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Effect Of Silicon On Corrosion Behaviour Of Al-Zn As A Low Voltage

Sacrificial Anode For Marine Environment
To cite this article: Yudha Pratesa et al 2019 IOP Conf. Ser.: Mater. Sci. Eng. 547 012056

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IC-DAEM 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

Effect Of Silicon On Corrosion Behaviour Of Al-Zn As A Low

Voltage Sacrificial Anode For Marine Environment

Yudha Pratesa*1, Ahmad A. Utama1, Ardi Erianto1, and Deni Ferdian1

1
Department of Metallurgy and Materials, Faculty of Engineering, Universitas
Indonesia, 16424, Indonesia

*Corresponding author (E-mail): yudha@metal.ui.ac.id

Abstract. A sacrificial anode is a method for material protection in the sea and coastal area. This
method is widely applied in marine, subsea and ship structure. Al-Zn-In, a commercial grade of
the sacrificial anode had a weakness in the possibility of stress corrosion cracking due to
overprotection. This study tried to substitute indium with silicon as the alloying element with
composition 0.5% and 1% wt. However, commercial grade Al ingot contained trace elements
such as iron in the significant amount, which could make a β-Al9Fe2Si2 as an iron-rich
intermetallic phase. Therefore, this study will also examine the effect of β-Al9Fe2Si2 on alloys
corrosion behavior. The alloy was produced through casting process with resistance furnace.
Corrosion behavior was characterized by cyclic polarization in 3.5% NaCl solution.
Microstructure characterization was performed using Scanning Electron Microscope, Energy
Dispersive Spectroscopy, and optical metallography. The result showed that the silicon increases
the corrosion rate of Aluminum Zinc (Al-Zn) and reduced the potential protection of the alloy in
high strength steel. Our research showed the corrosion took place along the interdendritic area
where the β-Al9Fe2Si2 intermetallic phase formed in a micro galvanic manner

Keywords: Aluminum, Marine Corrosion, Low Voltage, Sacrificial Anode, Ship Maintenance

1. Introduction
Various ways are already applied to inhibit corrosion attacks, such as inhibitors, coating, and
application of cathodic protection. Cathodic protection is considered a cheaper option than the
application of corrosion-resistant alloys such as stainless steel or a nickel-based alloy.
Furthermore, there are two methods of cathodic protection, impressed current and sacrificial
anode. The latter methods will be discussed further in this research.

Nowadays, the sacrificial anode Al-Zn-In has been used extensively as an aluminum sacrificial
anode. Salinas et al. found interdendritic zona is a susceptible area to be attacked by corrosion.
1 Moreover, this phenomena will produce self-corrosion that was the principal cause of

efficiency loss. Generally, indium (In) element is used to prevent the passivation of Aluminum.
However, in some cases have shown that Aluminum – Zinc – Indium (Al-Zn-In) sacrificial
anode could trigger hydrogen induced cracking in high-strength steel.2,3 Apparently, it
happened due to overprotection which made the steel potential reaches the hydrogen evolution
potential area.

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IC-DAEM 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

The sacrificial aluminum anode can be referred as "low voltage" if protection potential is
between -0.80 V to -0.85 V vs. SCE.4 Hence, a sacrificial anode with lower voltage potential
was developed with the additions of silicon or copper. Some other alloying element has been
proposed for replacement of indium such as mercury and tin. 5,6 Nevertheless, the problem with
mercury is an environmental issue while Tin did not give sufficient efficiency for the sacrificial
anode. Pautasso found Al-0.1% gallium alloy could be used as the low voltage sacrificial
anode.7

Other researchers stated that the addition of bismuth could improve the efficiency of sacrificial
anode alloys Al-5Zn-0.25Sn. 8 Bismuth acted by widening the aluminum (Al) matrix and make
tin (Sn) dissolved into the aluminum matrix. Murai et al. developed a new alloy using bismuth
ranging between 0.005-1.0% with improved efficiency between 65 and 71%.9 Furthermore, the
efficiency has been increased more than 83% by the addition of 2% Mg. Muazu et al. found
protection potential of carbon steel is less than or equal to -0.5 V SHE after a couple with the
low voltage sacrificial anode. It is sufficient to change the steel behavior from active to immune
region based on pourbaix diagram. 10

