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REVIEW

Trans. Indian Inst. Met.


Vol.57, No. 6, December 2004, pp. 593-610

PITTING CORROSION OF HEAT-TREATABLE


ALUMINIUM ALLOYS AND WELDS: A REVEIW
K.Srinivasa Rao and K.Prasad Rao
Department of Metallurgical and Materials Engineering, IIT-Madras,Chennai-600036
E-mail:arunaraok@yahoo.com
(Received 12 April 2004 ; in revised form 18 October 2004)

ABSTRACT
This review attempts to present the current understanding of the mechanism of pitting corrosion of heat treatable
aluminium alloys and their welds. The role of alloying elements and intermetallic phases on the corrosion
behavior of these alloys has been discussed. Pitting mechanism of aluminium- copper alloys is specifically
discussed. Finally effect of welding on the pitting corrosion of these alloys is also presented.

1. INTRODUCTION
Heat treatable aluminum alloys are widely used in
aircraft structural applications and are susceptible to
localized corrosion in chloride environments, such as
pitting, crevice corrosion, intergranular corrosion,
exfoliation corrosion and stress corrosion cracking.
This article reviews the some aspects of passivity and
pitting of Al alloys. Specifically, metastable and
stable pits, pitting mechanism, effect of intermetallics
and effect of welding parameters on pitting corrosion
of age hardenable Al-alloys.

2. PITTING
ALLOYS

CORROSION

OF

Al

Pitting corrosion is defined as localized accelerated


dissolution of metals that occurs as a result of a
breakdown of the protective passive film on the metal/
alloy surface1. In an aggressive environment,
typically containing halide ions, pits initiate and grow
in an autocatalytic manner, where the local
environment within the pits becomes more aggressive
because of decrease in pH and increase in chloride
concentration, which further accelerates the pit growth.
The pit growth usually takes a variety of shapes2
(Fig. 1). Pit shapes can be simply divided into
isotropic and anisotropic groups. Shapes in
Fig. 1 a-e are isotropic, while those in Fig. 1f are
anisotropic and are called microstructural orientated

pitting. The variation in pit shape could mainly depend


on the microstructure of metals or alloys such as
alloy composition and aspect ratio of grains. Even
though there are some differences in pitting corrosion
between stainless steels and Al alloys, e.g., hydrogen
bubbles form at the active pit surface in Al alloys,
both materials basically share a similar mechanism.
In general, pitting corrosion involves three stages:
pitting initiation, metastable pitting, and pitting
growth.
2.1 Pit Initiation
As mentioned above, aggressive anions such as
chloride are believed to cause passive film breakdown.
However, the exact mechanism of the passive film
breakdown is still unclear. A number of models have
been proposed to explain passive film breakdown or
pit initiation3-9. Three main models are 1) adsorption
mechanism 2) penetration mechanism and 3) film
breaking mechanism (Fig. 2). These models have been
reviewed in depth in the literature10-11.
The adsorption theory emphasizes the importance of
adsorption of aggressive anions like chloride ions.
A competitive adsorption of chloride ions and oxygen
finally may lead to film thinning. The penetration
model emphasizes the importance of anion penetration
and ion migration through the passive film.
MacDonald and coworkers5-7 have developed a point

TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

Fig. 1

: Variations in shape of Pits

defect model as a modified or related penetration


model. The point defect model addresses the transport
of cationic vacancies to the metal/oxide interface
controlling pit initiation instead of anion penetration.
The point defect model has been fitted to experimental
data such as pitting potential and induction time for
pitting corrosion of Al and Al alloys in halides.
However this model cannot explain metastable pitting,
and some assumptions such as the electrode potential
and vacancy migration in extremely high electric field
(on the order of 106 to 107 V/cm) are suspicious.
The film-breaking model involves the breakdown and
repair of the passive film simultaneously. Mechanical
stresses due to electrostriction and surface tension
cause the passive film breakdown, which is repaired
rapidly. According to this film-breaking model, pits
initiate as a result of the passive film breakdown
only when stable pits grow afterward.
In summary, these models address important aspects
of pit initiation such as aggressive ion adsorption,

ion penetration and migration, and stress-induced


breakdown of passive film. Although these models
obtained some experimental support, no comprehensive
or universal model can account for pitting corrosion
in all metal/environment systems. This indicates that
pit initiation is rather complicated and a combination
of these models could explain pitting for a certain
metal/environment system.
2.2 Metastable Pitting
Metastable pits are pits that survive for a very short
lifetime in the order of seconds or less. They can
initiate and grow to the micron size at potentials far
below the pitting potential and also above the pitting
potential during the induction time prior to the onset
of stable pitting. Figure 3 shows typical metastable
pit current transients on stainless steels, in chloride
solution under an applied anodic potential. The current
increases corresponding to the growth of metastable
pit followed by a sharp current decrease due to

