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ORIGINAL ARTICLE

Corrosion behaviour of 6063 aluminium alloy in acidic


and in alkaline media
Deepa Prabhu, Padmalatha Rao
*
Department of Chemistry, Manipal Institute of Technology, Manipal University, 576104 Karnataka, India
Received 21 November 2012; accepted 28 July 2013
KEYWORDS
Corrosion;
6063 aluminium alloy;
Phosphoric acid;
Sodium hydroxide;
Tafel polarization;
EIS
Abstract The corrosion behaviour of 6063 aluminium alloy was investigated in different concen-
trations of phosphoric acid medium and sodium hydroxide medium at different temperatures. The
study was done by electrochemical method, using Tafel polarization technique and electrochemical
impedance spectroscopy (EIS) technique. The surface morphology was investigated using scanning
electron microscope (SEM) with Energy-dispersive X-ray spectroscopy (EDX). The results showed
that the 6063 aluminium alloy undergoes severe corrosion in sodium hydroxide medium than in
phosphoric acid medium. The corrosion rate of 6063 aluminium alloy increased with an increase
in the concentration of acid as well as with alkali. The corrosion rate was increased with an increase
in temperature. The kinetic parameters and thermodynamic parameters were calculated using
Arrhenius theory and transition state theory. Suitable mechanism was proposed for the corrosion
of 6063 aluminium alloy in phosphoric acid medium and sodium hydroxide medium. The results
obtained by Tafel polarization and electrochemical impedance spectroscopy (EIS) techniques were
in good agreement with each other.
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1. Introduction
Corrosion, which is an inevitable problem faced by almost all
industries can be considered as one of the worst technical
calamities of our time. Besides from its direct costs in dollars,
corrosion is a serious problem because it denitely contributes
to the depletion of our natural resources. Corrosion studies
have also become important due to increasing awareness of
the need to conserve the worlds metal resources (Stansbury
and Buchanan, 2000). Now-a-days more attention has been
paid to control the metallic corrosion, due to increasing use
of metals in all elds of technology.
Corrosion studies of aluminium and aluminium alloys have
received considerable attention by researchers because of their
wide industrial applications and economic considerations
(Christian Vargel, 2004; Kosting and Heins, 1931; Badaway
et al., 1999; Paul and Sigwalt Juniere, 1964). Aluminium and
aluminium alloys have emerged as alternate materials in aero-
space and in some chemical processing industries. Due to their
wide applications, they frequently come in contact with acids
or bases during pickling, de-scaling, electrochemical etching
*
Corresponding author. Tel.: +91 9880122680.
E-mail addresses: padmalatha.rao@manipal.edu, drpadmalatharao@
yahoo.com (R. Padmalatha).
Peer review under responsibility of King Saud University.
Production and hosting by Elsevier
Arabian Journal of Chemistry (2014) xxx, xxxxxx
King Saud University
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www.ksu.edu.sa
www.sciencedirect.com
1878-5352 2014 Production and hosting by Elsevier B.V. on behalf of King Saud University.
http://dx.doi.org/10.1016/j.arabjc.2013.07.059
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
and extensively used in many chemical process industries.
Most of the reported studies were conducted on corrosion of
various metals and alloys in HCl and H
2
SO
4
media (Paul
and Sigwalt Juniere, 1964; Ating et al., 2010; Umoren et al.,
2009; Obi-Egbedi et al., 2012; Nnanna et al., 2011).
Phosphoric acid medium is widely used for acid cleaning
and elector polishing of aluminium (Christian Vargel, 2004).
Even though dissolution rate of aluminium in phosphoric acid
medium is lower, compared to the dissolution of the same in
hydrochloric medium or sulphuric acid medium, it does cor-
rode aluminium and its alloys. Phosphoric acid medium is also
used in pickling delicate, costly components and precision
items where rerusting after pickling has to be avoided. Sodium
hydroxide is usually used for degreasing purpose. According to
the available literature, not much study has been done
regarding the corrosion behaviour of 6063 aluminium alloy
in phosphoric acid medium as well as with sodium hydroxide
medium. As part of our studies with corrosion behaviour of
aluminium and aluminium alloys in phosphoric acid medium
and sodium hydroxide medium and corrosion control of
the same using green inhibitors (Deepa and Padmalatha,
2013a,b) we report herein the results of corrosion behaviour
