www.elsevier.

nl/locate/jelechem Journal of Electroanalytical Chemistry 485 (2000) 13 20

Aniline electropolymerization on platinum and mild steel from neutral aqueous media
J.-L. Camalet a, J.-C. Lacroix a,*, T. Dung Nguyen a, S. Aeiyach a, M.C. Pham a, J. Petitjean b, P.-C. Lacaze a
a

Institut de Topologie et de Dynamique des Systemes de lUni6ersite Paris, 7 -Denis Diderot, Associe au CNRS (UPRES-A 7086), ` 1 rue Guy de la Brosse, 75252 Paris Cedex 05, France b USINOR, Recherche et De6eloppement, LEDEPP, 17 A6enue des Tilleuls, BP 70011, 57191 Florange Cedex, France Received 23 July 1999; received in revised form 4 February 2000; accepted 22 February 2000

Abstract Aniline has been electropolymerized on platinum from neutral aqueous electrolytes. The properties of the resulting polyaniline (PANI) lms are similar to those obtained in acidic media. PANI lms can be generated using multiple cyclic voltammetry or galvanostatically. In the former case, the molecular structure of the lms depends on the inversion potential and two types of material can be generated. When potential sweeps are restricted to an inversion potential of 0.8 V, the lms do not have a PANI-like structure, whereas an inversion potential of 1 V allows the deposition of short PANI-like chains, as demonstrated by SEC and MALDI-MS techniques. In the galvanostatic mode, the molecular structure of the lms depends on the applied current density. There is a current density window which makes it possible to grow PANI lms from neutral electrolytes with the same efciency as in acids and which depends drastically on the experimental conditions. In the case of a 2 M LiClO4 + 0.4 M aniline solution, a very high current density can be used for PANI deposition on platinum. These neutral aqueous electrolytes have been used for the deposition of PANI lms on mild steel. The lms are generated with less metal dissolution than when acid electrolytes are used and exhibit similar anticorrosion properties. 2000 Elsevier Science S.A. All rights reserved.
Keywords: Electropolymerization; Polyaniline; Corrosion protection; Mild steel

1. Introduction From an application point of view, polyaniline (PANI) is considered as one of the best organic conducting materials. Its synthesis is performed generally in aqueous acid solutions, either chemically or electrochemically and it is considered generally that good quality PANI lms cannot be obtained from neutral aqueous media. However, at the beginning of the 1990s, Duic et al. [1] reported that PANI lms could be produced from neutral aqueous perchlorate and nitrate solution. Simultaneously, several reports were published in which aniline derivatives were electropolymerized in non-aqueous solution without a proton donor [2 4].

* Corresponding author. Fax: +33-1-44276814. E-mail address: lacroix@paris7.jussieu.fr (J.-C. Lacroix)

Among the technological applications proposed for PANI, deposition on oxidizable metals for anticorrosion purposes has been the topic of several studies [512]. Indeed, PANI has been shown to be capable of reducing mild steel oxidation considerably and replacement of stainless steel by PANI-coated mild steel has been claimed recently [13]. Electropolymerization of aniline on oxidizable metals is difcult because the oxidation potentials of these metals are much more negative than that of aniline and, consequently, dissolution of the metal will occur before electropolymerization starts. Therefore, to form PANI lms on oxidizable metals, it is necessary to nd conditions which will strongly passivate the metal without impeding electropolymerization. Most studies of the electropolymerization of aniline on oxidizable metals have used acid aqueous electrolytes in which passivation of the oxidizable metal is not obtained easily. We have reported recently, PANI electrosynthesis on mild steel

0022-0728/00/$ - see front matter 2000 Elsevier Science S.A. All rights reserved. PII: S 0 0 2 2 - 0 7 2 8 ( 0 0 ) 0 0 0 8 0 - 2

