Corrosion Science 77 (2013) 222229

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion inhibition by lithium zinc phosphate pigment

E. Alibakhshi a, E. Ghasemi b,, M. Mahdavian c
a

Institute for Color Science and Technology, Tehran, Iran Inorganic Pigment and Glazes Department, Institute for Color Science and Technology, Tehran, Iran c Department of Surface Coatings and Corrosion, Institute for Color Science and Technology, Tehran, Iran
b

a r t i c l e

i n f o

a b s t r a c t
Lithium zinc phosphate (LZP) has been synthesized through a co-precipitation process and characterized by XRD and IR spectroscopy. The inhibitive performances of this pigment for corrosion of mild steel have been discussed in comparison with the zinc phosphate (ZP) in the pigment extract solution by means of EIS and in the epoxy coating by means of salt spray. The EIS and salt spray results revealed the superior corrosion inhibitive effect of LZP compared to ZP. Moreover, adhesion strength and dispersion stability of the pigmented epoxy coating showed the advantage of LZP compared to ZP. 2013 Elsevier Ltd. All rights reserved.

Article history: Received 14 April 2013 Accepted 6 August 2013 Available online 13 August 2013 Keywords: B. EIS B. XRD B. IR spectroscopy C. Neutral inhibition C. Polymer coating

1. Introduction In recent decades, phosphates have been used as soluble inhibitors and conversion coating materials [13]. Zinc phosphate (ZP) as low soluble metal phosphate has been used as corrosion inhibitive pigment in organic coatings [4,5]. The well-known corrosion inhibition mechanisms for zinc phosphate pigment after penetration of water in the organic coatings are pore plugging [6] and formation of a complex precipitate on the surface [7]. However, other mechanisms have also been suggested by some authors [8,9]. Inappropriate corrosion inhibition of ZP compared to chromates has been a great challenge for the researchers to synthesize a novel generation of ZP pigment. Various techniques such as modication or replacement of the cationic or anionic parts of the ZP have been proposed to enhance inhibition performance [1012]. There are several compounds of cationically modied zinc phosphate pigment. Among them, aluminum zinc phosphate [13,14], iron zinc phosphate [15] and potassium zinc phosphate [16,17] have so far been synthesized and examined for their corrosion inhibition effect. In this paper, the cationic modication of ZP by lithium has been investigated. No study has been carried out on the corrosion inhibition effect of lithium zinc phosphate (LZP) in literature. Previous related works on LZP are mainly focused on the study of the crystal structure, characterization, and thermal decomposition kinetics [18,19]. Although the inhibitive activity of potassium zinc phosphate (PZP) was previously reported [16], the relatively small ionic radius
Corresponding author. Tel.: +98 2122051484; fax: +98 2122947537.
E-mail addresses: eghasemi@iust.ac.ir, eghasemi@icrc.ac.ir (E. Ghasemi). 0010-938X/$ - see front matter 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.corsci.2013.08.005

of lithium as compared to potassium could result in differences in the crystalline structure, solubility of the synthesized pigment and consequently, its corrosion inhibition performance. In this paper, we have successfully synthesized and characterized the LZP, and then its corrosion inhibition performance was compared to the ZP using the EIS for the bare mild steel samples in the pigment extracts in 3.5% NaCl solution and by the salt spray for the pigmented epoxy coatings. Moreover, dispersion stability and adhesion strength were evaluated. 2. Experimental 2.1. Pigment preparation Zinc chloride (Merck, 8.1 g) was added to an 85 wt.% phosphoric acid solution (Merck, 6.2 ml) and water (100 ml). This mixture was stirred until complete dissolution was achieved. Then, triethanolamine (Merck, 3.5 ml) was added to this mixture, and the mixture was stirred for 15 additional minutes. Another solution was prepared with a solution of LiOH (Merck, 2.85 g) in deionized water (80 ml) which was added to the above solution and stirred for 3 h, and heated at 100 C for 24 h. The resulted residue was recovered by ltration, washed to neutral pH and dried at 100 C. ZP pigment was obtained from Nubiola. 2.2. Characterization of synthesized pigment The X-ray diffraction (XRD) was performed on prepared LZP powder using a Philips X-ray spectrometer, PW 1800 type (Netherlands) with Cu Ka lament. The FTIR analysis was carried out using