of 6063 aluminium alloy in phosphoric acid medium and
sodium hydroxide medium of different concentrations at
different temperatures.
2. Methods
2.1. Material
The experiments were performed with specimens of 6063 alu-
minium alloy. The composition of the 6063 aluminium alloy
specimen is given in Table 1.
Cylindrical test specimens were sealed with Acrylic resin
material in such a way that the area exposed to the medium
was 1.0 cm
2
. It was polished with 180, 280, 400, 600, 800,
1000, 1500, and 2000 grade emery papers. Further polishing
was done with disc polisher using levigated alumina to get
mirror surface. It was then dried and stored in a desiccator
to avoid moisture before using it for corrosion studies.
2.2. Medium
A stock solution of phosphoric acid medium was prepared
using analytical grade phosphoric acid medium (85%) and
double distilled water. It was standardized by potentiometric
method. Phosphoric acid medium of concentrations 1.0 M,
0.1 M and 0.01 M was prepared by appropriate dilution. A
stock solution of sodium hydroxide was prepared by dissolving
analytical grade sodium hydroxide pellets in double distilled
water and standardized by volumetric method using phenol-
phthalein indicator. Solutions of required strengths 0.05 M,
0.25 M and 0.5 M were prepared by appropriate dilutions as
and when required. Experiments were carried out using a
calibrated thermostat at temperatures 30 C, 35 C, 40 C,
45 C and 50 C (0.5 C).
2.3. Electrochemical measurements
Electrochemical measurements were carried out by using an
electrochemical work station, CH600D-series, U.S. Model
with CH instrument beta software. The electrochemical cell
used was a conventional three-electrode compartment having
glass cell with a platinum counter electrode and a saturated
calomel electrode (SCE) as reference. The working electrode
was made up of 6063 aluminium. All the values of potential
were measured with reference to the saturated calomel elec-
trode. The polarization studies were done immediately after
the EIS studies on the same electrode without any further sur-
face treatment.
2.3.1. Tafel polarization studies
Finely polished 6063 alloy specimens with 1.0 cm
2
surface area
were exposed to corrosion medium of different concentrations
of phosphoric acid (0.01 M, 0.1 M and 1.0 M) and different
concentrations of sodium hydroxide (0.05 M, 0.25 M and
0.5 M) separately at a temperature range of 303323 K.
The potentiodynamic currentpotential curves were recorded
by polarizing the specimen to 250 mV cathodically
and + 250 mV anodically with respect to open circuit poten-
tial (OCP) at a scan rate of 0.01 V/s.
2.3.2. Electrochemical impedance spectroscopy (EIS) studies
Electrochemical impedance spectroscopy (EIS) measurements
were carried out using a small amplitude ac signal of 10 mV
over a frequency range of 100 kHz0.01 Hz.
Both techniques were repeated at least three times. The
average value of best three agreeing values was reported.
-7 -6 -5 -4 -3 -2
-1.1
-1.0
-0.9
-0.8
-0.7
-0.6
-0.5
E
(
V
/
S
C
E
)
log i (Acm
-2
)
0.01M
0.1M
1.0M
Figure 1 Tafel polarization curves for 6063 aluminium alloy in
different concentrations of H
3
PO
4
at 30 C.
Table 1 Composition of the 6063 aluminium alloy specimen
(% by weight).
Element Composition (%)
Si 0.412
Fe 0.118
Cu 0.0570
Mg 0.492
Al Balance
2 P. Deepa, R. Padmalatha
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
2.4. Scanning electron microscopy (SEM) and Energy-
dispersive X-ray spectroscopy (EDX) studies
The scanning electron microscope images were recorded to
establish the interaction of acid medium and alkaline medium
with the metal surface using EVO 18-15-57 scanning electron
microscope with Energy-dispersive X-ray spectroscopy. The
surface morphology of 6063 aluminium alloy immersed in
phosphoric acid medium and sodium hydroxide medium was
compared with that of polished metal sample.
3. Results and discussion
3.1. Tafel polarization measurements
The effect of phosphoric acid medium and sodium hydroxide
medium on the corrosion rate of 6063 aluminium alloy sample
was studied using Tafel polarization technique. Figs. 1 and 2
represent the potentiodynamic polarization curves of 6063
aluminium alloy in different concentrations of phosphoric acid
medium at 30 C and in different concentrations of sodium
hydroxide medium at 30 C respectively. Corrosion parameters
such as corrosion potential (E
corr
), corrosion current density
(i
corr
), anodic slope (b
a
) and cathodic slope (b
c
) are obtained
from the Tafel polarization curves. Results are tabulated in
Tables 2 and 3. The corrosion rate was calculated using Eq. (1).
t
corr
mmy
1