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Fig. 2

: Schematic of pit initiation models

repassivation process. Since metastable pits experience


initiation, growth, and repassivation, a better
understanding of these three stages for the stable pit
can be gained through study of metastable pitting.
Metastable pitting phenomenon was first observed in
stainless steel in the early 1970s12. Frankel and
coworkers used the term of metastable pitting for the
first time13. Over the past 30 years, metastable pitting
has been systematically investigated by analyzing pit
current density for individual metastable pits and
stochastic approaches to groups of metastable pits.

These detailed studies show that the early


development of stable pits appears to be identical to
that of metastable pits, and the probability of stable
pitting is directly correlated to the intensity of
metastable pitting events. Metastable pits repassivate
probably when the porous cover ruptures and the pit
electrolyte is diluted. In contrast to a huge amount of
studies on corrosion of stainless steels, literature on
corrosion of Al or Al alloys is limited. Pride14 et al.
studied metastable pitting on pure Al. They found
that the number of metastable pits and the current

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TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

Fig. 3

: Metastable pit transients observed on 302 stainless


steel polarized at 420mV SCE in 0.1M NaCl
solution.

spikes increase with increasing applied potential below


pitting potential and the chloride concentration. A
critical transition from metastable pitting to stable
pitting in Al has been found in their study.
2.3 Pit Growth
Above the pitting potential, stable pits grow at a rate
depending on alloy composition, local pit environment
and pit bottom potential. Due to the autocatalytic
nature of pitting corrosion, the local pit environment
and bottom potential is severe enough to prevent
repassivation. Pit growth can be controlled by each
or combinations of three factors mainly chargetransfer, ohmic and mass transport 15-18. For a
hemispherical pit, different rate controlling factors
would lead to specific relationships between current
I, current density i, pit radius or depth r, time t, and
potential E.
.

Under charge transfer control, Tafels law


describes i exp E.

Under ohmic control, it can be derived I r


and i I/r2 1/r. From Faradays law,
i dr/dt, leading to r t 1/2 and thus
I t 1/2 and i t -1/2. Ohms law determines
i E .

Under mass transport control, according to Ficks


laws, i 1/r, thus i t-1/2. i is E independent.

The similar i-t relationship for ohmic control and


mass transport control makes it difficult to distinguish.
For a 3D bulk sample, the non-steady state nature of

pit deepening and the problem with accurate


measurements of pit current density complicate the
clear identification of the i-E relationship . In a
conventional measurement of i-E relationship, current
may come from several pits with unknown active
surface areas and presumably is evenly distributed on
the pits. However, the assumption of even distribution
is not possible since different pits initiated at different
potentials grow at different rates. Artificial pit
electrodes, formed by imbedding a wire in epoxy
have been extensively used to study iron and stainless
steel behavior 19. The artificial pit electrode geometry
forms a single pit in which the whole electrode area
is active, generates a natural pit environment, and
provides an ideal one-dimensional transport condition.
For Al and Al alloys, similar to artificial pit
electrodes, artificial crevice electrodes have been used
since large crevice area facilitates the escape of H2
bubbles 20,21. The results indicate that pits can grow
either in the active state without salt film precipitation
or in a salt-film-covered state. The active state is
dominated by ohmic control while a salt-film-covered
state is dominated by mass transport control. Other
single pit techniques include the exposure of small
area, laser irradiation of a small spot, and implantation
of an activating species at a small spot 22-25.
These studies suggested different viewpoints of either
ohmic control or mass transport control.Besides the
electrochemical methods, non-electrochemical
techniques have been also used. Hunkeler and Bohni 26
measured the time for pit to penetrate Al foils of
varying thickness to determine the pit growth rate.
They found that at fixed applied potential, pit depth
d and current density i were time dependent:
d t1/2 and i t-1/2. Pit growth on Al was ohmic
controlled since the growth rate was correlated to the
conductivity of the electrolyte. Detailed studies of
2D pit in Al and other types of thin films by Frankel
and coworkers 13 found that the high current density
increased linearly with potential and reached a limiting
value at higher potentials (Fig. 4). Therefore, the pit
growth at the beginning is controlled by ohmic control
and after some time controlled by the mass
transport 27-29.
2.4 Pitting Stability
Local pit environment and chemistry are believed to
be very important for pit growth and repassivation.

