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Anti-Corrosion Methods and Materials

The kinetics of anodic and cathodic polarization of aluminium and its alloys
Dr. Zaki Ahmad
Article information:
To cite this document:
Dr. Zaki Ahmad, (1986),"The kinetics of anodic and cathodic polarization of aluminium and its alloys", Anti-Corrosion
Methods and Materials, Vol. 33 Iss 11 pp. 4 - 11
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http://dx.doi.org/10.1108/eb020492
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The k i n et i c s of anodi c and cat hodi c
pol ar i zat i on of al u mi n i u m and i t s al l oys
b y Dr . Z ak i A h mad , Mechani cal Eng i neer i ng Depar t ment Uni v er si t y of Pet r ol eum & Mi ner al s Dh ah r an 3 1 2 6 1 , Saudi A r ab i a
The relatively complex corrosion mechanism of alumi-
nium has been studied by several authors. Corrosion of
aluminium occurs only when the metal protective oxide
layer is damaged and when the repair mechanism is
prevented by chemical dissolution
1
. Polarization methods
have been extensively used to investigate the mecha-
nism of localised corrosion and processes that lead to
localised corrosion. The potential-pH diagrams are
shown in Fig. 1A. In using potentiostatic techniques, the
potential is controlled and current is determined as the
independent variable
2
. Potentiostatic and potentiody-
namic techniques have been applied by several authors
to study the corrosion of aluminium in different
environment
3_8
. Both anodic and cathodic polarization
curves have been used to interpret the kinetics of pitting
corrosion of aluminium in chloride containing environ-
ments. Both the anodic and cathodic process are com-
plex and the interpretation of the anodic and cathodic
polarization curves of aluminium is often tedious. The
situation arises partly from the fact that the role of film
formation on the kinetics of corrosion is not clearly
understood. Previously there is not established mecha-
nisms of initiation and propagation of pits in aluminium
and its alloys. Several parameters such as pitting poten-
tial, breakdown potential, active passive transition
potential, related to the pitting process of aluminium, are
full of controversy
9_11
. Numerous references on the
above can be found in literature
12_15
).
It is the purpose of this paper to show how the anodic
and cathodic polarization curves can be used to inter-
pret the corrosion processes.
A nodic polarization
A typical anodic polarization curve is shown in Fig. 1B.
The curve is marked by two important regions, A and B.
The region A shows a gradual increase in the current
with the applied potential. As soon as region A is
crossed, a sharp rise in the current is observed. This is
characteristic of region B. The break in the curve is due
to the onset of pitting as a consequence of breakdown of
the oxide layer. Cyclic polarization technique have been
extensively used for investigating pitting corrosion of
aluminium. In order to be able to interpret the anodic
polarization curves it is essential to understand their
characteristics. Another anodic polarization curve is
shown in Fig. 2. Epp represent the protection potential
and Ep, the critical pitting potential. This diagram can be
divided in three regions.
1. Region A: In this region pitting initiates and propaga-
tion takes place on and above a critical pitting potential
designated by Ep, where a marked increase in the anodic
dissolute current occurs.
2. Region B: This is the region between Ep (pitting poten-
tial) and Epp(protection potential). In this region new
pits will not initiate but the existing pits would continue
to propagate.
The protection potential (Epp) is defined as the poten-
tial below which there would be no propatation and
initiation of pits. There is, however, a disagreement on
the existence of a protection potential and pits have
been observed to propagate below Epp
16_17
.
3. Region C: This region represents immunity to pitting
and at potentials more negative than Epp pitting is not
likely to propagate. However, pitting of a different nature
(alkaline) has been observed below Epp
16_17
).
The relative position of corrosion potential with respect
to pitting potential has been used in interpretation of the