Effect of Silicon on precipitate will vary depending on the bonded metal in the precipitate. Zeng
Feng et al. found the preferential dissolution of metal in precipitate Mg 2Si. The first step was
Mg dissolution. After a significant amount of Mg dissolve, Mg 2Si potential changed to a
positive direction.11

Schnatterer et al. found another effect of silicon in an aluminum alloy. They found precipitate
silicon formation will affect the adjacent area of precipitate due to the reduction of silicon
content in this area. 12

Most of the research is used more than one alloy to increase the efficiency of sacrificial anode.
However, they are considered more expensive compared with Al-Zn-In. Nevertheless, previous
work by Pratesa et al. used copper to substitute indium and found a significant effect in the
reduction of Open Circuit Potential (OCP) the aluminum alloys. 13,14 This study used silicon as
a substitution for indium in the aluminum sacrificial anode. Therefore, this alloy could be more
easy to produce and cheaper than the other proposed alloying element

2. Materials and Methods

Fabrication of sacrificial anode was performed using casting methods with resistance melting
furnace. Commercially high purity aluminum ingot (99.98%), Zinc ingot (99.7%) and Silicon
(99.5%) were mixed to achieve the target composition (Al-5Zn, Al-5Zn-0.5Si, and Al-5Zn-
1Si). Melting process was conducted at temperature 800°C without any degassing treatment in
a graphite crucible. The casting product was characterized by the chemical composition test
using Optical emission spectroscopy (OES).

Corrosion behavior of the alloy was analyzed using cyclic potentiodynamic polarization in
3.5% NaCl solution with scanning rate 0,01 V/s at room temperature. Three electrode systems
were used for cyclic potentiodynamic polarization with graphite as a counter electrode and
Ag/AgCl as a reference electrode. The reversed of scan direction happened when the electrode
potential reached the anodic potential of 0 V. Polarization testing was conducted to determine
the value of pitting potential (Epitt), re-passivation potential (Eprot) and corrosion potential
(Ecorr). Electrochemical impedance spectroscopy (EIS) was conducted in 3.5% NaCl water
with PGSTAT302N and Nova 1.8 for the analysis. It used 100kHz – 10mHz and amplitude
10mV after preconditioned in the same solution for 30 minutes.
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IC-DAEM 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

Immersion test was conducted for three days for corrosion morphology examination. Protection
potential of low carbon steel pipe was measured using galvanic coupling methods and measured
using saturated calomel electrode (SCE) reference electrode. After the immersion test, the
sample was viewed under a microscope directly without the etching process. For phase
identification, Scanning Electron Microscope (SEM), Energy Dispersive Spectroscopy (EDS),
and Differential scanning calorimetry (DSC) with scanning rate 10oK/min were done.

3. Results and Discussion

3.1 Chemical Composition

The chemical composition of the alloy was shown in Table 1. The result was achieved with
some minor deviation from the target in zinc composition. This condition is a result of the
melting temperature differences between zinc and aluminum, which make zinc easier to fade
out during the casting process.

Table 1 Chemical composition of product14

Element (%)
Alloy Al Si Ni Zn Fe
Al-5%Zn 94.9 0.120 <0.005 4.90 0.04
Al-5%Zn-0.5%Si 94.8 0.597 0.006 4.60 0.07
Al-5%Zn-1%Si 93.6 1.2 0.03 4.85 0.035

3.2 Cyclic polarization

Cyclic polarization test was conducted to analyze the pitting behavior of the alloys such as
breakdown potential (Epit), repassivation potential (Erep) and corrosion potential (Ecorr).
Breakdown potential (Epit) of the alloy was reduced as the silicon content increases in the alloy.
This condition could be a contribution of the intermetallic phase that formed in the
interdendritic region. However, the corrosion potential (Ecorr) escalated with the percentage of
silicon added to the alloy. The reason is due to the silicon that has higher potential than
aluminum and some of the silicon atoms dissolved in an aluminum matrix. Aluminum has a
maximum solubility limit for silicon at 1.25% atomic percent, while this alloy contains only
1% of silicon. It means silicon dissolved in the matrix α Al and caused increasing of corrosion
potential of aluminum.

