Volume 14 Preprint 36


Corrosion inhibition of bronze, copper and iron in urban-marine media by 3-amino 1, 2, 4-triazol

S. El Hajjaji*, N. Abid, N. Labjar, M. Serghini-Idrissi

Keywords: Bronze; copper; iron; electrochemical properties; surface analysis; Corrosion; triazole.

Abstract:
The 3-amino 1, 2,4-triazol, refereed as (ATA), was tested as inhibitor for different materials (copper, iron and bronze) corrosion in urban-marine solutions by electrochemical polarization methods and weight loss measurement. Results obtained in this study reveal that ATA is a good inhibitor and the potentiodynamic polarization studies clearly show that ATA is a mixed-type inhibitor for bronze, cathodic inhibitor for iron and anodic inhibitor for copper. The inhibition efficiency of ATA increases with the increase of inhibitor concentration and reaches an optimum value (up to 90 %) at 10-2 M in urban-marine solution for the different substrates. The SEM-EDX analysis of the protective layer of ATA after corrosion experiments shows that the inhibitor prevents metal corrosion by the formation of a protective layer and the adsorption of the inhibitor on the surface.

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ISSNCorrosion 1466-8858 Volume Preprint 36 30 August inhibition of bronze, copper and14,iron in urban-marine mediasubmitted by 3-amino 1, 2, 2011 4-triazol S. El Hajjaji*, N. Abid, N. Labjar, M. Serghini Laboratory of spectroscopy Infra Rouge, Faculty of Sciences, University Med V Agdal, Av. Ibn Battouta, BP 1014, M-10000 Rabat, Morocco *Corresponding author: selhajjaji@hotmail.com Abstract The 3-amino 1, 2,4-triazol, refereed as (ATA), was tested as inhibitor for different materials (copper, iron and bronze) corrosion in urban-marine solutions by electrochemical polarization methods and weight loss measurement. Results obtained in this study reveal that ATA is a good inhibitor and the potentiodynamic polarization studies clearly show that ATA is a mixed-type inhibitor for bronze, cathodic inhibitor for iron and anodic inhibitor for copper. The inhibition efficiency of ATA increases with the increase of inhibitor concentration and reaches an optimum value (up to 90 %) at 10-2 M in urban-marine solution for the different substrates. The SEM-EDX analysis of the protective layer of ATA after corrosion experiments shows that the inhibitor prevents metal corrosion by the formation of a protective layer and the adsorption of the inhibitor on the surface. Keywords: Bronze; copper; iron; electrochemical properties; surface analysis; Corrosion; triazole. © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 1. Introduction Volume 14, Preprint 36 submitted 30 August 2011 The archaeological objects exposed in museums have often been adversely affected due to spontaneous aggressiveness of the environment of museums. Now, the objects buried for centuries in the ground or in the aqueous environment have gained certain stability with this environment. The corrosion processes were so slow that they became negligible. However, after excavation, the sudden change of environment and sometimes exposure in a corrosive atmosphere such as marine and/or urban provokes the restart of the corrosion. The protection of the metallic objects of cultural heritage becomes of a great importance [1-13]. Among the methods used to enhance the stability of the materials is the inhibition that delays the corrosion rate by acting in several ways depending on the nature of the material and the inhibitor. In general, organic compounds containing polar groups including nitrogen, sulfur, phosphorus, and oxygen, and heterocyclic compounds with polar functional groups and conjugated double bonds [14–18] have been reported as good corrosion inhibitors. The inhibiting action of these organic compounds is usually attributed to their interactions with the metal surface via their adsorption [19-21]. In most of the cases, the interaction with the metal is favored when the inhibitor is a planar conjugate molecule with a high p/lone-pair electron density [22–25]. However, the adsorption of an inhibitor on a metal surface depends on the nature as well as the surface charge of the metal, the adsorption mode, the inhibitor’s chemical structure, and the type of the electrolyte solution [26]. Many authors have investigated the corrosion control of copper, iron and steels in various media using large numbers of organic and inorganic compounds [27 - 41]. Many works can be found in the literature about inhibitor properties of aminotriazole (ATA) and its action [4244]. They have established that this molecule acts by formation of a tridimensional film as an organic revetment. The aim of the present work is to study the inhibiting efficiencies of aminotriazol (ATA) in corrosion process of bronze, copper and iron in urban-marine medium. The investigation is performed using electrochemical methods, weight loss measurements and the surface analysis. 