14

J.-L. Camalet et al. / Journal of Electroanalytical Chemistry 485 (2000) 1320

from oxalic [8,9] and tosylic [10] acid solutions. With both electrolytes it is possible to reach a passivation state without blocking the surface toward aniline oxidation, but this surface state is obtained after dissolution of a rather thick layer of the mild steel substrate. The ease of oxidizable metal passivation in neutral aqueous media has incited us to reinvestigate the possibility of PANI electrodeposition from such electrolytes. The rst objective of this work is to investigate aniline oxidation on a platinum electrode in order to determine the electrochemical conditions that allow the growth of PANI lms with properties similar to those obtained in aqueous acids. The second is to use these neutral electrolytes to electrosynthesize PANI on mild steel and to minimize metal dissolution in the deposition process.

tron multiplier (Thorn-EMI, EM 643). The polymer solution in DMF is mixed with a THF solution of a-cyano-3-hydroxycinnamic acid (the matrix). The nal solution is deposited onto stainless steel substrates and allowed to dry in air before analysis.

3. Results and discussion The potentiodynamic response between 0.2 and 1 V of a platinum electrode in 2 M LiClO4 +0.2 M aniline solution was rst investigated. The rst cycle shows aniline oxidation starting at around 0.5 V and in the following cycles a positive shift of the aniline oxidation peak associated with a strong intensity decrease is observed. This indicates that some material has deposited on the electrode. This material is slightly electroactive in 2 M LiClO4 + 0.2 M aniline solution as judged by comparing the level of the background current in the 0.1 to 0.5 V region in the second or third cycle with that of bare platinum. This behavior has already been reported for aniline oxidation in neutral aqueous electrolytes. However, after a few cycles, the aniline oxidation peak starts to increase, indicating that the deposited material does not block the platinum surface. Thick, homogeneous and adherent black green lms are generated on the surface. Their thickness can be controlled by adjusting the number of cycles. Fig. 1 compares the electrochemical properties for the rst three cycles in the usual 2 M H2SO4 medium of a lm deposited from a 2 M LiClO4 + 0.2 M aniline solution by sweeping the potential between 0.1 and 0.7 V at a sweep rate of 50 mV s 1. Even though two distinct peaks can be seen in the lm reduction signal, it is clear that the electrochemical behavior is similar to

2. Experimental Electrochemical syntheses were carried out in a single-compartment three-electrode cell using an EG&G PAR 362 potentiostat in the potentiodynamic mode. Platinum coated glass, a 3 cm2 iron plate (Weber metals) with %Fe\ 99.5 and mild steel (provided by SOLLAC) were used as working electrodes, and the counter-electrode was a platinum grid. All potentials were measured with respect to a saturated calomel electrode (SCE). The pH values of the so called neutral solutions were slightly basic prior to the electropolymerization process and aniline derivatives were mostly completely soluble (homogeneous solution) as long as the electrolyte was highly concentrated. With a lower electrolyte concentration or in pure water, most of these species are not soluble in such concentrations. This probably reveals some sort of association complexation between aniline and the electrolyte salt which has not been investigated fully. IR spectra were recorded on a Nicolet SX 60 Fourier transform spectrometer. XPS spectra were recorded on a Vacuum Generators Escalab MK1 spectrometer equipped with an unmonochromated Mg Ka X-ray source (power applied to the anode= 100 W) at pressures in the 10 8 mbar range. The analyzer was operated at constant pass energy (20 eV). The spectra were digitized, summed, smoothed and reconstructed using Gaussian-shaped components. Binding energies are referred to C1s 285 eV. Molar mass measurements were carried out using GPC and MALDI techniques on a 0.5 1% DMF solution of deprotonated PANI synthesized as lms on mild steel electrodes. For GPC, the measurements were performed on a system consisting of a Waters 510HPLC pump and a Waters 486 tunable absorbance detector. For MALDI, the mass spectra were recorded by using a TOF spectrometer (P= 2 10 7 Torr) and a pulsed nitrogen laser (VSL 337 ND, Laser Science Inc.) The ions are detected with a venetian blind secondary elec-

Fig. 1. Electroactivity in 2 M H2SO4 of a PANI lm generated in 2 M LiClO4 +0.2 M aniline aqueous solution by sweeping the potential between 0.1 and 1 V at a sweep rate of 50 mV s 1: (a) after the rst cycle; (b) after three cycles.

