Materials and Corrosion 2013, XXX, No.

XXX

DOI: 10.1002/maco.201307287

Investigation of corrosion behavior of 6060 and 6082 aluminum alloys under simulated acid rain conditions
H. Gerengi*, P. Slepski, E. Ozgan and M. Kurtay
Instantaneous impedance changes of 6060 and 6082 type aluminum alloys in pure water, and simulated acid rain poured into the pure water was investigated by dynamic electrochemical impedance spectroscopy (DEIS). In this way, the inuence of aluminum content on the corrosion behavior of 6060 and 6082 type aluminum alloys immersed in simulated acid rain was determined.The corrosion rate of the alloy decreased with increasing Al content, which may be related to the distribution of the Alrich phase. The surface morphology of studied alloys was also examined with scanning electron microscopy.

1 Introduction
Aluminum alloys have low density, high ductility, high thermal, and electrical conductivity, good corrosion resistance, attractive appearance, and they are nontoxic. Despite their high cost, this remarkable combination of qualities makes them a preferred choice for many critical applications in aerospace, automobiles, food handling, building, heat exchange, and electrical transmission [1,2]. AlMgSi (6000series) alloys are generally regarded as corrosion resistant [3]. These alloys are usually exposed to outdoor atmosphere without protection due to the formation of an oxide (passive) lm, which naturally develops on the alloy surface under normal atmospheric conditions. The oxide lm formed on the aluminum alloy surface is nonuniform, thin and noncoherent. Therefore, it imparts a certain level of protection under normal conditions [4,5]. However, it is in industrial and marine environments that corrosion occurs quite rapidly due to the highly corrosive nature of airborne pollutants [6]. It is well known that pollution increases rapidly due to industrialization, population explosion, deforestation, vehicular exhaust, and by the burning of fossils fuels, which contain nitrogen, sulfur and carbon. Sulfur, nitrogen, and carbon do not undergo complete combustion, which evolves in atmosphere and reacts with atmospheric oxygen converted

to oxides of nitrogen, oxides of sulfur, and oxides of carbon (NOx,SOx,COx). There comes out an increase in the concentration of these gases in the atmosphere leading to Equations (14)[7,8]:

SO2g H2 Os ! H2 SO3aq 2SO2g O2g ! 2SO3g SO3g H2 Os ! H2 SO4aq 2NO2g H2 Os ! HNO2aq HNO3aq

1 2 3 4

H. Gerengi, M. Kurtay Corrosion Research Laboratory, Kaynasli Vocational College, Duzce University, 81900, Kaynasli, Duzce (Turkey), E-mail: husnugerengi@duzce.edu.tr P. Slepski Department of Electrochemistry, Corrosion and Materials Engineering, Gdansk University of Technology, Narutowicza 11/12, 80230, Gdansk (Poland) E. Ozgan Department of Construction Education, Technical Education Faculty, Duzce University, 81620, Duzce (Turkey)

A lot of research has been carried out on the inuence of different pollutants and ions on corrosion of aluminum alloys [913]. But, no study was performed about monitoring corrosion behavior of AA6060 and AA6082 aluminum alloys during acid rain instantaneously. In the present study, the inuence of Al content on the corrosion behavior of 6000series aluminum alloys in pure water and articial acid rain was investigated. The corrosion behavior of AA6060 and AA6082 aluminum alloys were investigated using electrochemical techniques such as potentiodynamic polarization and dynamic electrochemical impedance spectroscopy (DEIS) techniques. The advantage of measuring the inuence of articial acid rain during the measurement was discussed. The results of this study may prepare the basis for wider applications for developing online corrosion monitoring systems.

2 Experimental method
2.1 Materials Electrochemical measurements were carried out in a three electrode type cell with separate compartments for the reference electrode (Ag/AgCl), the counter (Pt) and the working (copper manganesealuminum alloy) electrodes with the area of 0.2 cm2.