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KBr disk method in the region of 4000450 cm1 by FTIR Perkin Elmer Spectrum One (USA). 2.3. Pigment extract preparation To prepare the pigment extracts, 1 g of each pigment was stirred in 1 L of 3.5% NaCl solution for 24 h, then was ltered to achieve saturated conditions at room temperature (24 1 C). As a reference solution, a blank solution of 3.5% NaCl with no pigment was also prepared. In order to measure the concentration of dissolved species in the pigment extracts, an inductively coupled plasma-optical emission spectrometer [Varian Vista Pro ICP-OES] was used. 2.4. Evaluation methods 2.4.1. EIS Electrochemical properties of the pigments in the pigment extracts were studied by EIS. To this end, steel samples were cut down into the pieces of 1 cm2 surface area. In the following, a braided wire was attached to one side of steel pieces by brazing; the steel samples were then mounted using unsaturated polyester. Later, the mounted samples were abraded using 600 and 800 grit emery papers. Finally, the samples were washed using methanol to remove any remaining contamination. The steel samples were exposed to the test solutions for 1, 4 and 24 h, respectively. This was done by an Ivium Compactstat with the perturbation of 10 mV within the frequency of 10 mHz to 10 kHz, respectively. The test was done in a standard electrochemical cell including steel sample, Ag/AgCl (3 M KCl) electrode and graphite electrode as working, the reference and auxiliary electrodes, respectively. Using Ivium software, the EIS results were analyzed. The mild steel with the mass percent composition of C 0.19, Mn 1.39, S > 0.005, Si 0.42, Cu 0.04, Cr 0.03, Mo 0.02, Co 0.06 and Fe (balance) was used in this study. 2.4.2. Surface analysis Scanning electron microscopy and energy dispersive X-ray spectroscopy (SEM/EDX, Philips XL30) were utilized to analyze the surface lm morphology and the composition on the mild steel surface after being exposed to extract solutions. 2.4.3. Turbidity measurements The pigments (0.5 g) were added separately to the solution of epoxy resin (Shell, Epikote 828, 16 g) based on diglycidyl ether of bisphenol A (DGEBA) and methyl ethyl ketone (Merck, 4 g) in a particular glass cell. The mixtures were ultrasonicated at 50 W for 10 min. Then, the mixture remained undisturbed for 24 h at room temperature, and subsequently turbidity measurements were carried out using Hach turbidimeter. 2.4.4. Preparation of coated specimens The pigment dispersion in resin was prepared by addition of each pigment (5% v/v) to 4 g epoxy resin (Shell, Epikote 828). Then, the mixture was ultrasonicated to obtain neness of 16 lm and degassed for further 3 h in a vacuum oven at 70 C, to remove trapped air during the mixing steps. Once the appropriate dispersion was achieved, a stoichiometric amount of curing agent (Shell, Epicure F205), was added to the dispersion, and stirred for 3 min. The mild steel panels were abraded by emery paper 800 and then cleaned by acetone. The coatings were applied using 90 lm bar coater (Model 352, Erichsen Co.) on mild steel panels. All coatings were cured at 80 C for 40 min. The coatings were maintained for 27 days at 25 2 C and 30 2 RH before salt spray and pull off adhesion strength measurement. The samples

