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Electrochemical study of corrosion in

aluminium cans in contact with soft drinks


L. Esteves1, E. M. Garcia2, M. das M. R. Castro1 and V. F. C. Lins*1
This work evaluates the corrosion resistance of the inner surface of the aluminium cans in
guarana, cola flavoured and tonic water soft drinks using electrochemical impedance spectroscopy (EIS) measurements. The less aggressive electrolyte was tonic water. One time constant
was identified for the aluminium can in contact with guarana and tonic water. In the most
aggressive medium of cola flavoured soft drinks, two time constants were identified and a charge
transfer resistance was obtained associated to a corrosion of aluminium in contact with the
electrolyte.
Keywords: Packaging, Aluminium, Soft drinks, Corrosion, Electrochemical impedance spectroscopy (EIS)

Introduction
The various sectors of beverage packaging have brought
many technological developments, aiming to increase
the packing properties, to reach the requirements for
protection of drinking and the conquest of markets and
consumer preference.
The metal, plastic and glass containers are progressively lighter. The cans exhibit different formats or
reliefs, opening systems, and internal protection. The
plastic containers have shown significant improvements
in barrier properties aimed primarily at meeting the
requirements of the protection of the beer. The glass
containers have shown greater mechanical resistance
caused by a greater control of the thickness distribution,
have received external coatings for the protection and
improvement of performance in relation to the breakdown and introduction of new colours. Initially, the
containers for storing carbonated beverages were made
of glass. The beer and the soft drink markets have been
modified by the introduction of PET (polyethylene
terephthalate), tinplated steel and aluminium cans.
The corrosion process in metal packaging exhibits an
electrochemical mechanism. The electrochemical techniques for corrosion resistance evaluation are relatively
rapid, reproducible, reliable, and provide information
about the corrosion mechanism involved.
The inner lacquer coating is the most widely used
method for reducing metal can corrosion.1 Several papers
about the corrosion process of steel and tinplate cans in
contact with beverages and various types of food are
found in literature.110 Pournaras et al.10 detected flaws in
the organic coating layer using electrochemical impedance spectroscopy analysis, which were not identified
neither with the naked eye or using microscopic analysis.

Federal University of Minas Gerais, Antonio Carlos Avenue 6627, 13565905, Brazil
Federal University of Sao Joao Del Rey, Brazil

*Corresponding author, email vlins@deq.ufmg.br

2014 Institute of Materials, Minerals and Mining


Published by Maney on behalf of the Institute
Received 8 February 2014; accepted 29 May 2014
DOI 10.1179/1743278214Y.0000000197

Detection of corrosion induced metal release from


tinplate cans has also been done using EIS, electrochemical noise (EN), and inductively coupled plasma mass
spectrometer.2 According to our knowledge, EIS data of
aluminium cans in soft drinks electrolytes are not found
in literature. A study of evaluation of aluminium content
in beers was found in literature.11
The selected beverages were guarana, cola based and
tonic water that are widely consumed soft drinks in
Brazil. Cola flavoured soft drinks contain carbonated
water, sugar, caffeine, extract of the cola nut, caramel
colouring, acidulant (phosphoric acid) and natural
flavouring compounds.12 Guarana soda should mandatorily contain a minimum of two hundredths of a gram
of guarana seed (Paullinia gender), or its equivalent in
extract, per hundred millilitres of beverage. The
therapeutic properties of guarana and its extracts have
been attributed to guaranine, which is a complex of
caffeine and tannins or to a new xanthine natural
product.13 Quinine tonic water must contain three to five
milligrams of quinine or its salts, expressed in anhydrous
quinine per hundred millilitres of beverage.14,15 Tonic
water contains carbonated water, liquid sugar, extract of
quinine, natural aroma, conservatives and acidulants.
Thus, this paper has academic and technological
relevance, contributing to the elucidation of the mechanisms of corrosion of the inner surface of aluminium cans
in the midst of carbonated beverages using the electrochemical impedance spectroscopy technique.

Experimental
The CaboQC carbonation measuring equipment, coupled
with the DMA 45 000 Anton Paar was used to measure
the content of carbon dioxide and Brix degree. The DM32 Digimed conductivity measurement equipment and a
Digimed pH meter Model DM-22 were used to measure
the conductivity and the pH of the beverage.
Electrochemical measurements were performed using
an AUTOLAB PGSTAT 302 with an impedance
module, FRA and GPES software. The working

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Esteves et al.