2. Experimental procedure 2.1. Materials and solution © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Copper (99%wt), Volume(its 14, chemical Preprint 36compositions was submitted August iron (99%wt) or bronze given in 30 table 1) 2011 were used as the working electrode. Metal electrode for corrosion studies have a surfaces area of 0.785 cm² for bronze, 1.1 cm² for iron and 1.4 cm² for copper. These samples were first mechanically polished using SiC paper in successive grades from 500 to 1200, washed with deionized water thoroughly, degreased with absolute ethanol and dried. We used for the corrosion tests, a solution constituted of 0.2 g. L-1 of Na2SO4 + 0.2 g. L-1 of NaHCO3 + 0.2 g. L-1 of NaCl. The pH was adjusted to 3 by the addition of HCl. This middle represents the environment of urban-marine zone. For the inhibition study, we used an organic molecule; the aminotriazole (ATA) of chemical formula C2H4N4. Table 1: Composition of the bronze (% wt). Element Fe Ni Al Cu % wt 4⋅2 8⋅97 8⋅66 78⋅26 2.2. Weight Loss Measurements Gravimetric experiments were carried out in a double glass cell. The weight loss (in mg cm-2) was determined at different immersion times by weighing the cleaned samples before and after hanging the sample into 30 mL of the corrosive solution in the absence and presence of various ATA concentrations. At the end of the tests, the specimens were carefully washed in distilled water and dried in hot air and then weighted. All tests have been performed at room temperature in aerated solution. Duplicate experiments were performed in each case and the mean value of the weight loss is reported. Weight loss allowed calculation of inhibition efficiency of our extract according to the following equation: Where W and W° are the weight loss of alloy samples obtained in corrosive solution in the presence and in the absence of inhibitor, respectively. 2.3. Polarization Measurements Electrochemical measurements were carried out in a conventional three electrode cylindrical glass cell, containing 100mL of electrolyte at room temperature. A standard three-electrode cell was used with Platinum electrode as a counter electrode and a saturated calomel electrode © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 (SCE) as a 14, Preprint 36 submitted 30 August reference electrode. AllVolume potentials are reported vs. SCE. Before each Tafel 2011 experiment, the working electrode was allowed to corrode freely and its open circuit potential (OCP) was recorded as a function of time up to 60 min. After this time, the potentiodynamic Tafel measurements were started from Ecorr to the anodic or cathodic direction in the absence and in the presence of inhibitor molecule (ATA), with a scan rate of 2 mVs−1. For polarisation measurements, a potentiostat Voltalab 301 PGZ monitored by a PC computer and Voltamaster 4.0 software were used for run the tests, collect and evaluate the experimental data. During each experiment, the test solution was mixed with a magnetic stirrer. The inhibition efficiency (E %) was calculated using the following equation: Where I° and I are, respectively, the corrosion current densities obtained in corrosive media in the absence and the presence of inhibitor. 2.4. Surface and solution analysis The surface morphology and chemical analysis of alloy specimens after polarization measurements in urban-marine media in the absence and the presence of inhibitor (ATA) were studied using a scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) techniques. X-Ray Diffraction measurements were performed using a XRD 3003-TT diffractometer equipped with secondary monochromator and with a Cu K radiation source (K1= 1.54) in order to reveal the nature of phases. A goniometer θ-θ (vertical) was used for XRD studies. A scanning electron microscopy (Quanta 200 Fci Company with EDS) was coupled to these characterizations to qualify corrosion layers and morphologies. Spectroscopy induction coupled plasma was used to analyze the solution. The calibration is made in the studied solution in order to eliminate the effect of matrix. 