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Materials and Design 29 (2008) 806810

An investigation on the use of indium to increase dissolution of AlZn anodes in sea water
A. Zazoua *, N. Azzouz
partement de Chimie Industrielle, Laboratoire Interaction mate riaux-Environnement, Universite de Jijel, BP 98, Ouled Aissa, Jijel 18000, Algeria De Available online 26 January 2007

Abstract This paper presents the production and the electro-chemical characterization (in open and in closed circuits) of a AlZnIn anode. The aim is to use it as a protective material (cathodic protection) of metallic and immersed (in natural sea water) infrastructures. The reactivity of this material was examined using two electrochemical techniques: Evans diagrams and I = f(E) curves in surroundings of natural sea water. The optimised amount of indium (as the main element in the composition) was computed based upon corrosion tenue (the minimal dissolution rate value was aimed) of dierent samples having various content of this element. 2007 Elsevier Ltd. All rights reserved.
Keywords: Corrosion; Indium; Sea water; Aluminium anode

1. Introduction In order to face the relative eciency of mechanical protection (protection by surface coating) i.e., obstacles between marine environment and metals scientists have developed a new way of protection, based on consideration of the corrosion problem [1,2]. Why then should we try to protect steel from corrosion if we can make it impossible for the reaction, that causes promotes metal destructions, to take place? In order to achieve this, we could articially displace the natural corrosion potential, either by making the metal react as an anode (anodic protection) or as a cathode (cathodic protection) [3,4]. The present study concerns the realization and characterization of a sacricial anode (of the AlZnIn type, with a new formulation) used for the cathode protection of metallic structures that are immersed in natural sea water. The electrochemical study consists in quantifying the reactivity of this material in open circuit or closed circuit.

2. Experimental 2.1. Anode elaboration The composition of our material has been obtained using the following raw materials (in predetermined quantities): 1. Pieces of AlZn alloy at 98% aluminium and traces of iron and silica. 2. ZAMAC alloy with the following composition: 11% Al; 1% Cu; 0.025% Mg; 88% Zn. 3. Indium welding alloy with the following composition: 32.5% Bi; 16.5% Sn; 51% In. The addition of sample quantities of calcium carbonate and sodium chloride has been used to decrease the melting temperature of the mixture [5]. The cylindrical-shape anode has been elaborated by classical moulding in green-sand moulds. 2.2. Preparation of samples The test samples were prepared to make their surface electrochemically active. On the samples, we predetermined work area to be 1 cm2 surface.

Corresponding author. E-mail address: azazoua@yahoo.fr (A. Zazoua).

0261-3069/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.matdes.2007.01.010

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Nomenclature i E currents (A) potential (mV) m t mass (kg) time (year)

2.3. Intrinsic behaviour of the anode in natural sea water (open circuit) The reactivity of the samples (six samples from dierent mouldings) was tested in natural sea water by plotting curves log (I) = f(E). The potentiodynamic polarisation experiments were conducted with a scan rate of 1 mV. s1. The starting potential was 1100 mV/SCE. The experimental device to draw the curves is traditional device with three electrodes. To achieve this, a PotentiostatGalvanostat type PGP 201 piloted by the VOLMASTER 4 software was used. 2.4. Behaviour of the galvanic-coupling anode with the structure to be protected (closed circuit) The anodesteel coupling in sea water by the Evans method was studied. To this purpose, three surface ratios of the anodecathode were considered. This allows us to access the maximum battery current as well as the dual potential [6]. All of the tests were performed at ambient temperature without agitation. 3. Results and discussion 3.1. Tafel curves (open circuit)

current densities. The obtained values for the six samples vary between 5.17 and 6.88 lA cm2, with an average of 5.91 lA cm2. The results obtained by Reboul [9] for aluminium series 7000 (zinc alloy at 4.5% to 6% without copper) are values of 1.001.50 lA cm2 and potentials of about 1020 to 1100 mV (Ag/AgCl) in a sodium chloride solution having NaCl content similar to that of natural sea water. Consequently, our material is almost four times more reactive (in open circuit), because of the presence of indium, which accelerates the dissolution of aluminium. (Tin and mercury were abandoned for reasons of eciency and pollution). Let us note that in the preceding gures that for the current density values correspond penetration values in mm an1. The application of Faradays Law to the average current density gives the mass loss: M 1=96 500 27=3 i t Knowing that i = 5.91 lA cm2, t = 1 year, we get a mass of 173.8 g. This result is in accordance with those mentioned in the bibliography [10] for a more aggressive environment (see Figs. 17). 3.3. The evans diagrams (closed circuit)

Log I (A/cm)

The dissolving potentials (of corrosion) in open circuit (without galvanic coupling) are located in a spectrum between 911.1 and 975.9 mV measured versus the saturated calomel electrode (SCE). The potentials values correspond to 956.1 and 1020.9 mV/Ab/AgCl, which means an average potential of about 988/Ag/AgCl. This value is electronegative than that of unalloyed aluminium in sea water, which is 795 mV/Ag/AgCl. That is due to zinc which lowers the potential towards more electronegative values. According to Laque [7] and Vargel [8] the zinc element confers to aluminium more electronegative potentials. The resulting average potential is similar to the value found by others researchers for zinc-alloyed aluminium [8]. According to Vargel, based on the Pourbaix Diagram, too electronegative potentials (i.e., potentials that go beyond the stability spectrum of water) leads to cathode corrosion risks. 3.2. Density of the corrosion current (dissolution in open circuit) The extrapolation of the Tafel curves to the corrosion potential (of dissolution) permits to obtain the corrosion

The set structure to be protected anode works like a battery in the presence of a conducting electrolyte: It is galvanic corrosion. The Faradays Law applies to it. Thus, it is necessary to experimentally determine the current density of this battery. We can also access its dual potential. The couplings current density, which gives the importance of galvanic corrosion, depends on several factors [7] among which are:

3 2.5 2 1.5 1 0.5 -1.2 -1 -0.8 -0.6 -0.4 -0.2 0 -0.5 0 -1 -1.5

E (V)/CSE
Fig. 1. log I = f(E) curve (sample 01).

