1

Corrosão e Proteção dos

Materiais

Short review on open circuit potential tests of aluminum alloys

Lucas Veronez Goulart Ferreira1, Carlos Alberto Picone2.

1. Masters Student at UNESP Ilha Solteira - Mechanical Engineering Department;
2. Professor at UNESP Ilha Solteira – Chemistry and Physics Department;

Abstract: Aluminum alloys have an extensive range of research possibilities. Their corrosion behavior can be analyzed
through open circuit potential test (OCP). Composition, microstructure and heat treatments were the main
characteristics studied in this brief review. Aluminum alloys from the Al-Mg-Si system can show difference on their
OCP due to copper additions and Mg/Si mole ratio. Refined grain structures alter the pitting process and thus the open
circuit potential test results. Heat treatments, at the heat treatable aluminum alloys, not only change the mechanical
properties but also the corrosion behavior.
Key words: Aluminum; Aluminum alloys; Corrosion; OCP; Microstructure.

1 INTRODUCTION

Aluminum alloys, such as 6061, have a wide range of applications specially when light weight
or corrosion resistance is required (DAVIS, 1999). Alloying elements, microstructure and heat
treatments can strongly influence their corrosion resistance (ROCKEL, 2010).

Wang et al. (2017) explain that the overall results of an OCP test mainly reflects the corrosion
properties of the metal matrix. Under different compositions and aging periods Li et al. (2016)
showed a slight difference (ranging from -600 to -750 mVSCE) in the OCP value for many specimens
of Al-Cu-Li system with additions of Zn. Using specimens of Al-Cu-Li alloy under different aging
periods, Huang et al. (2018) correlated the open circuit potential with tensile strength and found the
biggest different of only about 100 mV.
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The curve obtained from the OCP test may contain fluctuations which can be associated with
the pitting process on aluminum alloys (ZOU, 2017). The destruction and formation of the passive
layer of aluminum oxides may contribute to this fluctuations (KIM, 2012). Different stable values of
OCP and rates of corrosion can also be found changing the medium of the test, as Jilani, Njah and
Ponthiaux (2014) showed in tests with distilled water and NaCl 3%wt. solution. Davó and
Damborenea (2004) obtained different potential transients after adding to a 3,56% wt. NaCl solution
rare earth salts in order to inhibit electrochemical corrosion.

The OCP test is usually conducted by using a Calomel electrode (SCE) in a NaCl 3 wt.%
(ZOU, 2017; WANG, 2017) but other electrodes such as Ag/AgCl can also be used (KIM, 2012).
The potential difference between the reference electrode and the working electrode is then recorded
for hours (JILANI, 2014) or even days (PROTON, 2014), normally until stability is verified (KIM,
2012).

2 OCP ON 6000-SERIES ALUMINUM ALLOYS

An electrochemical study on four specimens with different compositions – shown in Table 1

– was made by Zou et al. (2017) in order to evaluate the intergranular corrosion aspects of the 6000-
series aluminum alloys.

Table 1 – Compositions of specimens used on OCP test.

Alloy Mg Si Fe Mn Cu Mg/Si Mg+Si Al
A 0,62 1,10 0,16 0,06 0,06 0,55 1,73106 Bal
B 1,21 0,56 0,15 0,06 0,06 2,13 1,77824 Bal
C 0,63 1,10 0,15 0,06 0,47 0,56 1,73236 Bal
D 1,17 0,57 0,17 0,06 0,50 2,052 1,74836 Bal
Source: Zou et al. (2017).

For the OCP test, Fig. 1, a saturated calomel electrode (hence the use of the potentials in VSCE
unit) and a Pt-mesh counter electrode was used. A 3,5%wt. NaCl solution was the electrolyte. This
setup can be related to the work of Zeng et al. (2011) as they explain the micro interactions on
aluminum alloys containing Mg2Si and Si particles. The time lapsed of the OCP test was 1600s.

The OCP test shown in Fig. 1 shows the potential SCE of the four different alloys used in this
study. At the top of the figure not much difference can be seen between the A and B specimens, even
though they have different Mg/Si ratios and the same Cu content. However, specimen B showed a
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more noticeable fluctuation throughout the entire test. This is explained by Zeng et al. (2011) as being
the pitting process of the micro particles found in the alloy.

Figure 1 – OCP tests obtained along 1600s of the four specimens studied.

Source: Zou et al. (2017).

Another important feature of the OCP test shown in Fig. 1 is the stable potential difference
between all the specimens. As a result of this analysis, it is cited that the alloys with the lowest Cu
content showed the highest resistances, in the contrary alloys with high Cu content showed some
difference in the corrosion resistance as a function of the Mg/Si ratio.

3 HEAT TREATMENTS EFFECTS ON OCP

Wang et al. (2017) tested the 2024 Al alloy under different heat treatments conditions in a
35g/L NaCl solution. It is clearly seen in Fig. 2 that all the specimens reach stability at different
OCP’s which is related to the passive oxide layer formed before the test.

The AQ and CR curves are the OCP tests for the as-quenched (495 °C for 1h and then water
quenched) and the cold rolled (from a 7 mm thickness to 1 mm in room temperature) which showed
the most cathodic potentials among all the specimens. OA and RA specimens are almost equivalent
in regards to the heat treatments which is the over-aged state. Small fluctuations are observed in
almost all the curves due to pitting process. The PA curve represents the specimen at the peak-aged
state.
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Figure 2 – OCP test of 2024 Al alloys in 35g/L NaCl solution.

Source: Wang et al. (2017).