Figure 1 showed the effect of silicon in Al-5Zn alloy. Al-Zn-Si corrosion potential is -0.9 mV
while Al-Zn-In corrosion potential is about -1.3 mV15. It is an indication that Al-Zn-Si is a
potential candidate for the low voltage sacrificial anode. Size of the hysteresis loop (gap
between Epit and Erep) reduced after the addition of silicon. The larger hysterical loop will
vulnerable to the pitting corrosion. This is caused by harder reformation of the passive layer in
the alloys. The largest area of the loop is Al-5Zn, and it reduced after the addition of silicon.
Silicon has improved the potential repassivation (ERep) of the alloy and reduced the size of the
hysterical loop.

This result is different with the condition on Al-Mn/Al-Mg alloy. Addition of Mn or Mg to the
pure aluminum alloy with a composition between 0.5% wt and 1% wt did not cause any
difference on pitting behavior.16 Silicon acted differently compared with those metals. It could
be an effect of the intermetallic phase that more cathodic behavior than Mn or Mg precipitate.
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IC-DAEM 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

Based on figure 1 a and b, the Ecorr is always lower than the E repp. It showed that all of the
alloys would suffer by pitting corrosion mechanism and no crevice corrosion will form.

3.3 Galvanic Coupling

Galvanic coupling was measured between Al-Zn-Si and low carbon steel pipe. The coupled
potential of Al-5Zn is about -0.901 V, however, the addition of 1% silicon can increase the steel
potential to -0.860 V vs. SCE in Al-5Zn. Figure 2 showed the result of galvanic coupling
between Al-Zn-Si alloy with the other study for the comparison. Al-Zn-Si gave the lowest
potential compared with Al-Zn-In and existing “low voltage sacrificial anode (Al-Ga) ”5. Based
on this result, Al-Zn-Si alloy is a promising alloy for the low voltage sacrificial anode

a a
b

Figure 1 (a) Effect of Silicon in Al-5Zn (b) Cyclic polarization after addition of Zn and Silicon

-0.8

-0.85
Al-Zn-Si
-0.9 Al-Zn-In [11]
Al-Zn-In [10]
Al-Ga [3]
-0.95

-1

-1.05
Figure 2. Carbon Steel potential protection with different aluminum anode alloy 5,15

3.4 Phase Analysis

Phase analysis was conducted using metallography method and EDS analysis. Figure 3
showed the presence of intermetallic and eutectic silicon formed at the interdendritic area. The
intermetallic phase had a needle-like shape which is typical for the Al-Fe-Si intermetallic
compound. Iron (Fe) came from the impurities in aluminum and silicon ingot. The addition of
silicon reduced dendrite arm spacing of aluminum, which contributes to the escalating of the
intermetallic formation Energy dispersive spectroscopy (EDS) analysis confirm the formation
of an iron-rich intermetallic precipitate as shown in figure 4. The alloy had a composition ratio
of Fe/Si which less than 2, which tend to form as a β-Al9Fe2Si2 phase.17

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IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

Figure 3 Microstructure of (a) Al5Zn, (b) Al5Zn0.5Si and (c) Al5Zn1Si

EDS also showed that zinc composition is higher in the area around the intermetallic
precipitate (table 2). This condition is a result of low zinc solubility in the intermetallic
precipitate.
Table 2 Composition of each point EDS analysis
Location Element Wt% Possibility of
phase
1 Al 61.7 β-Al9Fe2Si2
Zn 4.41
Si 8.56
Fe 12.46
2 Al 80.2 α-Al
Zn 0.69
Si 6.48
Fe 0.05
3 Al 83.7 α-Al
Zn 2.68
Figure 4 location of EDS testing Si 7.54
Fe 2.95
Differential scanning calorimetry showed the formation of each phase by their solidification
temperature. Table 3 showed AlFeSi was formed at a temperature around 560°C. 17 The first
solidification was α-Al matrix phase at temperature 640 °C.
Table 3 Phase formation during solidification on Al-5Zn-1Si