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2.5

3 2.5

Log I (A/cm)

Log I (A/cm)

1.5 1 0.5 0 -1.2 -1 -0.8 -0.6 -0.4 -0.2 -0.5 -1 0

2 1.5 1 0.5 0 -1.2 -1 -0.8 -0.6 -0.4 -0.2 -0.5 -1 0

E (V)/CSE
Fig. 2. log I = f(E) curve (sample 02).

E (V)/CSE
Fig. 5. log I = f(E) curve (sample 05).
3 2.5

Log I (A/cm)

2 1.5

0.5 0 -1.2 Log I (A/cm) -1 -0.8 -0.6 -0.4 -0.2 -0.5 0 -1 -1.5 -2 -2.5 -3 -3.5 -4 E (V)/CSE

1 0.5 0

-1.2

-1

-0.8

-0.6

-0.4

-0.2

-0.5 -1

E (V)/CSE
Fig. 3. log I = f(E) curve (sample 03).

1.5 1 0.5

Fig. 6. log I = f(E) curve (sample 06).

Log I (A/cm)

-1.2

-1

-0.8

-0.6

-0.4

-0.2

0 -0.5 0 -1 -1.5 -2 -2.5 -3 -3.5

E (V)/CSE
Fig. 4. log I = f(E) curve (sample 04).

(a) (b) (c) (d) (e)

nature of the electrolyte, polarization phenomena, surface ratio of the two metals, distance, temperature.
Fig. 7. Variation of corrosion speed of the Al type 1050 in NaOH solutions.

A comparison of the dissolution potentials of the aluminium alloys can lead to some aberrations [8]. For example, we prefer alloys of 2000 family (copper alloys) whose dissolution potential is a lot more electronegative (about 650 mV) than those of 5000 family (magnesium alloys) which have more electronegative potentials (around

800 mV). The reason is that the latter ones have an excellent behaviour (resistance) to corrosion, whereas the rst ones are very sensitive to corrosion in natural environment.

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Fig. 8. Evans diagram galvanic coupling (surface ratio 1/1).

Consequently, it is more ecient to measure the density of the galvanic current. The results obtained are shown in Fig. 8. From these results, one notices that the battery functions under cathode control (cathodic polarization). On the diagram, shows a dual potential of 916.7 mV/SCE (that is 961.7 mV/Ag/AgCl) and a density of the dissolution current of 0.237 mA cm2. As to the current density 0.237 mA cm2 or 2.37 A m2, the application of Faradays Law gives an annual mass loss of 6.97 kg (that is the equivalent of 2.94 kg per each Ampere). As mentioned above, the surface ratio anodecathode plays an important role in the anode reactivity. As the battery functions under cathodic control, we have voluntarily increased the cathode surface up to 13.5 and 27 times the

anode surface in order to check this dependence. The obtained results are shown in Figs. 9 and 10: Indeed, the current densities have increased with an increase of the cathode surface by from 0.854 to 2.243 mA cm2. This lead to an increase of mass loss of, respectively 25.11 and 65.97 kg (that is annual amounts of 2.940 and 2.941 kg for an Ampere). 3.4. RDX characterization The material has been studied by ray diraction X in order to determine impurities or additions elements susceptible to be present in the matrix. The sample presents two types of structures: in majority phase, it is the alloy, Al cubic centered phase which can be substituted by Zn or

Fig. 9. Evans diagram galvanic coupling (surface ratio 1/13.5).

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Fig. 10. Evans diagram galvanic coupling (surface ratio 1/27).

Fig. 11. Determination of impurities and additions elements by ray diraction X.

Cu. The rays of BiO3 are in fact the rays of indium shifted (see Fig. 11). 4. Conclusions The study aimed at the reactivity of an AlZnIn anode used for the cathodic protection of a metallic installation that is immersed in natural sea water. To this purpose, two electrochemical techniques have been used to characterize this material in natural sea water solutions that are picked up regularly to achieve our tests. The obtained results have revealed that indium favours signicantly the reactivity of aluminium in natural sea water, which gives anode a better yield in the cathodic protection of immersed marine installations.

References
[1] Shibli SMA, Gireesh VS, George S. Corros Sci 2004;46:81930. [2] Shibli SMA, Gireesh VS. Appl Surf Sci 2003;219:20310. [3] Liou YM, Chung SC, Tsai WJ, Shih SC. Corros Prevent Contr 2000;47:62. [4] Schaer GB, Huo SH, Drennan J, Auchterlonie GJ. Acta Mater 2001;49:2671. [5] Venugopal A, Raja VS. Corros Sci 1997;39:2053. [6] Baptistia W, Jose CM. Mater Perform 1999;38:34. [7] Laque FL. Marine corrosion causes and prevention. New York: John Willey; 1975. nieur Conseil en Corrosion de laluminium. Corrosion [8] Vargel C. Inge de laluminium. Dunod; 1998. thodes de mesure de la corrosion ge ne ralise e de [9] Reboul M. Me laluminium et de ses alliages. Revue de lAluminium 1973;419:399412. [10] Oldeld JW. Electrochemical theory of galvanic corrosion. ASTM STP 1988;978:522.