pitting behavior of aluminium alloys. The corrosion
resistance of aluminium depends on the formation of
protective films; such films are formed when the metal is
anodically polarized in solution where pH is not too far
removed from neutrality. The breakdown of the protec-
tive film would occur when the anodic potential exceeds
a certain value. It is generally agreed that the breakdown
of the hydrate oxide is caused by halide ions. The initia-
tion of pitting is shown in a E vs. I diagram, discussed
above, by a sharp increase in the current density. This is
shown in Fig. 2. The break in the curve shown corres-
ponds to pitting potential (Ep), the potential at which pits
initiate. The existence of a pitting potential is, however,
disputed
18_19
. As the corrosion behavior of aluminium up
to the point of film breakdown is controlled by the anodic
process, it is to be expected that anions rather than
cations would play a major role up to the point of break-
down
20
. It has been observed that pitting would occur
only if the critical pitting potential is lower than the
corrosion potential
21
. Pitting would be inhibited if Ecorr
is lower than Ep. Previous data suggests that during
anodic polarization, film thickening occurs in all solute
except chloride. It was found that anodic treatment
thickened the film by about 28 A with 0.1 N solution of
chromate (pH + 8.41), sulphate (pH + 7) but no evidence
of oxide thickness was obtained with 0.1 N chloride (pH
+ 7)
22
. Under conditions of steady state the film break-
down is balanced by film repair. The initial process dur-
ing anodic polarization is repair of hydrated oxide film
and replacement of the oxide film by a non steady state
film
23
. Curves ABC, A'B'C and A"B"C represent anodic
polarization curves for aluminium dissolution as a func-
tion of pH (Fig. 3). At low potentials (AB, A'B' and A"B")
the rate of the anodic reaction is independent of the
electrode potential but increases with increasing pH.
The rate of corrosion in this region is controlled by the
rate of mass transport of hydroxide ions to the oxide-
solution interface
4
. It has been suggested that the above
reaction controls the rate of corrosion
4
. The pitting
potential of aluminium becomes less noble with increas-
ing chloride concentration.
The presence of small amounts of cathodic alloying
elements leads to an increase in the pitting potential
more positive than the pitting potential
24
. The critical
pitting potential is also increased by inhibitor addition
(Fig. 4.). The anodic behavior of aluminium has been
used to study the mechanism of pitting and intergranular
corrosion. Galvele
25
observed that pitting of aluminium
4 ANTl-CORROSION November 1986
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is related to a critical potential which does not depend on
induction period. The behavior of 99.9 A1 when potential
is changed from the passive range to the pitting range is
shown in F ig. 5. It was observed that on holding the
specimen at a low potential, the current decreased to a
very small value, whereas at a higher potential (more
noble) within the pitting range, the current increased by
two or three orders of magnitude. This suggests that if
pitting were to be independent of potential, once the
pitting starts, it would not be possible to stop it by
decreasing the potential. It has been shown by polariza-
tion technique that commercial aluminium is passive
within the potential limits (0.76 mV
SEC
to 1.38 mV
SE-
C
)
16
. Pitting occurs above the higher limit, whereas the
lower limit marks the point where the film becomes
unprotective. The upper limit marks the pitting potential
whereas the lower limit marks the active to passive
transition.
In recent studies conducted the lower limit has been
found to be 1.5 mV
SCE
17
. It has been observed that in
both acid and basic solutions of halides two distinct rate
controlling reactions occur. Below the critical pitting
potential the diffusion of aluminium ions appear to be
the rate controlling reaction. The growth of the film
(barrier type) proceeds by diffusion of the metal ions
through N-type oxide (excess metal ions)
26
. Above the
critical pitting potential, which is independant of pH,
anodic polarization does not proceed further. If pH is
increased due to increased alkalinity (OH

