Corrosion Science 45 (2003) 777788 www.elsevier.

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Corrosion control of galvanized steel using a phosphate/calcium ion inhibitor mixture

I.M. Zin a, S.B. Lyon
a

b,*

, V.I. Pokhmurskii

Karpenko Physico-Mechanical Institute, Ukrainian Academy of Sciences, Naukova Str., 5, Lviv, 79601, Ukraine b Corrosion and Protection Centre, UMIST, P.O. Box 88, Manchester, M60 1QD, UK Received 11 February 2002; accepted 7 June 2002

Abstract The corrosion inhibition of galvanized steel was studied in articial acid rain solution using extracts of pigments normally used in organic coatings for corrosion control. It was established that a combination of zinc phosphate/molybdate and calcium ion exchange silica has a signicant synergetic anticorrosion eect in the acid rain solution compared to the pigments used alone. Further, the charge transfer resistance of galvanized steel in acid rain solution saturated by the above pigment blend approaches that of strontium chromate in articial acid rain solution. Use of the pigment blend was found to lead to development of a protective lm, which is thought to be a complex mixture of calcium phosphates and zinc phosphate. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Inhibitive pigments; Organic coated galvanized steel; Chromate free

1. Introduction Due to the hazards associated with chromates, there is an intensive worldwide research eort in identifying possible replacements. Phosphates are one such alternative and are usually classied as non-oxidising anodic inhibitors eective usually only in the presence of oxygen [1,2]. However, under certain conditions, phosphates may also act as cathodic inhibitors. Here the phosphate ions in solution react with metal ions released due to corrosion and precipitate a surface lm. The quality of

Corresponding author. Tel.: +44-161-200-4846; fax: +44-161-200-4865. E-mail address: stuart.lyon@umist.ac.uk (S.B. Lyon).

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such a lm (i.e. the barrier properties) denes the inhibition eciency. Further, Uhlig et al. [3] found an enhanced inhibition eciency of polyphosphate where divalent Ca2 or Zn2 ions were also present in solution. This phenomenon was associated with the formation, on cathodic areas, of a barrier layer impeding access of oxygen to the iron surface. Szklarska-Smialowska and barrier layer impeding access of oxygen to the iron surface. Szklarska-Smialowska and Mankowski [4] have found from measurement of the potentiokinetic polarization of iron in dilute aerated orthophosphate solutions containing Ca2 , that orthophosphates inhibit the cathodic process by covering the surface with a lm of sparingly soluble calcium phosphate as the result of the reaction: 2HPO2 2OH 3Ca2 Ca3 PO4 2 2H2 O 4 The OH ions involved in the reaction are derived from the cathodic reduction of oxygen. This lm is claimed to be eective by limiting access of dissolved oxygen to the metal surface. Andrzejachek [5] has found that the cathodic reduction of oxygen on iron in tap water was inhibited by acidied Na3 PO4 solution because of cathodic adsorption of positively charged colloidal particles of calcium and magnesium phosphates. It was suggested that the formation of these particles, and their further adsorption onto metal surfaces did not depend on the oxygen content in solution. Thus, it is well known that a highly protective lm can be deposited onto metal surfaces in solutions containing phosphate inhibitors and calcium salts. The objective, then, of this work was to study the inhibition of galvanized steel corrosion using phosphate and calcium ions containing pigments that might be used in coated galvanized sheet steel.