3.Results and discussion 3.1. Potentiodynamic tests Polarization measurements have been carried out in order to gain knowledge concerning the kinetics of the anodic and cathodic reactions for different materials in the absence and © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858of presence Volume 14, media. Preprint The 36 obtained polarization submittedcurves 30 August ATA molecule in urban-marine of 2011 materials in urban – marine solution without and with different ATA concentrations are shown in Fig. 1. The values of the electrochemical kinetic parameters (corrosion potential (Ecorr), corrosion current density (Icorr)), determined from these experiments are summarized in Table 2. They show that the addition of the inhibitor decrease the attack of the metal working electrode. The corrosion potential (Ecorr) in solutions containing inhibitor is shifted towards more positive values with the increase of its concentration (Table 2). The addition of ATA had influence on anodic and/or cathodic part depending on the nature of material. The corrosion current decrease is more pronounced when the concentration ATA increases. Compared to the blank samples (Fig. 1) the cathodic curves indicate that all the cathodic polarization curves for iron and bronze in the absence and presence of ATA are parallel which suggests that the hydrogen evolution is activation controlled and the presence of inhibitor decrease the current without changing the mechanism of reduction reaction [45, 46]. For iron, no remarkable influence on the anodic part is observed but the addition of ATA substantially reduces the cathodic current density. The efficiency rate obtained from the polarization curves reached a maximum value of 91% for concentration of 10 mM in ATA. For copper (Fig 1b), the anodic curves of the copper electrode in the urban-marine solution shift obviously to the direction of current reduction as adding the ATA, which implies that the organic compound can suppress the anodic reaction (copper dissolution). Based on the marked decrease of the anodic current densities upon introducing the inhibitor in the aggressive solution, this inhibitor is considered as an anodic inhibitor for copper. For bronze (Figi1c and 1d), we note the reduction of the cathodic and anodic current densities. This means that the addition of ATA reduces the anodic dissolution and also retards the cathodic hydrogen evolution reaction. Fig.2 presents the variation of inhibitor efficiency versus the logarithm of the concentration in inhibitor. It results from the linear dependence observed that the adsorption of ATA compound on the surface of alloy follows an isotherm of Temkin:  RT ln A0C q0 © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Where  is Volume 14, Preprint 30 August 2011 the coverage of an electrode surface by an 36 adsorbed inhibitor, submitted q0 the adsorption temperature,  and A0 the constants of the system at constant temperature. Table 2: Electrochemical parameters of iron, copper and bronze in urban-marine media in the presence of different concentrations of ATA. Cathodic part alloy Iron Copper Bronze [ATA] Anodic part Ecor icor (mM) (mV/ECS) (µA.cm²) 0 -627 829 - 0.1 -611 311.5 62.4 1 -582 184 77 10 -543 74.8 91 E (%) Ecor icor E (mV/ECS) (µA.cm²) (%) 0 -92 863 - 0.1 -20 701 19 1 -63 164 81 10 -82 64.7 92.5 0 -132 135 - -138 897 - 0.1 -50 58.9 56.3 -45 522 41.8 1 -140.8 46.5 65.5 -93 330 63.2 10 -141 40.9 69.7 -136 131 85.4 3.2. Dissolution rate in the passive state Copper and bronze dissolution rate were studied at +600mV/ECS, in urban-marine media in the absence and in the presence of different concentration of ATA molecule (Fig. 3). Current © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858decrease densities Volume Preprint submitted 30 August quickly and take very low14,values. In36the presence of 10mM of ATA, the 2011 dissolution rate in the passive state is the lowest and the rate of formation of passive film is highest (stationary state is achieved after few minutes). The decrease of the dissolution kinetics in the presence of ATA suggested the film became less porous and more protective owing the introduction of ATA in the film. 3.3. Gravimetric measurements The gravimetric measurements corroborate the electrochemical results. The inhibitor efficiency and the corrosion rate were calculated by weight loss measurements for an immersion period of 24h or 7 days and varying concentrations in ATA. Corresponding data are given in Table 3. Examination of Table 3 shows that the addition of ATA reduces the corrosion rate of alloys. For copper and 10mM of ATA, the immersion time influences the corrosion rate without changing the efficiency of inhibitor. For the iron, we noted the formation of a thick film on the surface that induces an increase the mass of sample after immersion period of 24H. The best efficiency is obtained for 10mM of ATA. © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 Table 3: Inhibitory efficiency and corrosion rate determined 30 August 2011 by weight losssubmitted measurements after 24 hours and 7 days of immersion period. Time 24H 7 days corrosion rate alloy [ATA] (mol/L) Corrosion rate E% -2 -1 E% -2 (mg.cm .h ) -1 (mg.cm .h ) 0 0.022 - 10-4 0.011 50 10-3 0.011 50 10-2 0.025 - 0 3.4.10-2 - 6.6.10-3 - 10-4 1.7. 