ion produc-
tion) the protective film dissolves. The shape of the
anodic polarization curves indicate whether the film is
being formed, repaired, or destroyed, hence, the kinetics
of pitting can be studied by anodic polarization curves. lt
has been suggested that the magnitude of pitting poten-
tial is dependent on the thermo-dynamic potential for
the formation of
26
. The anodic reaction takes
place nearly on all the surfaces, whereas the cathodic
reaction takes place only on impurities and grain boun-
daries
27_ 28
). The cathodic reaction stops as soon as the
cathodic sites are destroyed and the film achieves an
equilibrium thickness.
The following are the main anodic reaction
29
:
3H
2
O A1(OH)
3
AI + 2H
2
O A1 (OH) +3H
+
+ 3e
H
2
O A1
2
O
3
The film breakdown as a consequence of formation of
complexes such as
The films formed on aluminium have a dominant influ-
ence on the kinetics of anodic reaction. The nature and
formation of films has been the subject of numerous
investigations
30_ 35
. It has been widely accepted that
duplex type of films are formed. On immersion in water
oxide film can grow up to a thickness of 10 A. The
duplex film on aluminium (F ig. 6) consist of a protective
inner barrier oxide layer and a bulk (outer oxide) layer.
The composition of amorphous bulk hydrated oxide film
is dependent on the interaction corroding medium.The
role of pH is important, as it affects the solubility (F ig.
6a). Also it has been suggested that film formation is
completed in three stages, the first being the formation
of amorphous aluminium hydroxide AI(OH)
3
, the second
mono-hydrate orthorhombic crystalline boehmite
A1
2
O
3
, 3H
2
O [or A1O (OH] and the third being the
trihydrate monoclinic bayerite Al
2
O
3
or hydragellite
[ Al
2
O
3
, 3H
2
O] [36]. It has been suggested that the.
overall corrosion rate is affected by the thickness and
nature of the bulk film, which in most instances is a film
of oxide layer which takes place are reflected by the
change in the shapes of the anodic polarization curve.
Pitting proceeds by disruption of the outer oxide layer by
chloride or other halide ions due to the formation of
AICI
4
complex as stated above. The dissolution of the
oxide film is slower in acids than in alkaline solutions
4
. In
alkaline solutions it has been observed that the rate of
anodic reaction decreases with time at constant pH and
constant solution velocity
4
. The rate of anodic process
also appears to be influenced by the rate of corroding
specimen to the solution volume and rate of refreshment
of bulk solution.
In addition to the kinetics of corrosion, the anodic
polarization curves have been used to study the effect of
alloying elements on the corrosion resistance of
aluminium.
ANTI-CORROSION November 1986 5
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Effect of alloying elements
The effect of addition of alloying elements of Cu, Mn and
Cr on the anodic polarization of Al 99.7 in Arabian Gulf
water is shown in Figs. 7-9
37
. Copper addition increases
the pitting potential, hence, it weakens the resistance to
pitting. Thus, a shift of Ep to more noble value does not
always signify a higher resistance to pitting. The pitting
resistance of Al 99.7 containing Cr and Mn is superior to
that of Al 99.7 containing 0.3 or 0.3 copper. Al 99.7
containing 0.2 chromium shows a higher potential and a
higher pitting resistance then Al 99.7 containing Mn.
The anodic polarization curves of pure aluminium and
various binary alloys in 1 N-NaCI are shown in Fig. 10.
The pitting potentials of pure aluminium and aluminium
alloys are shown in Table 1. The relation between pitting
potential of binary aluminium alloys and content of alloy-
ing element in 1 N-NaCI solution at P >10.0 is shown in
Fig. 11. It is observed from Fig. 11 that increasing Mg
content lead to a decrease of pitting potential Incremen-
tal addition of Mn shifts the pitting potential slightly in
the noble direction, whereas, Fe addition does not cause
any appreciable change. Nickel and copper addition
shift the potential in the noble direction as suggested
earlier. The following order for some binary aluminium
alloys in NaCI was obtained in terms of decreasing pit-
ting potential
38
from the anodic polarization studies:
AI-Cu>AI-Ni>AI-Si>AI-Mn>AI-Cr>AI-B>AI-Zr>AI-Ti>
Al-Mg>Al-Be
The variation of pitting dissolution current for the
some binary alloys is shown in Fig. 11. The following
order in terms of decreasing resistance to pitting has
been reported for the following alloying elements:
F e>Mg>Mn>Si>Cu.
In recent studies conducted by the author it has been
observed that Mg increases and Cr decreases the pitting
potential whereas Si does not have a major influence on
the pitting potential of AI-2.5 Mg alloy
37
. Anodic polariza-
tion curves have also been used in studying the effect of
ion implantation on the corrosion resistance of com-
mercially pure aluminium
39
. The polarization curves of
unimplanted aluminium in 0.01 M Na
2
SO
4
and 1000 ppm
CI are shown in Fig. 12. Similar curves in chloride free
6 ANTI-CORROSION November 1986
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environment are shown in Fig. 13. The cathodic regions
of the two sets of curves, the corrosion potential and
passive current densities, are same for both. However, in
CI