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Gerengi, Slepski, Ozgan and Kurtay

Materials and Corrosion 2013, XXX, No. XXX

The surface of the working electrode was prepared by grinding with abrasive papers of 4001800 grades. It was rinsed with distilled water and then degreased with acetone. During all measurements, the solution was stirred with a magnetic stirrer (300 rot/min) to obtain a homogenous solution. Compositions of working electrodes are given in Table 1. Chemical composition of the articial acid rain is also given in Table 2 [14]. The pH value of solution was 3.5 and electrical conductivity was measured as 4.82 mS/cm by Thermo Scientic Orion 5Star pH and conductivity meter. All chemicals were obtained from Merck.
Table 1. Chemical compositions of working electrodes (wt%)

The corrosion behavior of aluminum 6060 and 6082 alloys was investigated with potentiodynamic polarization and DEIS methods. The experimental procedure was performed for both setups in the following sequence: First establishing OCP for 120 min [15], and then carrying out the experiment. DEIS experiments were initially started with pure water and articial acid rain was started to be dripped into the environment 2 h later in order to see the corrosive effects of articial acid rain instantaneously. In this way, corrosion of the metal inside the cell were measured for another 3 h. Measurement setup of DEIS method is shown in Fig. 1.

Samples
AA6060 AA6082

Si
0.30.6 0.71.3

Fe
0.10.3 0.5

Cu
0.1 0.1

Mn
0.1 0.41.0

Mg
0.306 0.61.2

Cr
0.05 0.25

Zn
0.15 0.2

Ti
0.1 0.1

Al
9899 9597

Table 2. Chemical composition of the articial acid rain

Material
(g/L water)

H2SO4
0.032

HNO3
0.015

Na2SO4
0.0128

NaNO3
0.0084

NaCl
0.0336

(NH4)2SO4
0.0184

Figure 1. Measurement setup of DEIS method [(1) Reference electrode Ag/AgCl, (2) working electrode, (3) counter electrode Ptmesh]

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Materials and Corrosion 2013, XXX, No. XXX

Corrosion behavior of 6060 and 6082 Al alloys under acid rain

2.2 Methods 2.2.1 Dynamic electrochemical impedance spectroscopy (DEIS) DEIS technique has been applied in different experimental set ups [1619]. DEIS method employed the short time Fourier transformation (STFT) to instantaneous impedance evaluation [20]. This technique allows obtaining impedance changes during the time. Thus, the perturbation and response signals are registered continuously during the measurement [21]. This attribute allows analysis of nonstationary systems by the application of DEIS technique. Generation of the multisinusoidal perturbation was performed with a National Instruments Ltd. PCI4461 digital analog card. The same card was used to measure the current perturbation and voltage response signals. Fast homemade galvanostat equipment was used to supply galvanostatic condition and as well as a currentvoltage converter. Application dc current Idc 0 allows to achieve the open circuit potential (Ecorr) for all time of impedance experiment. The perturbation signal was a package composed of current sinusoids of the frequency range from 4.5 kHz to 700 mHz. The lowest frequency of the perturbation signal has to be higher than the rate of the investigated process. In other words; the low frequency limit depends on the time scale of the analysis performed [22]. The sampling frequency was 12.8 kHz. 2.2.2 Potentiodynamic polarization measurements Potentiodynamic polarization measurements were performed using Gamry Instrument Potentiostat/Galvanostat/ZRA. Polarization curves were recorded at a constant sweep rate of 1 mV/s at a 300 to 300 mV interval with respect to open circuit potential (Ecorr). Experiments were always repeated at least seven times so that good agreement was obtained.

2.2.3 Surface analysis The surface analysis of 6060 and 6082 type aluminum alloys were investigated by means of scanning electron microscopy (SEM; JEOL SEM5800) equipped with an EDS probe (accelerator voltage was 20 keV) after DEIS experiments. The surface analysis of the studied samples were investigated after DEIS measurements were made in the environment in which acid rain was started to be dripped into the cell.

3 Results and discussion

3.1 Dynamic electrochemical impedance spectroscopy (DEIS) Figures 2 and 3 display DEIS results obtained from studied samples in pure water for 2 h and articial acid rain was started to be dripped into the environment in order to see the corrosive effects of articial acid rain instantaneously. It was indicated that the shapes of DEIS plots of the two materials were very similar, which implied that the corrosion process of them may follow same mechanism. These results are parallel with potentiodynamic polarization measurements. The Nyquist plot diagrams show one capacitive time constant at high frequencies and a nonwell dened time constant (positive loop) at low frequencies, probably associated with diffusion processes also reported in the literature [23,24]. The analysis of the impedance spectra and tting of the experimental results to equivalent circuits were performed by using ZSimpwin 3.1 software, which allowed the chisquare (x2) value to judge quality of equivalent circuit tting. In order to obtain more qualitative information of the corrosion mechanism, the impedance data were analyzed by using of an electrical equivalent circuit R(QR). The circuit consists of the solution resistance Rs, the constant