10-2 50 4.96.10-3 24.8 Copper 10-3 0.6. 10-2 82.3 2.48.10-3 62.4 10-2 0.5. 10-2 85.3 0.9610-3 85.4 Iron 0 4.9.10-3 - 10-4 2.7.10-3 44.9 Bronze 10-3 1.57.10-3 67.9 10-2 0.45.10-3 90.8 3.4. Surface analysis by SEM-EDS For iron, the observation of the surface after immersion in urban-marine solution in the presence of 10mM of ATA for 7 days (Figure 4-b), shows the formation, on the surface of iron of a more homogeneous film that covers the entire surface. The EDS analysis shows the © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 presence of Volume Preprint 30on August peaks attributed to nitrogen and 14, carbon due36to the adsorption ofsubmitted inhibitor the 2011 surface. The XRD patterns of the iron after immersion in urban-marine media for 168h indicates that oxy-hydroxide of iron have formed at the surface. We observed the surface of copper electrodes after immersion in the urban-marine media in the absence and presence of ATA for 7 days (Fig. 5). In the presence of ATA, SEM micrograph (Figure 5-b) shows a uniform surface and did not present any corrosion form. We note the formation of a protective layer over the surface of copper. EDS analysis shows the presence of carbone and nitrogen and the absence of chloride on the surface. In the absence of ATA, The XRD patterns of the copper after immersion in urban-marine media for 168h indicates that CuO have formed at the surface. EDS analysis shows the presence of chloride adsorbed on the surface. SEM micrograph performed on the bronze electrode after 7 days of immersion in the corrosive solution in the presence of 10 mM ATA (Figure 6-b) shows the surface degradation significantly less than that observed in the absence of inhibitor (Figure 6-a). Analyze of each solution by ICP after 7 days of immersion period allows us to calculate the corrosion rate of alloys in corrosive medium (Table 4). These results are in good agreement with the obtained value of corrosion rate obtained by weight loss measurement. Table 4: Corrosion rate of alloys calculated using the ICP analysis of corrosive solution containing 10mM of ATA and after immersion of alloys for 7 days period at room temperature. Alloy Iron Copper Bronze 1.1 10-2 5.5 10-3 4.7 10-3 Corrosion rate mg.cm-2.h-1 4. Conclusion Electrochemical study and weight loss measurements showed that ATA acted as efficient corrosion inhibitors of bronze, copper and iron in urban-marine solution. The maximum inhibition efficiency reached exceeded 85%.The observed protecting effect of this inhibitor © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 was affected 14, Preprint 36 the inhibition efficiency submitted 30 August by the nature of alloy.Volume For 10mM of ATA, did not 2011 change significantly with increase in the immersion period. The inhibitor tested act by adsorption on the surface leading to the formation of protective inhibitory films. © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 References Volume 14, Preprint 36 submitted 30 August 2011 [1] R.J.Gettens,”Mineral alteration products on ancient metal objects-Dialogue between conservator and archaeologist and corrosion product on ancient metal objects”, in recent advances in conservation, edited by G.Thomson, Butterworths, London (1961) 89-92. [2] R..J.Gettens, ”Patina and nobles vile, in art technology a symposium on classical bronze”, eds. 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[11] L.Robbiola, C.Fiaud, S.Pennec, “New model of outdoor of bronze corrosion and its implication for conservation, in proc. 10th ICOM Meeting, 2 (1993) 796-802. [12] Payer, J.H.Bronze Corrosion: “rates and chemical processes, in Dialogue: 89- The conservation of bronze sculpture in the outdoor environment”, NACE, (1992) 103-121. [13] R.J.Taylor, I.D.MacLeod. Corrosion NACE 41 (1985) 100-104. [14] A. Chetouani, A. Aouniti, B. Hammouti, N. Benchat, T. Benhadda, S. Kertit, Corrosion science, 45 (2003) 1675. [15] P. Zhao, Q. Liang, Y. Li, J. Appl. Surf. Sci. 252 (2005) 1596. © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 [16] J.L. Yao, Volume Preprint submitted August 2011 B. Ren, Z.F. Huang, P.G. Cao,14, R.A. Gub, 36 Z.-Q. Tian, Electrochim. Acta3048 (2003) 1263. [17] M. Bazzaoui, L. Martins, E.A. Bazzaoui, J.I. Martins, Electrochim. Acta 47 (2002) 2953. [18] K. Zawada, J. Bukowska, M. Calvo, K. Jackowska, Electrochim. Acta 46 (2001) 2671. [19] M. Free, Corros. Sci. 46 (2004) 3101. [20] D. Zhang, L. Gao, G. Zhou, Appl. Surf. Sci. 225 (2004) 287. [21] D. Zhang, L. Gao, G. Zhou, Inhibition of copper corrosion by bis- (1 benzotriazolymethylene)-(2,5-thiadiazoly)-disulfide in chloride media, Electrochemical Research Group, Shanghai 200090, China (2003). [22] W. Qafsaqui, Ch. Blanc, N. Pe´be`re, A. Srhiri, G. Mankowski, J. Appl. Electrochem. 