containing environment breakdown of curve occurs


at a certain critical potential and a sharp rise in the
anodic current density is observed. The surface of
unimplanted alloy shows no pitting in CI

free environ-
ment, whereas in CI

environment it is badly pitted. It


has further been observed that the corrosion potential of
pure aluminium is raised by more than 500-700 mV
SCE
by
implanting Mo. The breakdown potential is also increased
by more than 200 mV
SCE
39
. The results therefore show
that anodic polarization studies can be useful in study-
ing the effect of ion implantation. The anodic polariza-
tion studies can, therefore, be used with advantage to
study the effect of different parameters on the corrosion
resistance of aluminium alloys. The technique is by no
means perfect and it is open to controversy and criti-
cism. Concentrated efforts would be required to make
this technique quantitative and more reliable.
Cathodic Polarization
Cathodic reactions occur on metals presumably by
migration of electrons through the surface oxide films
and subsequent interaction of those electrons with hyd-
rogen ions and dissolved oxygen at the film/solution
interface. Corrosion of aluminium and its alloys pro-
ceeds similarly by reduction of hydrogen and oxygen
and the rate of corrosion is controlled by the diffusion
limited current density for cathodic reduction. A sche-
matic representation of the cathodic polarization dia-
gram is shown in Fig. 14. The corrosion current density (I
corr) is obtained by extrapolating the linear Tafel region
of the curve to the steady state corrosion potential (E
corr
).
The exchange current density is obtained by extrapola-
tion of the linear part of the curve to the reversible hyd-
rogen potential. Although aluminium corrosion has
received much attention in the last decade, its electro-
chemical behavior is not fully understood.
ANTI-CORROSION November 1986
7
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The cathodic corrosion, particularly alkaline pitting of
aluminium in unbuffered chloride media has been inves-
tigated by potential controlled methods
16
. The polarizi-
bility of aluminium is increased by the presence of
impurity rich sites on the surface. As soon as the film is
broken down the cathodic reduction process estab-
lishes itself. The process of reduction occurs possibly by
migration of electrons through the oxide film and its
interaction with hydrogen ion and dissolved oxygen as
discussed above. It has been established that cathodic
reaction occurs over the localised cathodic sites
40
. Dur-
ing cathodic polarization hydrogen is evolved which
results in the production of excess of OH

ions adjacent
to the working electrode surface. The high local pH
converts the air formed oxide film to the hydrated oxide.
8 ANTI-CORROSION November 1986
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The degree of hydration depends on temperature, time,
ion concentration and pH.
F igure 14A shows the main points of a typical potenti-
ostatic polarization curve in air saturated solution of
NaCI and F ig. 14B shows the cathodic polarization
curves of Al alloys in sodium chloride clearly. The prob-
able reaction is
H
2
O +e OH