2. Experimental method The corrosion behaviour of galvanized steel was investigated using electrochemical impedance spectroscopy (EIS). The galvanized steel was commercially produced sheet in the as-received form. The measurements were carried out using a threeelectrode electrochemical cell with a sample testing area of 4.5 cm2 and with a platinum auxiliary electrode as a counter and saturated calomel (SCE) as reference electrode. The impedance measurements were carried out close to the corrosion potential using an ACM potentiostat and a Solartron Frequency Response Analyzer 1250 in the 10 kHz to 5 mHz frequency range with a signal amplitude of 10 mV rms. The impedance spectra were interpreted with the software program, known as equivalent circuit, written by Boukamp [6,7]. Polarization measurements on the same samples were carried out using a three-electrode electrochemical cell and an AutoTafel potentiostat from ACM Instruments. The commercial inhibitive pigments Actirox 106 (zinc phosphate modied by molybdate) and Shieldex CP-4 7394 (calcium ion exchange silica) were used in this study. A commercial paint grade of strontium chromate was used as a control. All electrochemical measurements were carried out in articial acid rain solution [8] saturated with extracts of the pigments. Four solutions were prepared: three from

I.M. Zin et al. / Corrosion Science 45 (2003) 777788 Table 1 Compositions of saturated solutions of pigment extracts (ppm) Pigment SrCrO4 Actirox Shieldex Composition of pigment extract (ppm) Sr 195 Cr 224 Ca 0.3 18.4 Zn 0.2 0.2 P 6.9 Mo 0.6

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the individual pigments Actirox 106, Shieldex CP-4 7394, strontium chromate and the fourth using a combination of Actirox and Shieldex. These were prepared by stirring 2 g of each pigment (or 1 g of each of the combination of pigments) in 1 l of acid rain solution for 24 h at room temperature prior to ltering. Solution analysis by inductively coupled plasmaatomic absorption (approximate sensitivity of 10 ppb) revealed the following compositions (Table 1). Thus, Actirox provides mainly phosphate ions while Shieldex delivers calcium ions into solution. An AMRAY 1810A scanning electron microscope (SEM) with a Link systems X-ray energy dispersive spectrometer (EDS) was used to study the compositions of any surface lms on the galvanized steel after exposure to the inhibited acid rain solutions. In addition, a VG Scientic ESCALAB Mark I X-ray photoelectron spectrometer (XPS) was used for quantitative determination of the species present on the sample surfaces before and after immersion. XPS spectra were obtained using an Al Ka radiation source. The instrument was calibrated against Au 4f 7=2 spectrum at 84.0 eV binding energy. Spectra were referenced to the C 1s peak of adventitious carbon xed at 285.0 eV. Spectral responses were also subjected to curve tting and deconvolution in an attempt to identify the chemical state of the species in the surface lm. Survey spectra and high-resolution spectra were recorded in the constant pass energy mode at 100 and 20 eV respectively. The quantication of elements was made by peak area measurements using empirical sensitivity factors. For the surface analysis experiments, pure zinc coupons, obtained from Goodfellow Metals, were used in order to eliminate interference from any factory-applied treatment of galvanized steel.

3. Results 3.1. Impedance of galvanized steel in pigment extract solutions The impedance spectra of galvanized steel, both in single extracts of the pigments and in the two-component mixture, all show a semicircular form characteristic of a parallel resistorcapacitor (RC) network (Fig. 1). However, with both conventional chromate and the novel zinc phosphate/molybdate calcium ion pigment mixtures, the full initial semicircle cannot be observed due to the high impedance resulting from eective corrosion inhibition.

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Fig. 1. Impedance diagrams of bare galvanized steel after 1 d exposure in acid rain solution saturated by: ) Shieldex, ( ) Actirox Shieldex, ( ) Strontium chromate. ( ) Actirox, (

Calculation of the impedance components for the system, galvanized steel saturated acid rain solution of the appropriate pigment, was carried out using the equivalent circuit Re Qdl Rt , where Re is the resistance of the electrolyte, Rt the metal transfer resistance, and Qdl a constant phase element term related to the capacitance. The replacement of conventional double layer capacitance by the Qdl in the equivalent circuit model gives a good simulation of the experimental data with a minimal error and is a well-established approximation. It can be seen from the time dependency (Fig. 2) that the initial charge transfer resistance is about 10 times higher for galvanized steel in chromate and the zinc

Fig. 2. The time dependence of charge transfer resistance of galvanized steel in the acid rain solution ) Actirox Shieldex, ( ) Shieldex, ( ) Strontium chromate. saturated by pigments: ( ) Actirox, (

