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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
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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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
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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Soft drinks
Corrosion potential
of aluminium
Polarisation resistance
can mV(Ag/AgCl) of aluminium can/kV cm2
1349
8070564
18 9001134
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
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
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.
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
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