30 (2000) 959. [23] E. Szocs, G. Vastag, A. Shaban, E. Ka´lma´n, Corros. Sci. 47 (2005) 893. [24] W. Mok, A. Jenkins, C. Gamble, Corros. Sci. 6 (2003) 1. [25] S. Ramesh, S. Rajeswari, Corros. Sci. 47 (2005) 151. [26] O.L. Riggs Jr., Corrosion Inhibitors, 2nd ed., Nathan, CC, Houston, TX, 1973. [27] A. Lgamri, H. Abou El Makarim, A. Guenbour, A. Ben Bachir, L. Aries, S. El Hajjaji Progress in Organic Coatings, 48, Issue 1, (2003) 63-70 [28] El-Sayed M. Sherif, A.M. El Shamy, Mostafa M. Ramla, Ahmed O.H. El Nazhawy, Materials Chemistry and Physics, 102, Issues 2-3, (2007) 231-239. [29] K. Marušić, H. Otmačić-Ćurković, Š. Horvat-Kurbegović, H. Takenouti, E. StupnišekLisac, Electrochimica Acta, 54, Issue 27 (2009) 7106-7113. [30] Simona Varvara, Liana Maria Muresan, Kamal Rahmouni, Hisasi Takenouti, Corrosion Science, 50, Issue 9 (2008) 2596-2604. [31] K. Rahmouni, H. Takenouti, N. Hajjaji, A. Srhiri, L. Robbiola, Electrochimica Acta, 54, Issue 22 (2009) 5206-5215. [32] A. Dermaj, N. Hajjaji, S. Joiret, K. Rahmouni, A. Srhiri, H. Takenouti, V. Vivier, Electrochimica Acta, 52, Issue 14 (2007) 4654-4662. [33] G. Brunoro, A. Frignani, A. Colledan, C. 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This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 14, Preprint 36 ListVolume of figures and tables submitted 30 August 2011 Figure 1: Polarization curves of iron (a), copper (b) and bronze (c and d) recorded in urbanmarine media at different concentrations of ATA. Figure 2 : Variation of inhibitor efficiency vs. the logarithm of ATA concentration Figure 3: The passive current transients of copper (a) and bronze (b) in urban-marine solution in the absence and presence of different concentrations of ATA. Applied potential=600mV/SCE Figure 4: micrograph of the electrode of iron after immersion in urban-marine media without (a) and with 10mM of ATA (b). Figure 5: micrograph of the electrode of copper after immersion in urban-marine media without (a) and with 10mM of ATA (b). Figure 6: micrograph of the electrode of bronze alloy after immersion in urban-marine media without (a) and with 10mM of ATA (b). Table 1: Composition of the bronze (% wt). Table 2: Electrochemical parameters of iron, copper and bronze in urban-marine media in the presence of different concentrations of ATA. Table 3: Inhibitory efficiency and corrosion rate determined by weight loss measurements after 24 hours and 7 days of immersion period. Table 4: Corrosion rate of alloys calculated using the ICP analysis of corrosive solution containing 10mM of ATA and after immersion of alloys for 7 days period at room temperature. © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 submitted 30 August 2011 (a) (b) (c) (d) Figure 1: Polarization curves of iron (a), copper (b) and bronze (c and d) recorded in urbanmarine media at different concentrations of ATA. © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 submitted 30 August 2011 Figure 2 : Variation of inhibitor efficiency vs. the logarithm of ATA concentration © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 submitted 30 August 2011 (a) (b) Figure 3: The passive current transients of copper (a) and bronze (b) in urban-marine solution in the absence and presence of different concentrations of ATA. Applied potential=600mV/SCE. © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 submitted 30 August 2011 (a) (b) Figure 4: micrograph of the electrode of iron after immersion in urban-marine media without (a) and with 10mM of ATA (b). © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 submitted 30 August 2011 (a) (b) Figure 5: micrograph of the electrode of copper after immersion in urban-marine media without (a) and with 10mM of ATA (b). © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 submitted 30 August 2011 (a) (b) Figure 6: micrograph of the electrode of bronze alloy after immersion in urban-marine media without (a) and with 10mM of ATA (b). © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work. ISSN 1466-8858 Volume 14, Preprint 36 submitted 30 August 2011 © 2011 University of Manchester and the authors. This is a preprint of a paper that has been submitted for publication in the Journal of Corrosion Science and Engineering. It will be reviewed and, subject to the reviewers’ comments, be published online at http://www.jcse.org in due course. Until such time as it has been fully published it should not normally be referenced in published work.