Electrochemical study of aluminium can corrosion

electrode used was a can of aluminium in a square


5?065?0 cm form. An electrochemical cell with a nozzle
size of the area being examined of 2?2 cm2 was used.
Measurements were made in triplicate, analysing different regions of the same can. This cell is pressed against a
sheet of aluminium can to avoid the appearance of
crevices. The portion of the work electrode that was in
electric contact with the potentiostat was polished with
sandpaper number 600 and washed with distilled water
before each experiment. The counter electrode was made
of platinum, with area equal to 3?75 cm2, and the
reference electrode was Ag/AgCl. All experiments were
performed without agitation of the electrolyte at a room
temperature. The electrolytes used were guarana, cola
and tonic water soft drinks. The following parameters
were selected after initial experiments for optimisation of
experimental conditions: measurements with 200 points,
the frequency range of 1 MHz to 50 mHz. The immersion
time of the aluminium can in the electrolyte was 20 days.
The open circuit potential (OCP) was monitored for 1 h
or up to stabilisation. Nine replicates of each test were
performed, and the mean resistance value was calculated.

Results and discussion


Characterisation of electrolytes
Table 1 shows the results of Brix degree, pH, conductivity and CO2 content of the soft drinks studied. Cola
flavoured soft drinks had the lowest pH and the highest
values of conductivity, Brix degree and CO2 content
among the electrolytes.

Open circuit potential measurement


Figure 1 shows the measurement of the open circuit
potential versus time for tonic water beverages. The
open circuit potential remained approximately constant
or increased and then decreased as the time increased. In
the last behaviour, a corrosion product layer was
produced and then dissolved as the immersion time
increased. Table 2 shows the average values of corrosion
potential of aluminium cans in the soft drinks studied.
The highest corrosion potential of aluminium cans was
observed for the tonic water beverage, highlighting the
noblest behaviour of aluminium in tonic water. The
lowest corrosion potential was observed for aluminium
in cola flavoured soft drinks.
Measurements were performed with in-nature samples, without removal of CO2 to try to reproduce the
service life of the product. The CO2 can be degas during
the experiment and can be replaced by O2, accelerating
corrosion by contributing to the cathodic reaction of
oxygen reduction in acidic media.

Electrochemical impedance spectroscopy study


Optimisation

EIS studies of can electrodes were conducted initially


using a frequency range of 50 mHz to 104 Hz with
amplitude of 10 mV. Data dispersion was observed for

1 Open circuit potential (OCP) of can electrodes versus


time in tonic water beverage

the low frequency region of 50 mHz. Using potential


amplitude of 50 mV, the dispersion of data was reduced
as shown in Fig. 2. Comparing values of impedance
using potential amplitude of 10 and 50 mV at low
frequency region similarity was observed, which indicated that the electrochemical impedance spectra meets
the condition of linearity. On the other hand, Kramers
Kronig transforms could have been used for impedance
data validation because the K-K relation links the real
and imaginary parts of the impedance.16 The amounts of
points were also increased from 100 to 200 points per
frequency decade to improve definition of diagrams.

Model development
The EIS data were fitted to different equivalent
electrochemical circuits. Tables 35 show the EIS results
for one replicate of the aluminium cans in contact with
tonic water, cola flavoured soft drinks, and guarana soft
drinks, respectively. A pure capacitor was used if n51
and a constant phase element was utilised if n would be
less than one. Nyquist and Bode diagrams of aluminium
cans in tonic water are shown in Fig. 3a and b. Bode
diagram (Fig. 3b) indicates the presence of one time
constant. Figure 4 shows the equivalent circuit proposed, considering that in some testing the constant
phase element could be replaced by a capacitor. In this
less aggressive electrolyte, the resistance R2 is associated
to the ionic resistance through the polymer coating
impregnated with the electrolyte.17 The phase angle
associated with the maximum peak is close to 90u,
indicating the capacitive character of the process.
Another equivalent electrochemical circuit possible
showed two time constants (Fig. 5) for the corrosion of
aluminium cans in cola flavoured soft drinks. The
Nyquist diagram is shown in Fig. 6a and the Bode
Diagrams (Fig. 6b) is shown in Fig. 6b. R2 is the ionic
resistance through the polymeric coating and R3 is the

Table 1 Physicochemical parameters of soft drinks

666

Soft drinks

Brix/uBx

Content of CO2

pH

Conductivity/mS

Cola flavoured
Guarana
Tonic water

10.750.20
10.000.20
7.600.20

3.60.2
3.10.2
3.30.2

2.500.1
3.100.2
2.800.2

1048.9
439.3
831.1

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2 Nyquist diagram using frequency range of 50 mHz


104 Hz with potential amplitude of 10 and 50 mV in
guarana beverage

charge transfer resistance of aluminium in contact with


the electrolyte due to defects in polymeric coating and
pores of aluminium oxide. Flaws in the organic layer
and in the oxide aligned and in the same position, expose
the aluminium to the solution. The cathodic reactions
are the hydrogen reduction and the oxygen reduction in
acidic media generating water as the carbon dioxide is
substituted by oxygen in solution during the analysis.
A diffusive control of the corrosive process was not
observed. The degassing of the solution during the
experiment can contribute to agitate the medium and
minimise the diffusive control.