No Fasa Suhu (oC)

1 Start α-Al 640
2 Peak α-Al 616
3 β-AlFeSi 560
4 Start Eutektik Si 555

Figure 5 DSC and derivative curve of Al-5Zn-1Si 5 Peak Eutektik Si 545

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IC-DAEM 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

3.5 Electrochemical impedance spectroscopy (EIS)

EIS was conducted for the surface electrochemical behavior of the alloy. The results were
analyzed by Randall's circuit. Figure 6 showed the Nyquist plot that silicon will make a semi-
circular diagram. Semi-circular Nyquist diagram showed silicon made double layer phenomena
in the material surface which also indication of passive layer formation. The corrosion process
is charge transfer controlled. Pure aluminum has the largest loop. However, the addition of
another alloying element, i.e zinc and silicon, reduce the size of the loop. This reduction indicate
the charge transfer resistance reduce, which also indicated silicon and zinc reduce the
uniformity of the passive layer of aluminum as showed in figure 6b. Table 4 shows the result
of EIS analysis with simple randals cell.

a b

Figure 6 Nyquist diagram from Al, AlZn, and AlZnSi (a) and the electrochemical circuit of each alloy (b)

3.6 Immersion test

Immersion test was conducted to analyze the effect of each phase in this alloy in 3.5% NaCl
solution. For 48 hours, Bruzzone et al. found the effect of the intermetallic phase to the
sacrificial anode efficiency. 18 They found self-corrosion at any phases in aluminum alloy would
be the reason for the sacrificial anode efficiency reduction. Based on figure 7, the intermetallic
and matrix creating an electrochemical cell. The intermetallic phase β-Al9Fe2Si2 acted as an
anode while the matrix acted as a cathode. The corrosion that attacked the intermetallic could
be caused a breakdown on a passive layer of aluminum by chloride ion

Table 4 EIS result form the EIS test

Alloy Rct N CPE
Al 13,2kΩ 0,798 19,4
Al-5Zn 8,72kΩ 0,77 64,8
Al-5Zn-0.5Si 5,81kΩ 0,736 107
Al-5Zn-1Si 4,54kΩ 0,827 44,8

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IC-DAEM 2018 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

This study showed different result compare with the previous study by Yoshikawa et al. that
stated intermetallic acted as an active cathode while the matrix is the anode. 19 The reason for
this condition is due to zinc percentage on the intermetallic phase that higher compared with
the matrix as shown in table 2. Higher zinc composition contributes to reducing the corrosion
potential of the intermetallic phase, hence acted as the anode.

Figure 7 Pit formation before immersion (a,b,c), after immersion without polishing (d,e,f) and after polishing (g,h,i). Blue
circle showed porosity condition before and after immersion while red circle showed corrosion propagated from
interdendritic phase

4. Conclusions
Silicon in Al-5Zn alloy will form a eutectic Si phase and in the presence of iron as an impurity
in commercial aluminum ingot will create intermetallic β-Al9Fe2Si2 phase. β-Al9Fe2Si2 phase
and eutectic Si make a passive layer that did not distribute uniformly in aluminum surface.
Silicon improved the Potential Repassivation (Erep) of the alloy and reduced the size of the
hysterical loop.

Immersion test showed that β-Al9Fe2Si2 phase acted as anode area while the aluminum matrix
served as cathode area. The amount of dissolved zinc changed the intermetallic β-Al9Fe2Si2
phase behavior to be more anodic than the matrix. The result showed that Al-Zn-Si alloy
increased coupling potential of low carbon steel and suitable for low voltage sacrificial anode
candidate.

5. Acknowledgments
The authors are grateful to PT INALUM Indonesia for providing the aluminum ingot and
DRPM-UI through PITTA grant 2017 for the financial support.