with a dry lm thickness of 42 1 lm were used for salt spray and pull off adhesion strength measurement. 2.4.5. Salt spray The edges and back of all panels were sealed using a beeswax colophony mixture. The samples were X-scribed then they were exposed to salt spray for 270 h according to ASTM B117 standard practice (NaCl concentration: 50 g/L and pH between 6.5 and 7.2). 2.4.6. Pull-off adhesion strength measurement The adhesion strength of the coatings was determined by a PosiTest pull-off adhesion tester (DeFelsko). The test was conducted at 25 2 C and 30 2 RH. 3. Results and discussion 3.1. Characterization of the synthesized pigment Fig. 1 displays the XRD results for synthesized pigment powders. Major phases in LZP form included LiZnPO4 and LiZn2PO4 (HPO4) while ZnO was detected as the minor phase in this gure. According to the relative intensity of the diffraction peaks, it can be concluded that the LiZnPO4 is the major phase. It is comparable with our previous work [16] for PZP in which the major phase was KZn2PO4(HPO4). SEM micrographs for LZP and ZP are presented in Fig. 2. It is clear that for LZP, the particles have rod-like shape with a mean aspect ratio of 5.6 0.7, while ZP does not have the uniform shape. LZP particles are smaller in size and aspect ratio compared to PZP one (aspect ratio of PZP = 6.9 0.4). Fig. 3 shows the FTIR spectrum of the synthesized LZP powder. The absorption band which is observed at 3436 cm1 is the characteristic of the OAH stretching vibrations of the free and hydrogen bonded surface hydroxyl groups [20]. A second typical absorption band at 1508 and 1611 cm1 is assigned to physically adsorbed water (HAOAH bending) [21]. The PAO stretching modes are known to appear in the 479950 cm1 region [21]. The absorption bands between 1263 and 1432 cm1 show stretched vibration of P@O [19]. The absorption bands of PO2 are appeared in the region of 1008 and 1038 cm1 [22]. The characteristic absorption bands of ZnO are observed at 20182322 cm1 [23]. An absorption band at the wavenumber of 1870 cm1 is witnessed for LiAO. The band at 955 cm1 is an indication of ZnAOAP vibration [24,25]. The above observed bands are evidence for the presence of lithium zinc phosphate and zinc oxide phases, which are in accordance with XRD results.

Fig. 1. XRD pattern of the synthesized LZP pigment.

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Fig. 2. SEM micrograph of the commercial ZP (a) and the synthesized LZP pigment (b).

Fig. 3. FTIR spectrum of the synthesized LZP pigment.

3.2. Studies on pigment extracts 3.2.1. Evaluation of the inhibitive properties EIS results for samples immersed in different electrolytes are presented in Fig. 4. One glimpse on the plots reveals that for the mild steel samples immersed in the LZP extract, the impedances at low frequencies were at least one order of magnitude higher than those immersed in ZP and blank solution. Besides, at the low frequencies, the impedance was slightly higher for the mild steel samples immersed in the ZP solution compared to those in the blank solution. The simple electrical circuit model of Fig. 5 was used to t EIS results. The electrical elements are Rs, Rct and CPEdl which represent the solution resistance, the charge transfer resistance at metal electrolyte interface and the constant phase element, respectively. The double layer capacitance was calculated by Eq. (1) [26,27]:

 1=n n C dl Y 0;dl R1 ct

Fig. 4. Bode plots for the mild steel samples after 24 h immersion in 3.5 wt.% NaCl solution containing () no pigment, (h) ZP and (j) LZP pigments.

where Y0,dl is the admittance of the CPE (in Sn X1 cm2) and n is an exponent related to surfacing heterogeneity. The results of curve ttings are listed in Table 1. Concerning the tting results depicted in Table 1, the value of Rct for mild steel samples in the LZP extract was higher than those of the samples immersed in the blank solution and the ZP extracts.

Also, the trend of Rct is ascending for the LZP extract, while for ZP extract and blank solution a descending trend is obtained. The results show the higher inhibition performance of LZP than ZP. Furthermore, the double layer capacitance of the mild steel samples immersed in LZP extract was lesser than those immersed in the

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Fig. 5. Typical tted Bode plots for the mild steel specimen exposed to LZP extract in 3.5 wt.% NaCl solution.

