrosive media.

4. Conclusion The results show that the coated polymer lms shift the electrode potential towards more positive potentials, but that this shift does not lead to passivation. However, a notable synergy exists between PPyundoped lm, oxygen reduction and iron dissolution. The potential of mild steel remains in the active dissolution region and a passive oxide layer is not possible in this region. PPy separates the metal dissolution process from the oxygen reduction process. This would prevent the local pH increase at the metal surface and subsequent delamination. The polarisation curves, EOCP and impedance measurements show that PPyundoped layers promise to be a good candidate for corrosion protection of reactive metals.

Acknowledgement Financial support of this research by the Spanish Ministry of Science and Technology is gratefully acknowledged (BQU2001-0149).

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