3270 M i
corr
q Z
; 1
where 3270 is a constant that denes the unit of corrosion rate,
i
corr
is the corrosion current density in A cm
2
, q is the density
of the corroding material (g cm
3
), M is the atomic mass of the
metal, and Z is the number of electrons transferred per atom
(Fontana, 1987). The results of Tafel polarization measure-
ments are reported in Tables 2 and 3 respectively.
The results indicate the increase in the corrosion rate (t
corr
)
with an increase in the concentration of phosphoric acid med-
ium and sodium hydroxide medium. The positive shift in the
corrosion potential (E
corr
) with the increase in the concentra-
tion of phosphoric acid medium and sodium hydroxide med-
ium indicates that the anodic process is much more affected
than the cathodic process (El-Sayed, 1997). This observation
is in accordance with Muralidharan (Muralidharan and Rajag-
opalan, 1979), who proposed dependence of E
corr
and i
corr
on
solution parameters. Tafel slopes remained almost unchanged
indicating that acid strength does not change the mechanism of
the corrosion process. It is evident from data of Tables 2 and 3
that corrosion rate is more in case of sodium hydroxide med-
ium than in phosphoric acid medium.
3.2. Electrochemical impedance spectroscopy (EIS)
measurements
The corrosion behaviour of 6063 aluminium alloy specimens
was also investigated by EIS techniques in various concentra-
tions of phosphoric acid medium and sodium hydroxide
medium. The impedance spectra were recorded and displayed
-6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5
-1.9
-1.8
-1.7
-1.6
-1.5
-1.4
-1.3
E