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Fig. 3. Time dependance of Qo for galvanized steel in acid rain solution saturated by pigments: ( ) Actirox Shieldex, ( ) Shieldex, ( ) Strontium chromate. Actirox, (

phosphate=molybdate calcium ion pigment mixture compared with the individual chromate-free pigments and remains higher for at least seven days. In the case of the pigment combination, this clearly demonstrates a strong synergetic protective eect, because the sum of the impedance values is considerably less than the impedance in the mixture. The time dependencies of the reactive component, (Qo )essentially the capacitanceshow little variation and lie within the range 1321 106 F, Fig. 3. The time dependence of the exponent parameter in Qdl lies in the range 0.70.85 demonstrating the predominant capacitive nature of the reactive term (Fig. 4).

Fig. 4. Time dependance of n of the Qdl for galvanized steel in the acid rain solution saturated by pig) Actirox/Shieldex, ( ) Shieldex, ( ) Strontium chromate. ments: ( ) Actirox, (

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Fig. 5. Polarization curves of galvanized steel after 3 h in articial acid rain solution saturated by pigments: ( ) Actirox, () Actirox/Shieldex, ( ) Shieldex, ( ) Strontium chromate.

3.2. DC polarization DC measurements were conducted with an aim to understand the electrochemical mechanism of the inhibition. It can be seen (Fig. 5) that cathodic control of the corrosion reaction appears to prevail over after 3 h of immersion for all of the pigment extract solutions. In addition, the chromate-containing solution shows a positive shift in corrosion potential of about 200 mV compared to the other pigment solutions and obvious anodic inhibition. After 2 d of immersion, a clear passivation plateau and positive shifts of corrosion potential are observed for galvanized steel both in chromate and in the pigment mixture (Fig. 6). Interestingly, however, comparing the cathodic curves after 3 h and

Fig. 6. Polarization curves of galvanized steel after 2 d exposure in acid rain solution saturated by pig) Actirox, () Shieldex, ( ) Strontium chromate. ments: ( ) Actirox/Shieldex, (

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2 d also shows a strong cathodic inhibition for both chromate containing and particularly the pigment mixture solutions. 3.3. Surface study of zinc exposed to the double pigment extract SEM/EDS data show that the surface lm developed on galvanized steel in the zinc phosphate/calcium ion pigment mixture extract consists of a relatively smooth and uniform coating with small grains with a survey analysis indicating that the lm contains Si, P, Ca, O and Zn species (Fig. 7). The Zn signal observed can derive both from the underlying zinc substrate and from the precipitated lm. On the uninhibited galvanized steel surface, EDS analysis showed only the presence of zinc and oxygen. This conrms the lack of any preexisting macroscopic corrosion product (e.g. sulphates).

Fig. 7. SEM image and EDS spectrum of surface lm on zinc formed after 2 d exposure in acid rain solution saturated by pigments Actirox and Shieldex (2000 magnication).

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Fig. 8. X-ray photoelectron spectrum of zinc surface after 2 d exposure in acid rain solution saturated by pigments Actirox and Shieldex.

An XPS survey spectrum of a pure zinc surface after 2 d exposure in the acid rain solution saturated by the combination of modied zinc phosphate and calcium ion exchange silica pigments reveals signals from Zn 2p, O 1s, C 1s, Ca 2p and P 2p (Fig. 8). Deconvolution of the high-resolution O 1s peak for oxygen (Fig. 9) reveals three basic components. The highest peak, with binding energy about 531.6 eV, can be related to oxygen species in the phosphate anion [9]. The second peak at a binding energy of 532.9 eV is due to hydroxyl oxygen either zinc hydroxide [10] or adsorbed water [11]. The absence of peaks close to binding energy of 529 eV indicates that the concentration of free zinc oxide on the metal surface is relatively small. The third peak found at 534.6 eV is much weaker and is caused by oxygen from organic contaminants on the metal surface (Table 2). The Auger Zn LMM spectrum for the same sample (Fig. 10) conrms that zinc is indeed present in the protective lm on the metal surface. The highest peak with

Fig. 9. The high-resolution O 1s X-ray photoelectron spectrum of zinc surface after 2 d exposure in acid rain solution saturated by pigments Actirox 106 and Shieldex 47394.