ZP and the blank solution. This might be resulted from a higher thickness of the double layer and/or a lower dielectric constant of the materials precipitated at the surface. Increase of charge transfer resistance and decrease of double layer capacitance could be related to mild steel surface blocking through precipitation of LZP or formation of the insoluble complexes on the surface [18]. In addition to resistance parameters extracted by equivalent circuit modeling, two parameters of Bode plot including phase angle (h) at 10 kHz and impedance magnitude at 10 mHz are presented in Figs. 6 and 7, respectively. Perusal of these two parameters can present the overall inhibition performance which can be directly read from the Bode plots with no need to t them. This way, fewer errors are expected to occur specially those resulted from tting process [28,29]. The impedance at low frequencies is an approximation of the resistance at DC test [6]. It is evident that for the steel samples exposed to the LZP solution, the extent of impedance magnitude was higher than that for the samples immersed in the ZP and blank solutions. The impedance at 10 mHz declined as time elapsed for those immersed in the ZP and blank solutions, while those immersed in the LZP solution showed an increase over an immersion period. The phase angle at 10 kHz was more negative for the samples immersed in LZP solution compared to the ZP and blank solution. It was shown that the more negative the phase angle the more capacitive would be the electrochemical behavior [30]. The higher capacitive behavior of the electrodes in LZP electrolyte means that current tends to pass through the double layer capacitance because of high charge transfer resistance. The corrosion inhibition of the LZP compared to that of PZP pigment published elsewhere [16], reveals that

Fig. 6. The phase angle (h) at 10 kHz for the samples immersed in 3.5% NaCl solution containing no pigment (blank solution) and the ZP, LZP pigment extract solutions for 24 h.

potassium in zinc phosphate provides higher inhibition than lithium. By taking a corrosion inhibitive pigment into consideration as a reservoir, solubility can play the role of a discharge valve which makes the inhibitor species kinetically available [31]. Table 2

Table 1 Electrochemical parameters evaluated from the impedance diagram for mild steel samples immersed in different test solution during 24 h immersion period. Pigment Time (h) Rct (X cm2) Mean Blank 1 4 24 1 4 24 1 4 24 1127.3 681.4 529 1272.5 1030.4 755.6 2901 2921.5 3681.5
a

Y0,dl (lsn X1 cm2) S.D.a 123.8 68.5 28.2 72.6 114 59.1 605 403 380 Mean 558.1 92.1 544.5 30.7 70.3 41.59 4.13 3.49 3.28 S.D.a 125.1 14.3 362 4.7 6.3 9 1.4 1.8 1.9

n Mean 0.71 0.65 0.64 0.59 0.58 0.53 0.66 0.65 0.7 S.D.a 0.02 0.03 0.01 0.03 0.03 0.04 0.02 0.02 0.01

Cdl (lF/cm2) Mean 446.2 20.8 270.35 3.2 10.5 1.93 0.42 0.29 0.49

ZP extract

LZP extract

S.D.: standard deviation.

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Fig. 7. The impedance magnitude at 10 mHz for the samples immersed in 3.5% NaCl solution containing no pigment (blank solution) and the ZP, LZP pigment extract solutions for 24 h.

presents the results of ICP-OES from the pigment extracts. The zinc concentration was lower in the LZP than the ZP extract. It was previously reported that the presence of zinc markedly accelerates the establishment of a protective lm and also lm repair [32]. It seems that the better inhibition performance of LZP in comparison with ZP is related to existence of the higher amount of phosphate and the presence of a high amount of lithium in the LZP extract solution compared to ZP.