Figure 2. 3D representation of impedance changes of AA6060 in pure water solution for 2 h and articial acid rain was started to be dripped into the environment presented in a form of Nyquist plot obtained from DEIS method

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Gerengi, Slepski, Ozgan and Kurtay

Materials and Corrosion 2013, XXX, No. XXX

Figure 3. 3D representation of impedance changes of AA6082 in pure water solution for 2 h and articial acid rain was started to be dripped into the environment presented in a form of Nyquist plot obtained from DEIS method

phase element (CPE) and the parallel resistance Rct, which corresponds to the charge transfer resistance. The impedance of CPE is given by using Equation (5).

Z CPE Qj vn 1

For n equal to one, Equation (5) represents the impedance of a capacitor. Lower values of n between 0.7 and 0.9 are often obtained with solid electrodes in aqueous solutions in the audio and subaudio frequency range. Much lower values of around 0.5 have been frequently observed with porous electrodes. The rougher the surface, the larger the deviation from the ideal capacitive behavior is. Therefore, the CPE might be a good tool to evaluate the sample surface roughness and heterogeneity [25]. The n parameter for AA6060 and AA6082 alloys were instantaneously measured with DEIS method and presented in Fig. 4. It was obvious that a passive lm with high insulating property had formed on the surface of studied aluminum alloy surfaces when we established OCP for 120 min in pure water. This can be seen from changes of n parameter (Fig. 4) and Rct during measurements (Figs. 56). Linear changes after 7200 s were previously attributed to the stepwise dissolution of the inner adherent barrier layer and the outer porous modication of Al2O3 on the metal surface, respectively [2628]. SEM and EDS results encouraged this opinion. Figures 5 and 6 demonstrate the changes of Rct results during DEIS experiment. For both studied samples, it can be seen that the passivation process was nished by dripping articial acid rain to the corrosion cell in nearly 15 min. Similar changes were obtained by Ono and Habazaki [29], when they studied the pit growth behavior of aluminum under galvanostatic control. The differences of Rct values of studied alloys in pure water, and articial acid rain are close to each other. Ezuber et al. [30], compared corrosion of AA1100 and AA5083 aluminum alloys in seawater by using potentiodynamic polarization and weight loss methods and obtained

resistance results that are also close to each other. These small changes were attributed to the oxide lm on the surface of aluminum alloys [31]. Potential (E) and Q values of studied aluminum alloys are displayed in Figs. 7 and 8. It was clear from these gures that E and Q values are almost constant after starting the experiment which indicates that the system becomes stationary when we establish OCP for 120 min before the DEIS experiment. Stationary state can also be observed when acid rain dripped to the cell as explained with Figs. 46. Changes of n, Rct, E, and Q values have same tendency during DEIS experiments and all results supported each other.

Figure 4. Surface heterogeneity (n) versus time of AA6060 and AA6082 alloys exposure in pure water for 2 h and articial acid rain was started to be dripped into the environment presented based on the DEIS results

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Materials and Corrosion 2013, XXX, No. XXX

Corrosion behavior of 6060 and 6082 Al alloys under acid rain

Figure 5. Rct changes of AA6060 alloy exposure in pure water for 2 h and articial acid rain was started to be dripped into the environment presented based on the DEIS results

Figure 6. Rct changes of AA6082 alloy exposure in pure water for 2 h and articial acid rain was started to be dripped into the environment presented based on the DEIS results

The value of Q (Fig. 8) for AA6060 has low interfacial capacitance compared to AA6082 alloy. Previous researches have already identied that n values increased while the Q values decreased [6,32]. The Q parameter has been connected to the mechanical changes of the sample surface roughness [33]. Correlation between n and Q shown in Figs. 4 and 8 also conrms this idea.