Table 2 Average values of electrolyte resistance, and


corrosion potential and polarisation resistance of
aluminium cans in soft drinks

Soft drinks

Corrosion potential
of aluminium
Polarisation resistance
can mV(Ag/AgCl) of aluminium can/kV cm2

Cola flavoured 268354


Guarana
255543
Tonic water
249329

1349
8070564
18 9001134

Table 3 EIS parameters obtained for aluminium cans in


tonic water
Parameter

Value

% Error

R1/V cm2
CPE1-T/F sn cm22
CPE1-P (n)
R2/V cm2
x2

2460
1.0661028
0.92
1.046108
261023

1.43
0.37
0.06
0.64

Table 4 EIS parameters obtained for aluminium cans in


cola avoured soft drinks
Parameter

Value

% Error

R1/V cm2
C (F cm22)
R2 (V cm2)
R3 (V cm2)
CPE2-T/F sn cm22
CPE2-P (n)
x2

2172
3.8961029
16 594
6.086106
1.5261028
0.89
1.0061023

2.05
1.17
2.23
0.34
0.96
0.17

3 Electrochemical impedance spectra: a Nyquist diagram


and b Bode diagram using frequency range of 50 mHz
104 Hz with potential amplitude of 50 mV in tonic water
electrolyte

In measurements in SEM/EDS the aluminium concentration decreases and the carbon concentration
increases near the can surface.18 On the inner surface
of this aluminium can there is a polymeric layer of
y3 mm.18
Table 2 shows the mean values of polarization
resistance of aluminium cans in contact with guarana
and cola based soft drinks, and in tonic water. The
aluminium cans in cola flavoured soft drinks showed the
lowest corrosion potential and the lowest polarisation
resistance. The aluminium cans exhibited the highest
corrosion resistance in the medium of tonic water.
In its composition, cola carbonated beverages have
phosphoric acid as the acidulant and therefore has the
lowest pH value (2?50) among other soft drinks studied
as shown in Table 1, and also have the highest
conductivity (1048?0 mS), a higher level of dissolved
CO2 (3?60?2) and a higher soluble solid content Brix
Table 5 EIS obtained for aluminium cans in guarana soft
drinks
Parameter

Value

% Error

R1/V cm2
CPE1-T/F sn cm22
CPE1-P (n)
R2/V cm2
x2

4628
2.6261028
0.86
8.206106
9.1023

5.12
1.33
0.24
0.99

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The electrochemical impedance spectroscopy is proposed as an efficient method of the quality evaluation of
the polymer coated aluminium cans.

4 Equivalent circuit proposed for corrosion of aluminium


cans in tonic water

5 Equivalent circuit proposed for aluminium can in cola


avoured soft drinks

Conclusions
The technique of electrochemical impedance spectroscopy was able to distinguish the efficiency of organic
coating applied to the aluminium can, with regard to the
barrier property of the coating, and to distinguish the
aggressiveness among the soft drinks. EIS results showed
the conditions of linearity, causality and stability in the
beverage electrolytes.
The less aggressive electrolyte was tonic water. One
time constant is observed for the aluminium in tonic
water and guarana beverage. In the most aggressive
medium of cola based soft drinks, two time constants
were identified and in the equivalent circuit proposed to
fit results, a charge transfer resistance is associated with
the Al/electrolyte interface.

Acknowledgements
The authors are grateful to the Brazilian government
agencies CNPQ, CAPES and FAPEMIG and Dr John
di Fiore for revision of the manuscript.

References

6 a Nyquist diagram and b Bode diagram of aluminium


cans in cola based beverages

(10?750?20uBx), therefore the highest aggressiveness of


the cola-flavoured soft drinks is justified. Tonic water is
composed of herbal extract of quinine and exhibits a
lower level of Brix grade (7?600?20uBx), showing the
lowest aggressiveness among the beverages studied.
Aluminium cans in tonic water showed the highest
corrosion potential and the highest polarisation resistance.

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