J.-L. Camalet et al. / Journal of Electroanalytical Chemistry 485 (2000) 1320

15

Fig. 2. IR spectra of lms generated in 2 M LiClO4 + 0.2 M aniline aqueous solution by sweeping the potential between (sweep rate 50 mV s 1): (a) 0.1 and 1 V; (b) 0.1 and 0.8 V.

Fig. 3. N1S XPS signal of lms generated in 2 M LiClO4 + 0.2 M aniline aqueous solution by sweeping the potential between (sweep rate 50 mV s 1): (a) 0.1 and 1 V; (b) 0.1 and 0.8 V.

what is obtained when acidic media are used for electropolymerization. Furthermore, a regular increase of the lm thickness with the number of cycles is seen. This result is in marked contrast with what is generally reported when neutral aqueous electrolytes are used for aniline oxidation; that is, no PANI-like structure can be generated [14]. The upper potential limit of the potential sweep has a dramatic impact on the lm deposited on the platinum electrode. When the inversion potential is only 0.8 V, progressive passivation of the electrode is observed, as in Ref. [14]; thick lms cannot be produced and those formed do not show the usual PANI electroactivity when cycled in 2 M H2SO4 solution. The lms were characterized using several spectroscopic techniques. Fig. 2 shows the IR spectra of lms deposited potentiodynamically in aqueous 2 M LiClO4 + 0.2 M aniline solution. It is clear that those generated with a potential sweep between 0.1 and 1 V do not have the same molecular structure as that generated between 0.1 and 0.8 V. The former shows the usual PANI bands, i.e. 1580 and 1500 cm 1, associated with the quinoid and benzenoid forms of PANI, 1380, 1300 and 1255 cm 1, attributed to C N vibrations and 830 cm 1 C H outof-plane vibration, indicating that the chains consists mainly of 1,4-disubstituted benzene units [15,16]. The lack of vibrations around 900 cm 1 and 800700 cm 1 indicates that 1,2- and 1,3-disubstitutions do not occur to a signicant extent. Furthermore, perchlorate IR bands at 1090 and 620 cm 1 are clearly visible [17]; this indicates that the material is doped and probably partially protonated during the electrosynthesis, despite the fact that the electrolyte solution is neutral. The latter shows additional IR bands at 1440, 930, 880, 752, 692 cm 1 which can be attributed to azo compounds and to mono and 1,2-disubstituted phenyl rings [16,17]. XPS measurements were performed in order to determine to what extent protonation takes place during potentiodynamic electrosynthesis. To do so, the lms were rinsed with the minimun amount of water and ethanol in order to avoid massive deprotonation of the upper layers in the rinsing procedure. Chloride atoms are detected in the general XPS spectra; however, no lithium signal is detected. This indicates that the rinsing procedure removes excess electrolyte and that the lms must bear positive charges in order to maintain electroneutrality. Analysis of the nitrogen signal gives more precise information about the PANI structure since amine, imine and protonated nitrogens can be distinguished. The nitrogen signal of a lm can be decomposed into four peaks located at 398.7, 399.8, 400.8 and 401.7 eV, labelled N1, N2, N3 and N4, respectively (Fig. 3). The N1 peak is associated with neutral imine, the N2 peak is attributed to neutral amine and N3, N4 to positively charged nitrogens N + = N3 + N4 [18,19].