3.2 Potentiodynamic polarization measurements The potentiodynamic polarization curves of AA6060 and AA6082 aluminum alloys in water and articial acid rain solution at room temperature are shown in Fig. 9. The curves show that the anodic and cathodic polarizations of the two samples are similar, i.e. they run the similar corrosion dynamic

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Figure 7. Potential (E) changes of AA6060 and AA6082 alloys exposure in pure water for 2 h and articial acid rain was started to be dripped into the environment presented based on the DEIS results

Figure 9. Potentiodynamic polarization curves for aluminum 6060 and 6082 alloys in pure water and acid rain solution

behaviors. It is found out that the anodic current density values of AA6082 are higher than AA6060 in all studied environments. For both aluminum alloys, a passive region is exhibited clearly in articial acid rain solution. The passivation is due to the formation of various protective compounds or corrosion products on the sample surfaces [34,35]. In the passive region, it is obvious that the average passive current density (ipass) of AA6082 alloy is higher than AA6060. The average ipass of AA6060 is 54.46 A/cm2, which is less than that of AA6082 alloy which is nearly 113.18 A/cm2. Passive potentials (Epass) versus

Ag/AgCl electrode of each alloy are shown in Fig. 9. Obtained average Epass values of AA6082 are also higher than AA6060 alloy. This result can also be found from DEIS Fig. 7. 3.3 SEM investigation and EDX analysis Figures 10 and 11 show the SEM photos of AA6060 and AA6082 alloy surface. It can be seen from these gures that the aluminum sample's surface appears to be under an aggressive attack of the corroding medium. One can see a large number of pits arising on the surface of studied alloys assisted by corrosion processes, which greatly increase the surface roughness (Fig. 4). It was observed that higher numbers of shallow pits formed on AA6060 surface. Distinct from AA6060, AA6082 has bigger pits. The pit morphology, shown in Figs. 10 and 11, suggests that shape and distribution of pits on aluminum alloy surfaces are related to electrochemical nature of the intermetallic phases [36].

Figure 8. Q parameter of the CPE element versus time of AA6060 and AA6082 alloys exposure in pure water for 2 h and articial acid rain was started to be dripped into the environment presented based on the DEIS results

Figure 10. SEM picture of AA6060 after DEIS measurements

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Materials and Corrosion 2013, XXX, No. XXX

Corrosion behavior of 6060 and 6082 Al alloys under acid rain

Figure 11. SEM picture of AA6082 after DEIS measurements

Figure 13. EDS analysis of AA6082 (Dot 1 and Dot 2) after DEIS measurements

The increased susceptibility of the AA6082 to pitting attacks has been reported in the literature as related to the high concentration of Mg content [37]. SEM pictures of AA6082 show a difference from that of AA6060 alloy. Thus, one more point selected on the AA6082 alloy surface for analysis with EDS. All EDS analysis are presented in Figs. 12 and 13. EDS results (Figs. 12 and 13) showed that the Mg content in the AA6060 alloy is lower than that of the AA6082 alloy. Oxygen percentage on the surface of AA6060 was 47.34%, but for AA6082 this value is bigger in selected place, (+1) 66.76% and (+2) 58.6%, respectively. From EDS, the presence of S element was also established. S possibly comes from preparation of articial acid rain by using H2SO4, which could react with Al(OH)3 to form hydrated aluminum sulfate [3840]. Calculated S element concentration on the surface of AA6082 is higher than AA6060. Therefore, this can be thought as one of the reasons of different SEM view of 6082.

4 Conclusions
1. The results obtained in this study indicate that the types of intermetallic particles in aluminum alloys are important in pit morphology of aluminum alloys. 2. The potentiodynamic polarization and DEIS results reveal that the pH of the studied environment is very effective on investigation of electrochemical corrosion process. Rct, CPE parameters: Q and n changes conrm this idea. The critical pitting potential calculated from the polarization data is in good agreement with DEIS data. 3. AA6060 and AA6082 have similar corrosion behaviors in pure and articial acid rain environments. Protection lm formed in the absence of acid rain has great importance against corrosion. 4. Compared to the other corrosion measurement methods, this research shows that the DEIS method has a big advantage that gives ability to collect data instantly.

Acknowledgements: This work was partly supported by the Duzce University Research Council for Science and Technology and by Scientic and Technological Research Council of Turkey (TUBITAKBIDEB 2224/July 2013).

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Figure 12. General EDS analysis of AA6060 after DEIS measurements

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