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the pitting potential and repassivation potential, and


determine the current density required to initiate pitting
and to sustain pit growth at a defect of a given size
in passive film such as crack. Although, for some
metals, other factors like chloride concentration are
more important than acidification, they will roughly
scale with acidification. Thus the critical value x.i
(sometimes Ipit/rpit used) can be used as criteria for
pitting stability. Williams et al.32 correlated pit
stabilization with metastable pitting. They suggested
that Ipit/rpit for metastable pits formed on steels must
exceed 4 10-2 A/cm2 for stable growth.

Fig. 4

: Anodic and net current densities change as a


function of potential for 100 nm Al film in 0.1M
NaCl solution.

Among the various species present within pits such


as metal cations, metal hydroxide, Cl- and H+,
acidification within pits as a result of hydrolysis is
generally recognized to be a critical factor.
Galvele 30, 31 calculated the acidification in 1D pits,
based on metal dissolution, hydrolysis, and mass
transport. He found that a critical value of the product
x.i (x is pit depth and i is current density), was the
critical acidification within pits to sustain pit growth
(Fig. 5). This critical product can be used to explain

At a higher current density during pit growth, a salt


film may form on the pit surface due to saturation of
ionic species. For Al pits in chloride solution, this
salt film was considered to be aluminum chloride
(AlCl 3 ) or aluminum oxy-chlorides such as
Al(OH)2Cl and Al(OH)Cl2 according to measured
pH and possible hydrolysis processes 33-36 . Upon salt
film precipitation, as described above, the pit growth
is under mass transport control. A salt film can
enhance pitting stability by acting as buffer of ionic
species that can dissolve into pit to sustain a severe
condition in the pit environment such as high acid
concentration.
The potential distribution in pits is considered to be
another important factor to stabilize pit growth. When
the IR drop is less than a critical value, pit growth
stops due to repassivation, if the alloy undergoes an
active/passive transition in the pit environment 37-39.
In fact, all of the factors above might be generalized
to pit growth current density, since a pit must maintain
a minimum current density for stabilized growth.
However, the critical pit current density and effect
of environment factors need to be investigated further.
2.5 Criteria for Evaluation of Pitting Corrosion
in Al Alloys

Fig. 5

: Concentration of Al3+, Al(OH)2+, and H+ as a


function of the product of the depth x and the
current density in a unidirectional pit.

Many electrochemical studies of pitting corrosion have


found that there exist characteristic potentials. Using
cyclic polarization techniques, two characteristic
potentials can be determined, which correspond to
pit initiation and repassivation (Fig. 6). One is pitting
potential (EP), sometimes called critical potential or
breakdown potential (EB), above which stable pits
initiate and grow rapidly. The other is repassivation
potential (ER), sometimes called protection potential,

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TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

(a)

Fig. 6

: Schematic cyclic polarization showing EP and ER

below which growing pits repassivate and stop


growing. It should be noted that the values of these
two characteristic potentials can depend somewhat
upon the methods used and potential scan rate.
Moreover, since pitting corrosion is considered to be
stochastic, stochastic approaches have been developed
to handle the scatter of pitting potential 40 . Both EP
and ER have been extensively used to evaluate the
susceptibility to pitting corrosion of various materials
in a given environment. It is generally recognized
that materials exhibiting higher EP and ER are more
resistant to pitting corrosion.
Electrochemical impedance spectroscopy (EIS) uses
a range of low magnitude polarizing voltages, like
linear polarization. However, EIS voltages cycle from
peak anodic to cathodic magnitudes using a spectrum
of alternating current (AC) voltage frequencies,
instead of a range of single magnitude and polarity
direct current (DC) voltages. Data recorded in the
form of Bode and Nyquist plots can provide electrode
capacitance and charge-transfer kinetics and as the
method does not involve a potential scan,
measurements can be made in low conductivity
solutions with high accuracy. Figure 7 shows a simple
electrochemical equivalent circuit and the
corresponding data plots41. The magnitude of the
high frequency impedance where the impedance
magnitude is independent of frequency corresponds
to Rs. The difference in magnitude between the low
frequency and the high frequency independent regions
corresponds to Rp.These resistances are identical to
those on the Nyquist format plot. Low frequency