(
V
/
S
C
E
)
log i (A cm
-2
)
0.05M
0.25M
0.5M
Figure 2 Tafel polarization curves for 6063 aluminium alloy in
different concentrations of NaOH at 30 C.
Table 2 Results of Tafel polarization studies and EIS studies of 6063 aluminium alloy in H
3
PO
4
.
Tafel polarization EIS
H
3
PO
4
(M) T (K) E
corr
(V vs. SCE) i
corr
(10
5
A cm
2
) b
a
(V dec
1
) b
c
(V dec
1
) t
corr
(mm y
1
) R
p
(X cm
2
) CPE (l Fcm
2
)
0.01 303 0.72 2.99 3.73 5.40 0.32 1922.6 45
308 0.73 3.39 3.56 5.76 0.36 1767.8 57
313 0.74 3.42 3.50 6.04 0.37 1512.1 63
318 0.77 3.76 3.69 5.97 0.40 1324.8 74
323 0.78 4.29 3.78 5.94 0.46 993.5 83
0.1 303 0.79 10.8 3.67 6.57 1.17 407.3 58
308 0.80 12.8 3.70 6.46 1.39 339.5 65
313 0.81 16.3 3.74 6.01 1.77 280.2 77
318 0.82 18.1 4.07 5.32 1.97 234.5 86
323 0.83 24.5 4.14 5.71 2.67 172.7 98
1.0 303 0.76 38.6 3.34 6.72 4.20 101.70 69
308 0.77 50.5 3.43 6.58 5.50 75.90 78
313 0.78 69.2 3.50 6.43 7.54 54.00 90
318 0.80 96.0 3.69 5.97 10.46 36.80 117
323 0.81 135.4 3.79 5.60 14.75 24.20 129
Corrosion behaviour of 6063 aluminium alloy 3
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
as Nyquist plots as a function of acid strength. Nyquist
plots for different concentrations of phosphoric acid medium
and sodium hydroxide medium at 30 C are shown in Figs. 3
and 4 respectively. The EIS results are reported in Tables 2
and 3.
As can be seen from Figs. 3 and 4, the impedance diagrams
show semicircles, indicating that the corrosion process is
mainly charge transfer controlled (Wit and Lenderink, 1996;
Lenderink et al., 1993).The depressed semicircles of the Ny-
quist plots suggest the distribution of capacitance due to inho-
mogeneous surface associated with the metal surface (Morad,
1999). The shapes of the curves are identical and it consists of a
large capacitive loop at higher frequencies (HF), inductive
loop at intermediate frequencies (IF), followed by a second
capacitive loop at lower frequency (LF) values (Brett, 1990).
Similar impedance plots have been reported in the literature
for the corrosion of aluminium and aluminium alloys in
various electrolytes such as, sodium sulphate (Brett, 1992),
sulphuric acid (Poornima et al., 2010), and sodium hydroxide
(Shao et al., 2003; Abdel-Gaber et al., 2008; Reena Kumari
et al., 2012). The HF capacitive loop is attributed to the
presence of a protective oxide lm covering the surface of
the metal. According to Brett (Brett, 1992), the capacitive loop
is corresponding to the interfacial reactions, particularly, the
reaction of aluminium oxidation at the metal/oxide/electrolyte
interface. The process includes the formation of Al
+
ions at
the metal/oxide interface, and their migration through the
oxide/solution interface where they are oxidized to Al
3+
. At
the oxide/solution interface, OH

or O
2
ions are also formed.
The fact that all the three processes are represented by only
one loop could be attributed either to the overlapping of the
loops of processes, or to the assumption that one process dom-
inates and, therefore, excludes the other processes (Morad,
1999). The other explanation offered to the high frequency
capacitive loop is the oxide lm itself. The origin of the
0 200 400 600 800 1000 1200
0
200
400
600
800
1000
1200
-
Z
I
I

(
o
h
m

c
m
2
)
Z
l
(ohm cm
2
)
0.01M
0.1M
1.0M
Figure 3 Nyquist plot for 6063 aluminium alloy in different
concentrations of H
3
PO
4
at 30 C.
0 2 4 6 8 10 12 14 16
0
2
4
6
8
10
12
14
16
-
Z
"