I.M. Zin et al. / Corrosion Science 45 (2003) 777788 Table 2 XPS analysis of zinc surface (at.%) Sample Unexposed zinc Zinc after 2 d exposure in the extract of the pigment blend Element (at.%) Zn 17.9 10.2 O 79.6 74.1 C 2.4 Ca 6.1 P 9.6

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Fig. 10. Zn LMM Auger peak for zinc surface after 2 d exposure in acid solution saturated by pigments Actirox and Shieldex.

kinetic energy at 987 eV can be related to dierent chemical compounds of zinc (in particular to Zn(OH)2 and Zn3 (PO4 )2 ) [12,13]. The second, smaller, peak at 990 eV also relates to zinc phosphate and zinc hydroxide as was found by Guimon [10]. The weakest peak at a kinetic energy of 993 eV is associated with un-oxidized zinc. The calcium high-resolution XPS spectrum of the same specimen reveals a pair of peaks due to Ca 2p3=2 and Ca 2p1=2 (Fig. 11). In this case, the spinorbit splitting dCa 2p3=2 Ca 2p1=2 is equal 3.5 eV, which is characteristic of calcium phosphate compounds. Similar spectra were observed by Demri and Muster for the salts CaHPO4 , Ca3 (PO4 )2 and CaH4 (PO4 )2 [13]. The values of binding energy for these peaks Ca 2p (347.5351 eV), and also P 2p (134 eV) both in the range known for calcium phosphate compounds [11,14].

4. Discussion 4.1. Electrochemical results The EIS data for the galvanized steel samples after 1 d of immersion in the solutions containing the various pigment extracts indicates that a strong synergistic

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Fig. 11. High-resolution Ca 2p spectrum of zinc surface after 2 d exposure in articial acid rain solution saturated by pigments Actirox and Shieldex.

eect is apparent in solutions containing the pigment mixture (i.e. essentially a solution containing phosphate and calcium ions at the ppm level). After 1 d, this eect produces an inhibitive eciency similar to chromate. At extended times up to 7 d, chromate maintains its eectiveness while the phosphate/calcium ion mixture appears to become less so. It is particularly interesting that the pigments individually (i.e. either phosphate or calcium ions) produced maximum inhibition eciency of less than 50%. These results, therefore, conrm the formation of a protective lm on the metal surface in the pigment mixture extract and that the lm must have the essential participation of both calcium and phosphate ions. One likely explanation of this eect is the formation of a protective surface lm on galvanized steel caused by an interaction of the solution species with the zinc (galvanized) surface. It has been found [15], that adding calcium salts to zinc phosphate solution during conventional phosphating leads to formation of a surface lm on mild steel with considerable reduction of grain size, decreased porosity and uniform thickness. The DC electrochemical data conrm the synergies apparent in the mixture and the comparative ineciency of the individual pigment extracts. Inspection of the polarisation data after 3 h of immersion show, in chromate and the mixture extracts, the initial stages of inhibition of zinc. Also, relative to the curve for the Actirox extract, inhibition of the cathodic reaction is observed in all other solutions. After 2 d of exposure, passivation of the zinc is evident both for the strontium chromate and for the pigment mixture extracts. In addition, comparison of the 3 h with the 48 h data show increasing cathodic inhibition with the pigment mixture extract the most eective. The electrochemical data conrm, therefore, that a phosphate/calcium ion mixture is eective by a combination of mild anodic inhibition of zinc dissolution combined with a very signicant inhibition of the cathodic reaction (predominantly oxygen