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IOP Conf. Series: Materials Science and Engineering 547 (2019) 012056 doi:10.1088/1757-899X/547/1/012056

6. References

1. Salinas, D. R., Bessone, J. B. & Garcia, S. G. Influence of alloying elements and

microstructure on aluminum sacrificial anode. J. Appl. Electrochem. 29, 1063–1071
(1999).
2. Ma, L., Li, K., Yan, Y. & Hou, B. Low Driving Voltage Aluminum Alloy Anode for
Cathodic Protection of High Strength Steel. Multi-Functional Mater. Struct. Ii, Pts 1
2 79–82, 1047–1050 (2009).
3. Batt, C., Dodson, J. & Robinson, M. J. Hydrogen embrittlement of cathodically
protected high strength steel in sea water and seabed sediment. Br. Corros. J. 37,
194–198 (2002).
4. Monzel, William (Jacob); Druschitz, Alan P.; Maxfield, M. Development of New,
Low-Voltage, Aluminum, Sacrificial Anode Chemistries. in Corrosion 4284 (2014).
5. Lemieux, E. J., Hogan, E. A., Lucas, K. E. & Grolleau, A. M. Performance
Evaluation of Low Voltage Anodes for Cathodic Protection. CORROSION 2002 11
(2002).
6. Ma L, Li K, Yan Y, et al. Development of Low Driving Voltage Sacrificial Anode.
in NACE East Asia & Pacific Rim Area Conference & Expo 2012 Paper No.12060
(NACE International, 2012).
7. Pautasso, J.-P., Le Guyader, H. & Debout, V. Low Voltage Cathodic Protection for
High Strength Steels: Part 1- Definition of a New Aluminum Galvanic Anode
Material. CORROSION 98 27 (1998).
8. Gurrappa, I. Cathodic protection of cooling water systems and selection of
appropriate materials. J. Mater. Process. Technol. 166, 256–267 (2005).
9. Murai Tosuke, Miura Shutoshi; Tamura Yuichi. Study on aluminum galvanic anode
(1st report) page 191–195 (1974).
10. Muazu, A. & Yaro, S. . Effects of Zinc Addition on the Performance of Aluminium
as Sacrificial Anode in Seawater. J. Miner. Mater. Charact. Eng. 10, 185–198
(2011).
11. Zeng, F. L. et al. Corrosion mechanism associated with Mg2Si and Si particles in Al-
Mg-Si alloys. Trans. Nonferrous Met. Soc. China (English Ed. 21, 2559–2567
(2011).
12. Schnatterer, C. & Zander, D. Influence of the grain boundary chemistry on the
intergranular corrosion mechanisms of a high-strength Al-Mg-Si alloy. Surf.
Interface Anal. 48, 750–754 (2016).
13. Ferdian, D., Pratesa, Y., Togina, I. & Adelia, I. Development of Al-Zn-Cu Alloy for
Low Voltage Aluminum Sacrificial Anode. Procedia Eng. 184, 418–422 (2017).
14. Pratesa, Y., Ferdian, D. & Togina, I. Effect of Copper and Silicon on Al-5%Zn Alloy
as a Candidate Low Voltage Sacrificial Anode. in IOP Conference Series: Materials
Science and Engineering 204, (2017).
15. Muñoz, A. G., Saidman, S. B. & Bessone, J. B. Corrosion of an Al–Zn–In alloy in
chloride media. Corros. Sci. 44, 2171–2182 (2002).
16. Aziz, P. M. & Godard, H. P. Pitting Corrosion Characteristics of Aluminum -
Influence of Magnesium and Manganese. Ind. Eng. Chem. 44, 1791–1795 (1952).
17. Ferdian, D. Effet de la vitesse de refroidissement sur la taille des grains, la
modification eutectique et la précipitation d’intermétalliques riches en fer dans des
alliages Al-Si hypoeutectiques. (2014).
18. Barbucci, A., Cerisola, G., Bruzzone, G. & Saccone, A. Activation of aluminium
anodes by the presence of intermetallic compounds. Electrochim. Acta 42, 2369–
2380 (1997).
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IC-DAEM 2018 IOP Publishing
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19. Yoshikawa, D. S., Terada, M., Assis, S. L., Costa, I. & Padilha, A. F. Correlation
between microstructure and corrosion behavior of two Al–Fe–Si alloys. Mater.
Corros. 67, 286–296 (2015).