(
o
h
m

c
m
2
)
Z' (ohm cm
2
)
0.05M
0.25M
0.5M
Figure 4 Nyquist plot for 6063 aluminium alloy in different
concentrations of NaOH at 30 C.
Table 3 Results of Tafel polarization studies and EIS studies of 6063 aluminium alloy in NaOH.
Tafel polarization EIS
NaOH (M) T (K) E
corr
(V vs. SCE) i
corr
(10
5
A cm
2
) b
a
(V dec
1
) b
c
(V dec
1
) t
corr
(mm y
1
) R
p
(X cm
2
) CPE (l F cm
2
)
0.05 303 1.55 40.4 4.84 4.86 4.40 101.8 66
308 1.56 46.9 4.87 4.83 5.11 82.5 72
313 1.57 52.6 5.21 5.31 5.73 80.2 75
318 1.58 57.2 4.83 5.33 6.23 77.3 79
323 1.59 59.8 4.45 5.44 6.51 75.6 85
0.25 303 1.57 209 5.04 4.84 22.78 24.9 76
308 1.59 244 4.90 4.92 26.59 18.3 84
313 1.60 281 5.11 4.47 30.62 17.3 96
318 1.61 307 4.80 4.70 33.46 15.0 107
323 1.62 331 4.93 4.73 36.07 14.4 114
0.5 303 1.59 326 4.92 4.71 35.53 12.2 83
308 1.60 374 4.92 4.91 40.76 11.5 95
313 1.61 424 5.03 4.88 46.21 9.9 101
318 1.62 437 4.67 4.84 47.63 9.7 111
323 1.63 455 4.92 4.96 49.59 8.3 123
4 P. Deepa, R. Padmalatha
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
inductive loop has often been attributed to the surface or bulk
relaxation of species in the oxide layer (Morad, 1999). The LF
inductive loop may be related to the relaxation process ob-
tained by adsorption and incorporation of phosphate ions
and hydroxide ions into the oxide lm (Lorenz and Mansfeld,
1981).
An equivalent circuit of nine elements depicted in Fig. 5a
was used to simulate the measured impedance data of the
6063 aluminium alloy, as shown in Fig. 5b. In this equivalent
circuit, R
s
is the solution resistance and R
t
is the charge trans-
fer resistance. R
L
and L represent the inductive elements. This
also consists of constant phase element; CPE (Q) in parallel to
the series capacitors C
1
and C
2
and series resistors R
1
, R
2
, R
L
and R
t
. R
L
is parallel with the inductor L. The polarization
resistance R
p
and double layer capacitance C
dl
are calculated
from Eqs. (2) and (3):
R
p
R
L
R
t
R
1
R
2
; 2
C
dl
C
1
C
2
: 3
The measured value of polarization resistance decreased
with increase while the CPE value increased with increasing
concentration of the phosphoric acid medium and sodium
hydroxide medium, indicating that the rate of corrosion in-
creased with increasing concentration of the phosphoric acid
medium and sodium hydroxide medium. This is in agreement
with the results obtained from potentiodynamic polarization
data.
3.3. Effect of temperature
The effect of temperature on the corrosion rate of the 6063 al-
loy was studied by measuring the corrosion rate at the temper-
ature range of 303323 K. Figs. 6 and 7 represent the
potentiodynamic polarization curves of 6063 aluminium alloy
in 1.0 M phosphoric acid medium and 0.5 M sodium hydride
medium at temperature range of 303323 K. Figs. 8 and 9
represent Nyquist plots for the same. From both gures it is
Figure 5 Equivalent circuit t for 6063 Al alloy in 1.0 M H
3
PO
4
at 30 C.
-6.5 -6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5
-1.1
-1.0
-0.9
-0.8
-0.7
-0.6
-0.5
E
(
V
/
S
C
E
)
log i(Acm
-2
)
30
o
C
35
o
C
40
o
C
45
o
C
50
o
C
Figure 6 Tafel polarization curves for 6063 aluminium alloy at
different temperatures in 1 M H
3
PO
4
.
-5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5
-1.9
-1.8
-1.7
-1.6
-1.5
-1.4
-1.3
E

(
V
/
S
C
E
)
log i (A cm
-2
)
30
o
C
35
o
C
40
o
C
45
o
C
50
o
C
Figure 7 Tafel polarization curves for 6063 aluminium at
different temperatures in 0.5 M NaOH.
Corrosion behaviour of 6063 aluminium alloy 5
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
obvious that the corrosion rate increased with an increase in
temperature. This results in the rapid dissolution of the oxide
lm, thereby enhancing the corrosion rate. This is attributable
to the enhanced chemical lm dissolution due to enriched
phosphate ions, OH

ions and depleted AlOH

4
ions at the
lm/solution interface. Thus with the increasing temperature
the oxide passive lm becomes thin, porous and less protective
as a result of dissolution of the lm by the electrolyte (Foley
and Nguyen, 1982).
The energy of activation of corrosion of 6063 aluminium
alloy was calculated from Arrhenius Eq. (4). The Arrhenius
plot (lnCR vs. 1/T) at all the concentrations of phosphoric
acid medium and sodium hydroxide medium is represented
in Figs. 10 and 11.
lnt
corr
B
E
a
RT
; 4
where B is a constant, R is the universal gas constant, and T is
the absolute temperature.
Enthalpy of activation (DH
a
) and entropy of activation
(DS
a
) were calculated from the transition state theory Eq. (5),
t
corr