16

J.-L. Camalet et al. / Journal of Electroanalytical Chemistry 485 (2000) 1320

The lm is protonated on the imine sites which are more basic than amine sites [18 20]. Protonated PANI does not show the 398.7 eV N1 component whereas it is detected in the lm which has been deprotonated. The ratio N + /Ntotal is a measure of the amount of protonated nitrogen while (N1 +N + )/Ntotal gives the proportion of oxidized aniline units in the chains. Table 1 shows the ratios of total carbon to total nitrogen (Ctotal/Ntotal), imine nitrogen to total nitrogen (N1/Nt), amine nitrogen to total nitrogen (N2/Nt), protonated nitrogen to total nitrogen (N + /Nt) and protonated nitrogen to chloride (N + /Cl) for a lm prepared by sweeping the potential up to 1 or 0.8 V. For comparison, the XPS nitrogen signal analysis of a PANI lm generated in tosylic acid solution on a mild steel electrode [11] is also included in Table 1. For these lms the Ctotal/Ntotal ratios are close to the theoretical value of 6. The discrepancy is attributed to the presence of contaminants on the lm surface (and to the inherent imprecision of XPS). Films prepared by sweeping the potential up to 1 V are obtained with a 45% oxidation level and 32% of the nitrogens are protonated. This is to be compared with PANI lms generated in conventional acidic media in which most of the imine sites are protonated. Considering a pKa value of 5.5 6.5 for the imine sites, it is probable that during the electropolymerization process the local pH in the vicinity of the electrode in aqueous 2 M LiClO4 + 0.2 M aniline solution can reach a value where most of these sites are protonated. Indeed, coupling reactions leading to the polymer are associated with deprotonation of the intermediate dihydrooligomers. On the other hand, lms obtained with an inversion potential of 0.8 V appear to be less oxidized and, more importantly, much less protonated since only 15% of the nitrogens are protonated. Even though a specic interaction with LiClO4 cannot be excluded at this point, it is likely that the difference in the regioselectivity of the coupling reaction observed on changing the inversion potential is mainly due to the difference in the local pH, which is lower in the rst case because many more radical-cations are generated. The molar mass of the polymer generated by sweeping the potential between 0.1 and 1 V was determined by two methods: GPC which gives relative

masses determined from standard polystyrenes, and MALDI-MS (matrix-assisted UVlaser desorption ionization) which gives absolute masses and was used in our recent studies focused on PANI deposition on mild steel in acids [10,11]. The GPC results obtained with UV detection show a broad peak and a weaker peak corresponding to molar masses of 6500 and 2 105 g mol 1, respectively. These values are below the molar masses estimated by GPC for PANI grown on a platinum electrode in H2SO4 solution [21,22]. The bimodal distribution observed for the PANI solution has already been reported [21,22] and the high molar mass peak was attributed to aggregates of polymer chains linked through hydrogen bonds. Therefore, the peak at 2105 Da does not correspond to chains of high molar mass. From the GPC results it can be concluded that the polymer generated from aqueous 2 M LiClO4 + 0.2 M aniline solution consists of chains of lower molar mass than the material generated from the usual acidic electrolyte. Molar mass determination using GPC is not very precise since it uses polystyrene standards whose chemical structure is not analogous to that of polyaniline. Consequently, GPC does not give the absolute molar mass but can be used to compare two polyaniline samples prepared under different conditions. On the other hand, the MALDI technique is ideal for the analysis of the mass distribution of non-conjugated synthetic polymers. The method is extremely sensitive (pmolfmol) with a relatively short analysis time (some minutes). The absolute molar mass of each chain of the polymeric sample can be determined, the repeat motif can be seen and molar mass distributions determined. When dealing with conjugated synthetic polymers, the MALDI-MS results must be taken with caution since high molar mass oligomers might not desorb as easily as lower molar mass oligomers. Fig. 4 shows the mass spectrum of our samples for values of m/z between 500 and 4500. Each signal corresponds to a polymer chain of mass m/z (z= +1) and its intensity is proportional to the number of chains of mass m/z. The molar mass that appears most frequently is below 1000, far from the values determined by GPC measurements, as already observed in our previous studies [10,11]. Several patterns are observed

Table 1 Quantitative analysis of N1s XPS signal for lms generated in 2 M LiClO4+0.2 M aniline aqueous solution by sweeping the potential between (sweep rate 50 mV s1) 0.1 and 1 V (PANI 1 V), 0.1 and 0.8 V (lm 0.8 V) and for a lm generated in 2 M tosylic acid+0.2 M aniline solution (PANI tos) Ctotal/Ntotal PANI 1 V Film 0.8 V PANI tos
a

N1/Ntotal 0.13 0.24 0

N2/Ntotal 0.55 0.61 0.55

N+/Ntotal 0.32 0.15 0.45

N+/dopant 1 1 1a

6.3 6.2 6.5

In the last case, N+/dopant refers to the N+/tosylic ratio.