(b)

(c)

(d)
Fig. 7

598

: (a) Equivalent electrical circuit model for simple


corroding electrode, (b), (c) its Bodes and
(d) Nyquist plots

SRINIVASA RAO AND PRASAD RAO : PITTING CORROSION OF HEAT-TREATABLE ALUMINIUM


ALLOYS AND WELDS

impedance value (Ohm.cm2), where the phase angle


approaches zero is accurate polarization resistance of
the alloy in a given environment. Recently EIS
technique has been recognized as the accurate method
of determining the corrosion resistance of aluminium
alloys in solutions containing aggressive halide ions.
Determining polarization resistance of the alloys
immersed in sodium chloride solution as function of
time and its variation may be criteria for the
measuring pitting corrosion resistance of aluminium
alloys. Recently Q.Meng et..al 42 studied the
corrosion behaviour of 7xxx alloys with varying
Copper content using immersion tests in aerated
chloride solutions (Fig.8) and concluded that the
polarization resistance decreases as the Cu content
increases, which has been attributed to the Cu
enrichment on the surface.

Fig. 8

Coarse intermetallic particles play a crucial role in


the corrosion behavior of Al alloys. The micro
galvanic coupling between the matrix and the
intermetallic particles is generally believed to result
in pitting corrosion and further develop intergranular
cracking (IGC) into the deep structure of Al alloys.
In this section, the role of alloying elements in solid
solution and intermetallic particles in pitting corrosion
of Al alloys will be reviewed.
3.1 Alloying Elements
Muller and Galvele43 first studied the role of alloying
elements in pitting corrosion of Al-Zn, Al-Mg, and
Al-Cu binary alloys in dearated 1 M NaCl. Zn, Mg,
and Cu as alloying elements have different effects on
the pitting potential of Al alloys (Fig. 9). Pitting
potential decreased greatly with increasing Zn content
up to 3wt% and remained the same with further
increase in Zn content. There was no influence of
Mg on pitting potential. Pitting potential increased

: Polarization resistance determined by EIS tests as


a function of immersion time for AA7xxx-T6 in
aerated 0.5 M NaCl.

3. ROLE OF ALLOYING ADDITIONS


AND
INTERMETALLICS
IN
LOCALIZED CORROSION OF Al
ALLOYS
Addition of alloying elements, especially Cu, can
significantly increase the mechanical strength of Al
alloys such as Al-Cu-Mg alloys (2xxx series) and
Al-Zn-Mg-Cu alloys (7xxx series) by precipitation
hardening. Due to the limited solubility of many
elements in aluminum, alloying elements are often
distributed not only in the Al solid solution, but also
in fine precipitates and coarse intermetallic particles.

Fig. 9

599

: Variations of pitting potential as a function of


alloying element content of a) Al-Cu b) Al-Zn and
c) Al-Mg binary alloys.

TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

dramatically with increasing Cu content up to 5wt%.