RT
Nh
exp
DS
a
R

exp
DH
a
RT

5
where h is Planks constant and N is Avagadros number.
A plot of ln(t
corr
/T) vs 1/T gives a straight line with
slope = DH
a
/T and intercept = ln(R/Nh) +DS
a
/R. The
plots of ln(t
corr
/T) vs. 1/T for the corrosion of 6063 aluminium
alloy in the presence of different concentrations of phosphoric
acid medium and sodium hydroxide medium are shown in
Figs. 12 and 13.
The values of energies of activation, enthalpy of activation
and entropy of activation are listed in Tables 4 and 5.
As indicated in Table 4, except for 0.01 M phosphoric acid
medium, value of energy of activation is greater than
20 kJ mol
1
.
This suggested that at higher strengths of acid, the whole
process is controlled by surface reaction (El-Neami et al.,
1995). This phenomenon may be due to the fact that the
activation energy for the corrosion reaction is independent of
concentration polarization (Oguzie, 2007) and mainly due to
activation polarization. However, in case of sodium hydroxide
medium, energy of activation at all studied concentrations
was less than 20 kJ mol
1
and E
a
decreased with an
increase in sodium hydroxide medium concentration, which
is suggestive of concentration polarization as a main reaction
at electrodeelectrolyte interface.
The entropy of activation is large and negative. This implies
that the activated complex in the rate determining step repre-
sents association rather than dissociation, indicating that a de-
crease in disorder takes place, in going from reactant to the
activated complex (Trowsdale et al., 1996). The value of DS
a
decreased with an increase in acid concentration reveals that
dissolution of alloy is facilitated as the concentration of the
acid medium increases.
0 20 40 60 80 100 120
0
20
40
60
80
100
120
-
Z
I
I

(
o
h
m

c
m
2
)
Z
I
(ohm cm
2
)
30
o
C
35
o
C
40
o
C
45
o
C
50
o
C
Figure 8 Nyquist plots for the corrosion of 6063 aluminium
alloy at different temperatures in 1.0 M H
3
PO
4
.
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Z' (ohm cm
2
)
-
Z
"

(
o
h
m

c
m
2
)
30
o
C
35
o
C
40
o
C
45
o
C
50
o
C
Figure 9 Nyquist plots for the corrosion of 6063 aluminium
alloy at different temperatures in 0.5 M NaOH.
3.1x10
-3
3.1x10
-3
3.2x10
-3
3.2x10
-3
3.3x10
-3
3.3x10
-3
3.4
3.6
3.8
4.0
4.2
4.4
4.6
4.8
5.0
5.2
5.4
5.6
l
n
(
C
R
)

(
m
m

y
-
1
)
1/T (K
-1
)
0.01M
0.05M
0.1M
Figure 10 Arrhenius plots for the corrosion of 6063 aluminium
alloy in H
3
PO
4
.
6 P. Deepa, R. Padmalatha
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
3.4. Scanning electron microscopic study
The SEM images of freshly polished surface of 6063 alumin-
ium alloy are given in Fig. 14 which shows polished surface
with few scratches due to polishing. The surface morphology
of the 6063 aluminium alloy sample was examined by SEM
immediately after corrosion tests in 1.0 M phosphoric acid
medium and 0.5 M sodium hydroxide medium. The SEM
image of corroded sample given in Figs. 15 and 16 shows the
degradation of alloy, with more or less uniform attack in
phosphoric acid medium and sodium hydroxide medium.
Fig. 17 represents EDX spectrum of the polished sample of
the 6063 aluminium alloy. The spectrum shows peaks for
aluminium and oxygen suggesting the presence of aluminium
oxide/hydroxide. Fig. 18 depicts the EDX spectrum for the
corroded sample in the presence of phosphorous indicating
the attack of phosphoric acid medium.
3.1x10
-3
3.1x10
-3
3.2x10
-3
3.2x10
-3
3.3x10
-3
3.3x10
-3
-2.2
-2.0
-1.8
-1.6
-1.4
-1.2
-1.0
-0.8
-0.6
-0.4
-0.2
l
n