J.-L. Camalet et al. / Journal of Electroanalytical Chemistry 485 (2000) 1320

17

Fig. 4. MALDI of a PANI lm synthesized in 2 M LiClO4 + 0.2 M aniline aqueous by sweeping the potential between 0.1 and 1 V.

consisting of peaks corresponding to different polymer chains. The two main peaks of two successive patterns are separated by Dm =90 or 91 g mol 1, which indicates that the polymer motif is indeed aniline. Fig. 4 shows details of the MALDI spectra for masses between 750 and 950. Each pattern shows secondary peaks detected at Dm =14 15 or 16 g mol 1 already observed in the MALDI-MS spectra of PANI lms generated from oxalic or tosylic acid solutions [10,11]. This seems to indicate the replacement of a NH group by a hydrogen. From these experiments it can be concluded that PANI electropolymerization from a neutral aqueous electrolyte using cyclic voltammetry is possible. The lms have properties similar to those obtained when acidic aqueous media are used even though shorter chains are generated. Cyclic voltammetry is not a suitable deposition technique for industrial applications. From an industrial point of view, galvanostatic deposition at high current density, in a one-step process, is a key criterion for most electrochemical deposition processes (especially onto oxidizable metals). Such a deposition mode is necessary for mass production at a reasonable cost. We have therefore investigated PANI electropolymerization from neutral aqueous electrolyte using galvanostatic conditions. The galvanostatic response of a platinum electrode in aqueous 2 M LiClO4 +0.2 M aniline solution depends on the applied current density. For current densities lower than 3 mA cm 2, the potential stabilizes at a value between 0.6 and 0.8 V. Black lms are generated. They are soluble in ethanol and only slightly electroactive in 2 M H2SO4 (Fig. 5(a)). These lms are probably similar to those obtained in the potentiodynamic mode with 0.8 V inversion potential but were not character-

ized fully. For current densities between 3 and 6 mA cm 2, the potential stabilizes at around 1.2 V, black green lms with PANI-like electroactivity in 2 M H2SO4 are produced as can be seen in Fig. 5(b). For higher current densities, the potential stabilizes above 2 V, the lms are of poor quality (overoxidized) and are poorly electroactive in 2 M H2SO4. Furthermore, at such a potential, oxygen evolution is likely to occur and compete with PANI electrodeposition. The efciency of electrosynthesis was measured by plotting the amount of charge Qs involved in the switching of the polymer between 0 and 0.6 V in 2 M H2SO4 (see Fig. 5) versus the charge Qp = jt consumed during electropolymerization. Fig. 6 compares the results obtained when the lms are grown from the 2 M LiClO4 + 0.2 M aniline solution at 5 mA cm 2 and from the usual 2 M H2SO4 + 0.1 M aniline medium. It can be seen that the PANI deposition yield in neutral lithium perchlorate solution is similar to that from the usual acid electrolytes.

Fig. 5. Electroactivity in 2 M H2SO4 of a PANI lm generated in 2 M LiClO4 +0.2 M aniline aqueous solution with a current density of: (a) 2 mA cm 2; (b) 5 mA cm 2.

18

J.-L. Camalet et al. / Journal of Electroanalytical Chemistry 485 (2000) 1320

Fig. 6. Qs involved in the switching of the polymer between 0 and 0.6 V in 2 M H2SO4 versus the charge Qp = jt consumed during electrodeposition: 2 M LiClO4 + 0.2 M aniline, j = 5 mA cm 2; +2 M H2SO4 +0.1 M aniline, j =0.25 mA cm 2.

Fig. 7. Qs measured between 0 and 0.6 V of a PANI lm generated with various current densities in 2 M LiClO4 and (a) 0.1 M aniline; (b) 0.2 M aniline; (c) 0.4 M aniline.