3.2.2. Surface analysis Fig. 8 displays surface morphology of the samples exposed to ZP and LZP after 24 h. SEM micrographs clearly show an existence of a precipitated layer on the surface. Also, SEM micrographs illustrate more compact corrosion products and uniform surface in the presence of LZP. While, the sample exposed to the ZP solution presents a porous lm of corrosion products on the surface. EIS results revealed only one time constant for ZP. Absence of the second time constant could be attributed to the porous structure of the corrosion products [33], which could be easily detected in the SEM micrograph. The micrographs of the samples immersed in test solutions show different kind of patterns on the surface which could be attributed to different nature of the lms on the surface [34]. The chemical composition of the surface lms detected by EDX analyzer showed the mass percentage of 0.7% Zn and 0.4% P and 1.5% Zn and 0.3% P for LZP and ZP extracts, respectively where Fe was the balance element. Detection of Fe, Zn and P elements on the surface could be connected to zinc phosphate, iron phosphate or their hybrid deposition, probably leading to oxide lm stabilization. A glance at the elemental composition obtained from the EDX and the charge transfer values extracted from the EIS results reveal that the phosphate concentration in the surface lm plays a major rule in corrosion inhibition performance; however, as the EDX could not detect lithium, its presence in surface lm and consequently its effect on corrosion inhibition could not be veried.

Fig. 8. SEM micrographs of the mild steel samples after 24 h immersion in the ZP (a) and LZP (b) pigment extracts in 3.5% NaCl solution.

3.3. Studies on pigmented coating 3.3.1. Dispersion stability The NTU (Nephelometric Turbidity Unit) of dispersion is related to size, shape and concentration of particles. The rate of sedimentation is related to density and surface chemistry of particles. Stronger repulsive forces between the dispersed particles and better compatibility between the particle and medium lead to lower rate of settling and higher NTU values in turbidity measurements. It means that the changes in NTU can more reliably be used as an indication of dispersion stability [35]. Turbidity measurements after 24 h remaining the dispersion undisturbed at room temperature revealed 10.1 NTU for the LZP and 5.8 NTU for the ZP in the epoxy medium which indicates higher dispersion stability of LZP compared to ZP. The sedimentation behavior could be an indication of dispersion stability. The well accepted sedimentation mechanisms are occulation and accumulation of dispersion [36,37]. It is noteworthy that the results of the turbidity measurements are in good agreement with visual evaluations of the dispersions haziness. The results for sedimentation test on samples are shown in Fig. 9. It could be observed that the LZP has slower settling rates than ZP, which could be related to higher stability of LZP dispersion compared to ZP. 3.3.2. Corrosion resistance Corrosion resistant coatings are supposed to protect metal in corrosive environments. The corrosion resistance of the coatings

Table 2 Concentration (ppm by weight) of Zn, P and Li in ZP and LZP extracts in 3.5 wt.% NaCl solution measured by ICP-OES. Zn ZP extract LZP extract 2.66 1.01 P 0.49 1.96 Li 0 11.6

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could be evaluated by accelerated salt spray test in laboratory. The coated mild steel samples formulated with and without of pigments were x-cut scribed then they were exposed to salt spray (5%) for 270 h. The appearance of the ZP and LZP pigmented epoxy coatings and blank coating after 270 h exposure to salt spray is demonstrated in Fig. 10. It is shown that incorporation of ZP in the coatings could diminish the corrosion initiated from the x-cut on the organic coatings [39,40]. It is shown that the application of the pigments in the coatings could lead to the formation of a thin interfacial inorganic layer that may affect adhesion and corrosion resistance of the coating on iron [38]. The protection mechanism of ZP is also associated to the barrier effects [39,40]. Fig. 10 shows a combination of small and large blisters along the scribed area for ZP and blank samples, while the coating contained LZP showed the lowest blisters from the scribed area. This means that corrosion protection of coated sample increases in the presence of LZP and ZP, and the highest protection is obtained in the presence of synthesized pigment (LZP). In other words, anodic undermining is greatly controlled in the presence of the synthesized pigment. The salt spray results coincided with the impedance spectra, implying that the addition of LZP can effectively improve corrosion performance via corrosion inhibitive action in the epoxy coatings.