(
C
R
/
T
)

(
m
m

y
-
1

K
-
1
)
1/T (K
-1
)
0.01M
0.05M
0.1M
Figure 11 Plots of ln(CR/T) vs. 1/T for the corrosion of 6063
aluminium alloy in H
3
PO
4
.
3.1x10
-3
3.1x10
-3
3.2x10
-3
3.2x10
-3
3.3x10
-3
3.3x10
-3
6.0
6.5
7.0
7.5
8.0
8.5
l
n

(
C
R
)

(
m
m

y
-
1
)
1/T (K
-1
)
0.05M
0.25M
0.5M
Figure 12 Arrhenius plots for the corrosion of 6063 aluminium
alloy in NaOH.
3.1x10
-3
3.1x10
-3
3.2x10
-3
3.2x10
-3
3.3x10
-3
3.3x10
-3
0.5
1.0
1.5
2.0
2.5
3.0
l
n

(
C
R
/
T
)

(
m
m

y
-
1

K
-
1
)
1/T (K
-1
)
0.05M
0.25M
0.5M
Figure 13 Plots of ln(CR/T) vs. 1/T for the corrosion of 6063
aluminium alloy in NaOH.
Table 5 Activation parameters for the corrosion of 6063
aluminium alloy in NaOH.
NaOH (M) E
a
(kJ mol
1
) DH
a
(kJ mol
1
) DS
a
(J mol
1
K
1
)
0.05 18.43 15.88 150.54
0.25 15.79 13.24 141.49
0.5 13.25 10.70 128.21
Figure 14 SEM image of freshly polished surface of the 6063
aluminium alloy.
Table 4 Activation parameters for the corrosion of 6063
aluminium alloy in H
3
PO
4
.
H
3
PO
4
E
a
(kJ mol
1
) DH
a
(kJ mol
1
) DS
a
(J mol
1
K
1
)
0.01 13.1958 10.644 180.99
0.1 31.6439 29.0923 109.652
1.0 50.2442 47.6926 37.8584
Corrosion behaviour of 6063 aluminium alloy 7
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media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
For aluminium there is deposition of aluminium phosphate
precipitate on the surface and for 6063 aluminium alloy due to
the alloying elements, it may be attributed to deposition of the
phase Mg
5
Al
8
which makes an anodic phase in the aluminium
matrix and Si acts as cathode and contributes to the intergran-
ular corrosion resulting in uniform attack and making it an
optimum region of dissolution (Scamans et al., 1987). Close
observation of SEM metal images indicates the deposition
of precipitates of aluminium phosphate and magnesium
phosphate on 6063 aluminium alloy.
Fig. 19 depicts the EDX spectrum for the corroded sample
in the presence of sodium hydroxide medium. The spectrum re-
veals the presence of sodium hydroxide medium, the increase
in the amount of oxygen can be attributed to the presence of
aluminium hydroxide lm formed due to the attack of hydrox-
ide ion on the surface of metal.
3.5. Mechanism of corrosion process
Aluminium and its alloys have air formed oxide lm of
amorphous c alumina which initially thickens on exposure to
neutral aqueous solution with the formation of a layer of
crystalline hydrated alumina (Hart, 1957).
In acid solution the mechanism of dissolution of aluminium
is as follows (Obot et al., 2010):
Al H
2
O ! AlOH
ads
H