Fig. 8. Qs measured between 0 and 0.6 V of a PANI lm generated with various current densities in 0.2 M aniline and (a) 2 M LiCLO4; (b) 2 M NaClO4; (c) 2 M KNO3; (d) 2 M LiCl.

PANI lms of similar thickness were grown (by adjusting the electrolysis time in order to have the same electrodeposition charge Qp =1 C cm 2 for all lms) at various current densities and with various monomer concentrations. Qs involved in the switching of the polymer between 0 and 0.6 V in 2 M H2SO4 was then measured (see Fig. 5(a and b)). It was approximately 180 mC cm 2, which means that the yield is approxi-

mately the same as when the synthesis is performed in an acidic solution. It is found that Qs is very sensitive to the electrochemical conditions and depends markedly on the current densities used, as shown in Fig. 7. There is clearly a current density window that makes it possible to grow PANI lms from neutral LiClO4 with the same efciency as in acidic media. Furthermore, it can be seen that increasing the aniline concentration, widens this current density window considerably. At 0.4 M, a current density as high as 40 mA cm 2 can be used and the width of the window extends over 30 mA cm 2. Above 40 mA cm 2 the potential stabilizes at a high value, oxygen evolution is likely to occur and probably prevents PANI deposition. On the other hand, at 0.1 M, the current density window for producing PANI lms in high yield is very narrow. The monomer type was varied in order to see if some substituted anilines which do not give materials with the polyaniline structure in acidic solutions (anilines with electron-withdrawing groups) [23] do so in neutral electrolytes. It is found that the substituted anilines (0.2 M) known to give poly(substituted aniline) lms in acid electrolytes are also capable of generating the same kind of lms in 2 M LiClO4. o-Toluidine, m-toluidine, o-diaminobenzene, o-aminophenol, o-methoxyaniline, m-methoxyaniline, o-ethoxyaniline and diphenylamine gave lms with similar electroactivity in 2 M H2SO4 as the materials produced with the usual acidic solutions. On the other hand, those that do not give the PANI like structure in acid electrolytes (anthranilic acid, o-nitroaniline and m-nitroaniline) do not do so in LiClO4 and yield very thin passivating lms. (When the solubility was not high enough to allow the use of 0.2 M monomer solutions, the experiments were performed with saturated solutions.) Furthermore, the current density window which can be used to grow poly(substituted aniline) lms from neutral LiClO4 with the same efciency as in acidic media depends on the monomer type. Qs versus current density curves have the same bell shape as for polyaniline but high yields are obtained at lower current for anisidine and toluidine than for aniline. Finally, other supporting salts were tested to check whether Li+ or ClO has a specic interaction with aniline which 4 makes it possible to orient the reactions towards 1,4 head-to-tail C N coupling. Fig. 8 shows that several electrolytes can be used to electropolymerize aniline: LiClO4, NaClO4 and KNO3 give essentially the same results. Electropolymerization from LiCl solution is also possible but the yield is somewhat lower than for the other electrolytes. The lms were characterized by several techniques. IR spectra of fully reduced and deprotonated PANI lms are very similar to those of PANI deposited from acidic media. Some differences can be seen in the

J.-L. Camalet et al. / Journal of Electroanalytical Chemistry 485 (2000) 1320

19

1000 600 cm 1 region where there are small bands at 750 and 695 cm 1 which can be attributed to monosubstituted or to 1,3-disubstituted benzene and could indicate that the lm probably consists of low molar mass oligomers. For lms generated at current densities close to the border of the electrochemical window, these IR bands are stronger (Fig. 9). MALDI-MS spectra of PANI, poly(anisidine) and poly(toluidine) lms deposited in 2 M LiClO4 +0.2 M monomer solution at the appropriate current density show that the lms still consist of low molar mass chains (molar mass B 1500) with the two main peaks of two successive patterns separated with a Dm = 90 or 91, Dm= 120 or 121 and Dm = 104 or 105 g mol 1, respectively. LiClO4 is known to passivate mild steel. Solutions of 2 M LiClO4 + 0.2 M aniline, anisidine and toluidine were therefore used to perform electropolymerization on this metal. Homogeneous, strongly adherent lms

Fig. 9. IR spectrum of a PANI lm deposited in 2 M LiClO4 + 0.4 M aniline at (a) j= 10 mA cm 2; (b) j = 15 mA cm 2; (c) j= 20 mA cm 2; (d) j=40 mA cm 2.