4 OCP AS AN INDIRECT FUNCTION OF GRAIN SIZE

Jilani, Njah and Ponthiaux (2014) studied the corrosion behavior of aluminum 99,1% with
specimens that went through ECAP (equal channel angular pressing) on 0 to 5 passes. This treatment
refines grain structure of metals (VALIEV; KORZNIKOV; MULYUKOV, 1993) through severe
plastic deformations. The higher the number of passes, the finer the grains. OCP test of the six
specimens studied are shown on Fig. 3.

Figure 3 – Aluminum 99,1% under different amount of passes. Curves are the immersion on 3% wt. NaCl (a) and
distilled water (b).

Source: Jilani, Njah and Ponthiaux (2014).

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The results seen in Fig. 3 are given on VSSE (Silver-Silver Chloride Electrode). Some noise is
observed on both mediums as a result of the pitting process. This phenomenon was also obtained by
Wang et al. (2017) and Zou et al. (2017) as it was shown in the previous sections. However, the
biggest noise is shown by the N=0 specimen, specially in the NaCl medium.

5 CONCLUSIONS

Three articles were analyzed in this work. Each of them showed a different aspect of corrosion
behavior through open circuit potential (OCP) tests with special attention to the microstructure of the
specimens tested. The main conclusions are:

• Composition of 6000-series aluminum alloys alters the corrosion performance, being

copper the main component that affects it, while Mg/Si mole ratio the second factor to
have its contribution;
• Aging heat treatment can lower the OCP when optimized parameters are not met.
Over-aged specimens had the worst corrosion resistance, while water quenched the
highest;
• Refined grain structures diminishes the pitting process on aluminum. ECAP, as a grain
refining method, can greatly change the response to corrosion on the immersion in
NaCl medium.

REFERENCES

DAVIS, Joseph R. Corrosion of Aluminum and Aluminum Alloys. Materials Park, Ohio:
Asm International, 1999.

DAVÓ, B.; DAMBORENEA, J.j. de. Use of rare earth salts as electrochemical corrosion
inhibitors for an Al–Li–Cu (8090) alloy in 3.56% NaCl. Electrochimica Acta, [s.l.], v. 49, n. 27,
p.4957-4965, out. 2004. Elsevier BV. http://dx.doi.org/10.1016/j.electacta.2004.06.008.

HUANG, Jia-lei et al. Correlation of intergranular corrosion behaviour with microstructure in

Al-Cu-Li alloy. Corrosion Science, [s.l.], v. 139, p.215-226, jul. 2018. Elsevier BV.
http://dx.doi.org/10.1016/j.corsci.2018.05.011.
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JILANI, Oussama; NJAH, Nabil; PONTHIAUX, Pierre. Transition from intergranular to
pitting corrosion in fine grained aluminum processed by equal channel angular pressing. Corrosion
Science, [s.l.], v. 87, p.259-264, out. 2014. Elsevier BV.
http://dx.doi.org/10.1016/j.corsci.2014.06.031.

KIM, Seong-jong et al. Electrochemical characteristics of Al–Mg and Al–Mg–Si alloy in sea
water. Transactions Of Nonferrous Metals Society Of China, [s.l.], v. 22, p.881-886, dez. 2012.
Elsevier BV. http://dx.doi.org/10.1016/s1003-6326(12)61820-2.

KIM, Seong-jong et al. Mechanical and electrochemical characteristics in sea water of 5052-
O aluminum alloy for ship. Transactions Of Nonferrous Metals Society Of China, [s.l.], v. 23, n.
3, p.636-641, mar. 2013. Elsevier BV. http://dx.doi.org/10.1016/s1003-6326(13)62510-8.

LI, J.f. et al. Intergranular corrosion of Zn-free and Zn-microalloyed Al–xCu–yLi alloys.
Corrosion Science, [s.l.], v. 105, p.44-57, abr. 2016. Elsevier BV.
http://dx.doi.org/10.1016/j.corsci.2016.01.001.

PROTON, Vincent et al. The influence of artificial ageing on the corrosion behaviour of a
2050 aluminium–copper–lithium alloy. Corrosion Science, [s.l.], v. 80, p.494-502, mar. 2014.
Elsevier BV. http://dx.doi.org/10.1016/j.corsci.2013.11.060.

ROCKEL, M. B. Sodium Chloride. In: SCÜTZE, Michael; WIESER, Dietrich; BENDER,

Roman. Corrosion Resistance of Aluminium and Aluminium Alloys. Frankfurt: Dechema, 2010.
p. 367-466.

VALIEV, R.z.; KORZNIKOV, A.v.; MULYUKOV, R.R. Structure and properties of

ultrafine-grained materials produced by severe plastic deformation. Materials Science And
Engineering: A, [s.l.], v. 168, n. 2, p.141-148, ago. 1993. Elsevier BV.
http://dx.doi.org/10.1016/0921-5093(93)90717-s.

WANG, Zhixiu et al. The intergranular corrosion susceptibility of 2024 Al alloy during re–
ageing after solution treating and cold–rolling. Corrosion Science, [s.l.], v. 114, p.156-168, jan.
2017. Elsevier BV. http://dx.doi.org/10.1016/j.corsci.2016.11.013.
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ZENG, Feng-li et al. Corrosion mechanism associated with Mg2Si and Si particles in Al–Mg–
Si alloys. Transactions Of Nonferrous Metals Society Of China, [s.l.], v. 21, n. 12, p.2559-2567,
dez. 2011. Elsevier BV. http://dx.doi.org/10.1016/s1003-6326(11)61092-3.

ZOU, Yun et al. The intergranular corrosion behavior of 6000-series alloys with different
Mg/Si and Cu content. Applied Surface Science, [s.l.], v. 405, p.489-496, maio 2017. Elsevier BV.
http://dx.doi.org/10.1016/j.apsusc.2017.02.045.