+H (ads) (1)
The increase of pH at the cathode has been experimen-
tally verified. The non Tafel portion of the slope appears
to be controlled by the limited cathodic current and
anodic reaction. The limiting cathodic current may be
caused by one of the following:
2H +2e H
z
(2)
2HO + O
2
+ 4e 40H (3)
The concentration of hydrogen ions is controlled by
reaction (2). Although oxygen may have a greater effect
on the corrosion rate of aluminium, the reduction of
hydrogen ion predominates. Dissolved oxygen, how-
ever, increases the tendency of the high purity alumi-
nium to pit. It has been suggested that pure aluminium is
insensitive to the effect of oxygen, whereas it exerts a
greater effect on the corrosion of aluminium alloys. The
effect of oxygen on aluminium alloys in chloride solu-
tions merits further study
17
. The solubility of the hydrox-
ide film depends largely on the magnitude of the basicity
or acidity. If oxygen is excluded from the solution reac-
tion (1) would be controlling reaction. On replacing
oxygen by nitrogen the amount of current was not found
to increase substantially which showed that reaction (3)
was not controlling the limited cathodic current. It has
also been shown that the limiting current is greater if
oxygen is absent as the amorphous film of hydroxide is
loosely adherent in the absence of oxygen and does not
provide a good resistance to aluminium ion flow. On the
other hand, the film formed in the presence of oxygen is
tenacious and compact and it therefore provides a
greater degree of protection.
Under the open circuit condition, the cathodic current
polarize the surface to the pitting potential. During
cathodic polarization the meal dissolution proceeds
mainly by alkalinization. At a certain potential the rate of
alkalinization (product of OH ions) become too high to
allow oxide to be formed and therefore the rate of corro-
sion is accelerated. The presence of impurities and
cathodic site in aluminium has been verified. As soon as
the cathodic sites are covered by oxide, repassivation
takes place
41
. If the exposed cathodic area is too small,
the available cathodic sites may not be sufficient to
maintain corrosion, and the surface may, therefore, stay
passive. Passivation may also be caused by parting of
the cathodic sites from the surface of the metal. The
solubility of the oxide film tends to increase with
increased alkalinity and consequently the rate of disso-
lution increases. It has been suggested that cathodic
reaction in alkaline solution is independent of pH (4).
Between pH 4-10 the rate of attack is reported to
decrease because of the deposit of hydroxide, but at pH
values higher or lower than the above range the rates are
constant in water
23
. At higher OH concentration, the
rate is limited by OH diffusion.
In alkaline solutions the corrosion current and corro-
sion potential is determined by the intersection of the
anodic polarization curve with the cathodic polarization
curve (F ig. 15). With increased OH concentration the
transport rate of anode process increases and the inter-
section of the anodic and cathodic polarization curves
shifts to more negative potentials and higher current
densities
4
. On the other hand with increasing acidity the
corrosion current increases with a greater discharge of
hydrogen. The rate of transport controlled anodic reac-
tion would become small compared to the cathodic reac-
tion and the potential would shift in the more noble
direction close to the pitting potential
41
. For instance the
pitting resistance of two alloys can be compared by
cathodic polarization studies.
ANTI-CORROSION November 1986
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In order to be able to protect aluminium corrosion it is
important to know the upper and lower potential limits
beyond which the alloy does not pit. The upper limit for
commercially pure alumimium in aqueous chloride is
reported to be 0.76 mV
SCE
and the lower limit 1.38
mV
SCE
17
. It has been suggested that the lower limit is the
result of shift of reactions from solution metal oxide
interface to the metal-metal oxide interface at that poten-
tial [42]. The increased rate of general corrosion
between 1.65 mV
SCE
appears to be related to the ionic
conductivity rather than electronic conductivity at
potential greater than 1.38mV
SCE
[17]. It has been sug-
gested that between the two limits the pitting of a differ-
ent nature, alkaline pitting, take place whereas above the
upper limit alkaline pits propagate due to local alkalini-
zation of the surface, however, once the cathodic sites
are destroyed, the surface repassivates.
Aluminium undergoes pitting corrosion at zero net
current when oxygen is present
43
. The failure of alumi-
nium surface to remain passive at high cathodic polari-
zation appears to be due to the increased rate of hydra-
tion of the oxide film with decreasing potential. The
above suggestion for a lower potential bond for alumi-
nium contradict the existence of a protection potential
for commercially pure aluminium. For modified alumi-
nium alloys a distinct protection potential (Epp) has
been observed by the authors
44
and pitting is not found
to occur below 1200 mV
SCE
.
The fact that pitting would not develop if the corrosion
potential were below the pitting potential, has been util-
ized to predict the pitting performance of aluminium
alloys
45
. More negative values of corrosion potential
indicate a decreasing susceptibility to pitting in alkaline
solution because the increased rate of corrosion at more
negative potential makes it difficult to polarize the alloy
to its breakdown potential. If the rate of general corro-
sion is high, pitting would not take place. The criteria
that pitting would not occur or the resistance to pitting
would not be high if Ecorr was more negative than Ep,
does not, however, provide a quantitative basis, and it
cannot be used to differentiate between the pitting
resistance of alloys slightly differing in composition. It
has been suggested that Ep is not a function of the alloy
content and it varies with the type of surface preparati-
on
46
. More accurate prediction can be made if the results
obtained from potential-time studies and metal log raphic
observations are also considered. Results based on Ep
value alone can be misleading. For instance, copper
shows a high value of Ep, however, it is prone to pitting.
The values of Ep obtained by potentiostatic induction-
time method
47
appear to be more accurate as shown by
recent studies.
The cathodic polarization curve can be used to com-
pare the corrosion resistance of alloys at least qualita-
tively as shown in Fig. 15. It can be observed from the
figure that the rate of corrosion of alloy 6061 is higher
than alloy 5454 because of the enhanced cathodic reac-
tion
4
. The high rate of dissolution of alloy 6005 maintains
the alloy in the range of pitting potential. The limit of
pitting resistance of aluminium and its alloys in chloride
solution is determined by the position of the pitting
potential with respect to the curves for cathodic polariza-
tion. Useful information on the pitting resistance of
aluminium alloys and the mechanism of pitting can
therefore be obtained from cathodic polarization curves.
Inspite of the advances in the electrochemical tech-
niques made in the last decade, a standard technique is
still to be realised. The film formation process in alumi-
continued on page 17
10 ANTI-CORROSION November 1986
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The kinetics of anodic and cathodic polarization of
aluminium and its alloys
continued from page 10
nium is highly complex and not completely understood.
There is still controversy on the existance and signifi-
cance of pitting potential, protection potential and
active-passive transition potential. With the growing
interest in aluminium as an economic material and the
development of new technique it is expected that some
of the controversies would be resolved.
ANTI-CORROSION November 1986 17
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ANTI-CORROSION November 1986
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This article has been cited by:
1. Rajendran Babhu Vignesh, Mathur Gopalakrishnan Sethuraman. 2014. Enhancement of corrosion protection of 3-
glycidoxypropyltrimethoxysilane-based solgel coating through methylthiourea doping. Journal of Coatings Technology and
Research 11, 545-554. [CrossRef]
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