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reduction). This mixed inhibition results in a net corrosion rate that is comparable to the rate when zinc is inhibited with chromate. 4.2. Surface study of inhibited zinc The surface analytical data presented in this work conrm that the inhibitor lm does indeed contain zinc, calcium and phosphorus species (in addition to oxygen). The presence of zinc is signicant as the Auger data indicate that the major component is associated with a bound species consistent with zinc phosphate or hydroxide and only a minority with metallic zinc or zinc oxide. Thus, in addition to the calcium and phosphorus species, zinc ions are incorporated into the inhibitor lm on the surface. High-resolution XPS analysis of the O peak is again consistent with the presence of phosphate as the majority component with the minority as hydroxide or bound water. Furthermore, the calcium and phosphorus XPS spectra are also consistent with the presence of a phosphate species. Thus, the XPS data conrm that the inhibitor lm on zinc, after exposure in the pigment mixture solution extract, consists of a mixture of calcium and zinc phosphates. However, it is not possible, from the data, to identify the degree of association between zinc or calcium and phosphate as the binding energies for the corresponding phosphates are at similar energies. Nevertheless, the Auger data for zinc imply that the majority of the signal derives from an oxidised species and very little from the underlying substrate. The atomic ratio of Ca=P in the inhibitor lm is equal to 0.63 and thus lies between that for Ca(H2 PO4 )2 (Ca=P 0:5) and CaHPO4 (Ca=P 1). Previous work by Bhar et al. [16] studied the surface nishing of mild steel in a zinc phosphate bath. X-ray diraction data of the deposited lms showed that incorporation of calcium ions changed the structure of the phosphate coatings essentially from phosphophylitehopeite (Zn2 Fe(PO4 )2 4H2 O/Zn3 (PO4 )2 4H2 O) to schlozitehopeite (CaZn2 (PO4 )2 2H2 O/Zn3 (PO4 )2 4H2 O). As a As a result, phosphate pretreatment with calcium ion additions into the bath was found to improve the corrosion resistance of painted steel panels. It is interesting that the ratio of Zn Ca=P is equal to 1.7 which is close to that in CaZn2 (PO4 )2 2H2 O Ca Zn=P 1:5. Hence, it is likely that the inhibitor lm consists of a mixed calcium-zinc phosphate of composition similar to schlozite. Finally, it is interesting to comment on the possible mechanisms of lm deposition on galvanized steel in the blend pigment extract. For example, Armstrong and Zhou [17] found that Shieldex pigment can release both Ca2 and polysilicate ions in solution with the latter adsorbing onto an iron surface and acting as a cathodic inhibitor. In addition, Tanizawa and Suzuki [12] have established that silica can promote precipitation of calcium phosphate in near neutral aqueous solutions. They concluded that silica provides favourable sites for calcium phosphate nucleation and that a large amount of precipitate forms as a result. Thus, there may also be a role for the polysilicate anions released from the Shieldex pigment in depositing on the surface and acting as nucleation sites for the formation of the coherent, compact inhibitor lm calciumzinc phosphate.

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5. Conclusions 1. The combination of zinc phosphate/molybdate (Actirox) and calcium ion exchange silica (Shieldex) has signicant anticorrosion eect for galvanized steel in an articial acid rain solution compared to the individual pigments. Solution analysis indicates that the species present in the extract are dominated by phosphate and calcium ions. 2. The charge transfer resistance of galvanized steel in articial acid rain solution saturated with the mixed pigment extracts approaches that of strontium chromate and is much greater compared with the single pigment extracts. Thus, the inhibitive eciency approaches that of chromate. Mechanistically, this is a mixed inhibitive eect, due to moderate anodic inhibition of zinc dissolution coupled with a strong inhibition of the cathodic reaction. 3. Analytical microscopy established that the use of the pigment blend extract leads to the development of a smooth, uniform and highly compact lm on galvanized steel, containing calcium, zinc, phosphorus, silicon and oxygen atoms. An XPS study conrmed that the surface lm is a mixed calciumzinc phosphate.

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