Fig. 10. Galvanostatic response of a mild steel electrode in a 2 M LiClO4 + 0.2 M aniline solution at various current densities: (a) j=5 mA cm 2; (b) j =1 mA cm 2; (c) j = 0.5 mA cm 2.

can be obtained galvanostatically. No induction period is observed in the galvanostatic response (Fig. 10) of the electrode; this indicates that passivation occurs readily. This is in marked contrast with the results obtained in oxalic or in tosylic acid solutions even though, in the latter case, metal dissolution can be minimized by using high current densities [24]. Metal dissolution can therefore be minimized by using such a neutral electrolyte. PANI deposition yields were measured for lms generated at 0.1 mA cm 2. An electrodeposition charge of Qp = 1 C cm 2 yielded lms 4 mm thick, which compares well with the literature results and indicates that the yield is close to 100%. Furthermore, yields of 90% were obtained by using mass measurements. MALDI and IR spectroscopy were used to characterize these lms. It is found that the molar mass of the PANI chains (DPB 10) generated is slightly lower than those deposited on platinum (DPB15). MALDI-MS spectra exhibits repeat patterns separated by Dm = 90 or 91 g mol 1. The FTIR spectra show the general features of a PANI-like material. Good quality, thick, PANI lms could not be obtained when the current density was increased. With 2 M LiClO4 + 0.2 M aniline a maximum current density of 0.2 mA cm 2 could be used to generate lms of controlled thickness. When the aniline concentration is increased to 0.4 M, strongly adherent PANI lms could be generated at 5 mA cm 2. At this current density, the lms were less homogeneous than at lower densities but lms with good homogeneity were produced by adding Triton X-100 to the solution. The effect of this surfactant was not fully investigated. At higher current densities, measured yields decreased sharply after a short initial period at which they are close to 90% (mass measurements). These results indicate that the concentration effect already seen on platinum substrates still applies with mild steel but also that electropolymerization in such a medium is very sensitive to the electrochemical conditions used. The maximum current density which can be used for the electrodeposition of good quality PANI lms on mild steel need to be improved for industrial application. Preliminary corrosion studies were performed on mild steel samples coated with PANI, poly(anisidine) and poly(toluidine) lms synthesized in 2 M LiClO4 + 0.2 M aniline with a current density of 2 mA cm 2. In this case, the polymerization yield is quantitative when Qp is below 300 mC cm 2, which corresponds to 1.3 mm PANI lms. The samples were dipped in a corrosive solution of 0.1 M HCl and 0.4 M NaCl. The extent of corrosion was measured by determining spectrophotometrically the amount of Fe2 + in solution, using an a-phenanthroline method [25]. The amount of Fe2 + in solution after 5 h immersion of such coated mild steel electrodes was signicantly less than for untreated elec-

20

J.-L. Camalet et al. / Journal of Electroanalytical Chemistry 485 (2000) 1320

trodes and no loss of adhesion occurred. Compared to a bare sheet, there is ten and 30 times less Fe2 + in solution with Fe/PANI and Fe/poly(anisidine) or Fe/ poly(toluidine) electrodes, respectively. Although, more detailed corrosion tests were not performed because electropolymerization at high current density failed, these results indicate that the conducting polymers protect the underlying metal against corrosion even though the material consists mainly of short oligomers. Oligo(anisidine) and oligo(toluidine) are more effective than oligo(aniline) as has already been observed in the literature [26,27].