; 6
AlOH
ads
5H
2
O H

! Al
3
6H
2
O 2e

; 7
Al
3
H
2
O ! AlOH
2
H

; 8
AlOH
2
X

! AlOHX

: 9
Thus soluble complex ion formed leads to the dissolution of
the metal.
In case of sodium hydroxide medium corrosion of metals is
known to proceed by the action of local cells, which are
established by metals, comprising a partial anodic reaction
and a partial cathodic reaction occurring simultaneously on
the metal surface (Uhlig and Revie, 1991). So, in order to
Figure 15 SEM image of 6063 aluminium alloy after immersion
in 1.0 M H
3
PO
4
.
Figure 16 SEM image of 6063 aluminium alloy after immersion
in 0.5 M NaOH.
Figure 17 EDX spectrum of the polished sample of the 6063 aluminium alloy.
8 P. Deepa, R. Padmalatha
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
follow the mechanism underlying the corrosion of metals, it is
necessary to explore which partial anodic reactions and partial
cathodic reactions involve and to determine which of them pre-
vails in the gross corrosion reaction to a greater extent. In
addition, the presence of the native surface oxide lm should
be considered in studying the corrosion mechanism of
aluminium in alkaline solution. The anodic aluminium
dissolution reaction in the presence of the oxide lm can be
classied into a direct metal dissolution reaction by the move-
ment of aluminium ions through the lm and an indirect metal
dissolution reaction by consecutive oxide lm formation and
dissolution (Moon and Pyun, 1998; Moon and Pyun, 1999).
It is generally accepted (Wernick et al., 1987; Brock and
Wood, 1967) that the lm formation proceeds electrochemi-
cally by the incorporation of hydroxide ions into the lm
and migration through the lm towards the aluminium/lm
interface in the presence of a thick oxide lm on the surface
of aluminium as (11):
Al 3OH

! AlOH
3
3e

10
The aluminium hydroxide lm formed electrochemically will
be dissolved chemically by OH- attack at the lm/solution
interface:
AlOH
3
OH

! AlOH

4
11
where AlOH

4
represents the aluminate ions. A partial ano-
dic dissolution reaction of aluminium in alkaline solution
can be obtained by combining electrochemical lm formation
(10) and chemical lm dissolution (11), which can be written
as:
Al 4OH

! AlOH

4
3e

12
The electrons produced by the partial anodic Reaction (12)
will be consumed immediately by such partial cathodic reac-
tions as the oxygen reduction reaction:
3=4O
2
3=2H
2
O 3e

! 3OH

13
and/or the water reduction reaction:
3H
2
O 3e

! 3=2H
2
3OH

14
Figure 19 EDX spectrum of 6063 aluminium alloy after immersion in 0.5 M NaOH.
Figure 18 EDX spectrum of 6063 aluminium alloy after immersion in 1.0 M H
3
PO
4
.
Corrosion behaviour of 6063 aluminium alloy 9
Please cite this article in press as: Deepa, P., Padmalatha, R. Corrosion behaviour of 6063 aluminium alloy in acidic and in alkaline
media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059
The short-circuited corrosion reaction of pure aluminium in
alkaline solution can be obtained by combining Reactions
(12) and (13):
Al OH

3=4 O
2
3=2 H
2
O ! AlOH

4
15
and/or by combining Reactions (12) and (14):
Al 3H
2
O OH

! 3=2 H
2
AlOH

4
16
As a consequence of the overall corrosion Reaction (15), alu-
minium metal dissolution occurs. On the other hand, hydrogen
evolution takes place simultaneously with the dissolution of
aluminium metal as a result of the overall corrosion Reaction
(16). The observation of gas bubbles on the corroding
aluminium surface shows that the corrosion of aluminium in
alkaline solution proceeds mainly by water reduction (Pyun
et al., 1999) according to Reaction (16).
Therefore, it is concluded that the overall corrosion reac-
tion of aluminium in alkaline solution can be divided into
two substeps of a partial anodic reaction comprising the elec-
trochemical formation and chemical dissolution reactions of
the lm, and a partial cathodic reaction of water reduction
reaction.
4. Conclusions
6063 aluminium alloy undergoes corrosion both in phos-
phoric acid medium and in sodium hydroxide medium.
The corrosion rate increases with an increase in the concen-
tration of phosphoric acid medium as well as sodium
hydroxide medium.
The corrosion rate increases with an increase in
temperature.
The corrosion of 6063 aluminium alloy is more severe in
sodium hydroxide medium than in phosphoric acid
medium.
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Corrosion behaviour of 6063 aluminium alloy 11
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media. Arabian Journal of Chemistry (2014), http://dx.doi.org/10.1016/j.arabjc.2013.07.059

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