3.3.3. Adhesion measurements The corrosive electrolyte diffusion into the coating/metal interface may lead to a decrease in the adhesion of coating on the metal substrate. It has been shown that the relationship between dry adhesion and corrosion resistance of an organic coating is not necessarily straightforward [4144]. The wet and dry pull-off adhesion strengths of the pigmented and blank coatings were measured and displayed in Fig. 11. According to the results, dry and wet adhesion strength of the epoxy coating containing the LZP are considerably higher than the blank and ZP coatings. The least value of adhesion strength was observed in the blank sample. It is well known that when the electrolyte reaches the coating/ metal interface, the hydrolysis of adhesion bonds can be responsible for the decrease in adhesion strength. Formation of corrosion products, i.e. iron oxy-hydroxides and OH ion, beneath the coating can also be responsible for the decrease in coating adhesion [45].

Fig. 10. The blank epoxy coating (a), epoxy coating containing ZP (b) and epoxy coating containing LZP (c) after 270 h exposure to 5 wt.% salt spray.

Fig. 9. Extent of sedimentation of ZP (a) and LZP (b) in the epoxy resin medium.

Application of corrosion inhibitive pigments not only improves wet adhesion strength but also enhance the dry adhesion strength. It seems that the humidity of the atmosphere could also play a role when dry adhesion strength is measured. The water vapor could penetrate to the coating and could partially dissolve the pigments forming a thin layer of phosphate on the metal surface, which is responsible for improved dry adhesion strength. Naderi and Attar [46] showed similar behavior of zinc aluminum phosphate where enhancement of adhesion strength was observed in comparison with ZP.

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E. Alibakhshi et al. / Corrosion Science 77 (2013) 222229 [3] K. Ogle, R. Bucheit, Conversion coatings, in: A.J. Bard, M. Stratmann (Eds.), Encyclopedia of the Electrochemistry, vol. 5, Wiley-VCH, Weinheim, 2003, p. 460. [4] D. El-Hamid, G. Blustein, M. Dey, B. Del Amo, R. Romagnoli, The anticorrosive performance of zinc-free non-toxic pigment for paints, Mater. Chem. Phys. 127 (2011) 353357. [5] C. Deya, B. Del Amo, R. Romagnoli, Ceramic microspheres to improve anticorrosive performance of phosphate paints, Ceram. Int. 38 (2012) 2637 2646. [6] M. Mahdavian, A.M.M. Attar, Investigation on zinc phosphate effectiveness at different pigment volume concentrations via electrochemical impedance spectroscopy, Electrochim. Acta 50 (2005) 46454648. [7] B. Rossenbeck, P. Ebbinghaus, M. Stratmann, G. Grundmeier, Corrosion protection of Zn-phosphate containing water borne dispersion coatings on steel. Part 1: Design and analysis of model water based latex lms on iron substrates, Corros. 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Fig. 11. Pull-off adhesion strength of the blank epoxy coating and the coatings containing ZP and LZP pigment in wet and dry states.

Comparing the pull-off strength and the EIS results (Section 3.2.1) shows a direct relationship between adhesion and corrosion inhibition. These mean that LZP can reduce adhesion loss of coating by increasing the resistance of the coating against the corrosion. 4. Conclusion Assessing the results of electrochemical techniques as well as ICP-OES and surface analysis on pigment extracts and turbidity, salt spray and pull-off tensile strength on the pigmented coating led to the following conclusions: 1. EIS measurements depicted increase of charge transfer resistance, phase angle (at high frequency) and impedance magnitude (at low frequency) as well as double layer capacitance decline in the presence of LZP conrming better inhibitive performance in comparison to ZP. 2. LZP showed superior corrosion inhibition effect in comparison to ZP in EIS measurements, which could be attributed to higher phosphate content and the presence of lithium in the extract solution as corroborated by ICP. 3. SEM-EDX demonstrated existence of a precipitated layer on the surface. 4. Turbidity results showed improved dispersion stability of LZP in epoxy medium in comparison to conventional ZP. 5. The salt spray results revealed improved corrosion protection of epoxy coatings in the presence of LZP. 6. Adhesion strength retention was greatly enhanced using of the modied pigment (LZP). 7. LZP could be an effective corrosion inhibitive pigment for the epoxy coatings.

Acknowledgement The authors would like to thank National Iranian Drilling Company (NIDC) for nancial supports. References
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