References
[1] L. Duic, Z. Mandic, J. Electroanal. Chem. 335 (1992) 207. [2] N. Kobayashi, K. Yamada, R. Hirohashi, Electrochim. Acta 37 (1992) 1091. [3] K. Yamada, K. Teshima, N. Kobayashi, R. Hirohashi, J. Electroanal. Chem. 394 (1995) 71. [4] M.C. Miras, C. Barbero, R. Kotz, O. Haas, J. Electrochem. Soc. 138 (1991) 335. [5] D.W. DeBerry, J. Electrochem. Soc. 132 (1985) 1022. [6] G. Troch-Nagels, R. Winand, A. Weymeersch, L. Renard, J. Appl. Electrochem. 22 (1992) 756. [7] B. Wessling, Adv. Mat. 6 (1994) 226. [8] W.K. Lu, R.L. Elsenbaumer, B. Wessling, Synth. Met. 71 (1995) 2163. [9] J.L. Camalet, J.C. Lacroix, S. Aeiyach, K.I. Chane-Ching, P.C. Lacaze, J. Electroanal. Chem. 416 (1996) 179. [10] J.L. Camalet, J.C. Lacroix, S. Aeiyach, K.I. Chane-Ching, P.C. Lacaze, Synth. Met. 93 (1998) 133. [11] J.L. Camalet, J.C. Lacroix, S. Aeiyach, P.C. Lacaze, J. Electroanal. Chem. 445 (1998) 117. [12] D. Sazou, C. Georgolios, J. Electroanal. Chem. 429 (1997) 81. [13] B. Wessling, Synth. Met. 93 (1998) 143. [14] T. Ohsaka, Y. Ohnuki, N. Oyama, G. Katagiri, K. Kamisako, J. Electroanal. Chem. 161 (1984) 399. [15] A.G. MacDiarmid, J.C. Chiang, M.-S. Halpern, W. Huang, S. Mu, N.L.D. Somasiri, W. Wu, S.T. Yaniger, Mol. Cryst. Liq. Cryst. 121 (1985) 195. [16] J. Tang, X. Jing, B. Wang, Synth. Met. 24 (1988) 231. [17] G. Socrates, Infrared Characteristic Group Frequencies, Wiley, New York, 1980. [18] H.S.O. Chan, S.C. Ng, W.S. Sim, S.H. Seow, K.L. Tan, B.T.G. Tan, Macromolecules 26 (1993) 144. [19] S.M. Kumar, F. Gaillard, G. Bouyssoux, A. Sartre, Synth. Met. 36 (1990) 111. [20] C. Menardo, M. Nechtsein, A. Rousseau, J.P. Travers, P. Hany, Synth. Met. 25 (1988) 311. [21] C. Visy, J. Lukkari, J. Kankare, Macromolecules 27 (1994) 3322. [22] P.N. Adams, D.C. Apperley, A.P. Monkman, Polymer 34 (1993) 328. [23] J.C. Lacroix, A.F. Diaz, J. Electrochem. Soc. 135 (1988) 1457. [24] J.C. Lacroix, P. Garcia, J.P. Audiere, R. Clement, O. Kahn, New J. Chem. 14 (1990) 149. [25] A.J. Vogel, A Text-book of Quantitative Inorganic Analysis, third ed., Longmans, London, 1961. [26] H. Kaesche, N. Hackerman, J. Electrochem. Soc. 105 (1958) 191. [27] S. Sathiyanarayanan, K. Balakrishnan, S.K. Dhawan, D.C. Trivedi, Electrochim. Acta 39 (1994) 831.

4. Conclusions It is possible to electrosynthesize PANI in high yield from neutral aqueous electrolyte on platinum but it requires precise electrochemical conditions. High current densities can be used when the monomer concentration is high enough. The process can be extended to the polymerization of substituted anilines that are known to give materials with a polyaniline-like structure in acidic solutions. The properties of the lms are similar to those obtained when acidic media are used even though shorter chains are generated. Several neutral electrolytes can be used, and the coupling reactions are probably oriented towards 1,4 C N bond formation by the decrease in the local pH in the vicinity of the electrode. Such electrolytic media can be used to generate PANI or substituted PANI lms on mild steel with little dissolution of the oxidizable substrate. The lms exhibit anticorrosion properties but the maximun current density which can be used for aniline electropolymerization on such substrates needs to be improved for industrial applications.

Acknowledgements The authors wish to thank SOLLAC (USINORSACILOR) for nancial support of this work.