Furthermore, they studied the corrosion morphology
of these three binary alloys. It was found that tunnellike pits formed on Al-3Zn, and crystallographically
shaped pits on Al-3Mg and Al-3Cu. Sato4 studied
metastable pitting on Al-Zn alloys. They found that
the rate of pit nucleation was potential dependent
regardless of the alloying addition. It was suggested
that Zn addition influenced the pit growth instead of
the pit nucleation events.
Since the mid 1980s, many studies have been conducted
on surface chemistry and corrosion properties of
stainless Al alloys containing W, Ta, Mo, Nb,
and Cr 44-49. These studies provide some clues to
explain the role of alloying elements on pitting
potential. Due to the low solubility of the above
alloying elements in aluminum, thin films of
supersatuarated Al binary alloys have been prepared
by non-equilibrium methods such as sputter
deposition. The electrochemical studies revealed that
the pitting potential of aluminum can be dramatically
increased by the addition of these elements. One of
explanations is that enrichment in the passive film
plays an important role in improving pitting resistance.
Moshier and coworkers44-45 using X-ray Photoelectron
Spectroscopy (XPS) conducted surface analysis of the
passive films formed on Al-Mo, Al-Ta, Al-Cr, and
Al-W alloys. They found significant incorporation
of the alloying elements into the passive film. It was
suggested that a more protective passive film enriched
with the solute atoms was responsible for improved
pitting resistance by impeding the ingress of chloride
ion through the passive film. Smialowska 50 suggested
that the solute elements in the active pit surface play
the critical role instead of solute in the passive film.
She proposed that the low solubility of the solute
oxide in the acidic pit environment is responsible for
improved pitting resistance. Another explanation has
been proposed by Frankel and coworkers27-29 based
on their measurement of thin film pit growth kinetics
for Al-Nb, Al-Mo, and Al-Cr thin films by sputter
deposition. They found that stable pits initiated at
potentials only about 30 mV higher than they
repassivated (Fig. 10). It was suggested that the
addition of noble alloying elements increased the
pitting and repassivation potential by ennobling the
dissolution kinetics of pit growth rather than the
passive film effect. However, the exact mechanism
by which alloying elements alter the dissolution

Fig. 10 : Pitting potentials for freshly deposited samples, Ep


and aged samples Epa along with repassivation
potentials ER, for pure Al and AlNb alloys.

kinetics is still unclear. Regardless, this dissolution


kinetics viewpoint provides a new insight to understand
the role of alloying elements such as Zn, Mg, and
Cu in Al alloys in pitting corrosion. In the light of
the dissolution kinetics viewpoint, Ramgopal and
Frankel21 recently studied the dissolution kinetics of
Al-Zn, Al-Mg and Al-Cu binary alloys using the
artificial crevice electrode technique. It was found
that Zn, Mg, and Cu addition had different effects
on repassivation potential and the dissolution kinetics.
The addition of Cu increased the repassivation
potential and lowered the dissolution kinetics. The
addition of Zn decreased the repassivation potential
and enhanced the dissolution kinetics. The addition
of Mg had little or no effect on the repassivation
potential by changing the dissolution kinetics. They
suggested that the role of alloying elements was to
mainly change the surface overpotential and thus
shifted the repassivation potentials.
3.2 Intermetallic Particles
Intermetallic particles (IMCs) can be grouped into
coarse intermetallic particles and fine precipitates. In
Al alloys, coarse intermetallic particles form during
the solidification process, while fine precipitates
including hardening precipitates in the matrix and
grain boundary precipitates form during the aging
process. The type and composition of intermetallics
varies with the Al alloy composition and heat
treatment 51. The primary coarse intermetallics found
in Al-Cu-Mg alloy such as AA2024-T3 are Al2Cu

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(S),Al2CuMg (S) and Al20Cu2(Fe Mn)3 52-53. The


coarse intermetallics Al3Fe, Al7Cu2Fe, Al2CuMg, and
Mg2Si are found in Al-Zn-Mg-Cu alloys such as
AA7075-T6. The fine precipitates for AA2024-T3
and AA7075-T6 are Al2CuMg and Mg (Zn Cu Al)2,
respectively. As mentioned earlier, intermetallic
particles play a crucial role in localized corrosion of
Al alloys. The coarse intermetallic particles mentioned
above can be further divided into two groups: active
and noble particles relative to the Al matrix. Al2Cu,
Al3Fe, Al7Cu2Fe, and Al20Cu2 (Fe Mn)3 are found
to be noble to the matrix, while Al2CuMg and Mg2Si
are active to the matrix. Buchheit 54 compiled the
corrosion potentials of various intermetallic phases in
Al alloys, showing that the intermetallics exhibit
different electrochemical properties from the matrix.
Pits are readily found at the periphery of noble
particles in Al alloys during exposure to chloride
solution. It is generally accepted that noble Fe- or
Cu-containing intermetallic particles act as cathodes
and support oxygen reduction. As a result, a high pH
local environment is established at the noble particles,
which causes grooving of the surrounding Al matrix
by alkaline dissolution. The alkaline attack must then
somehow switch to acid attack to result in a stable
pit, which requires an acid environment.
Electrochemical studies have been conducted on Al3Fe
and Al2Cu 55-57. Nisancioglu found that near the
open circuit potential in NaOH solution, Al3Fe
underwent a preferential dissolution of Al, which
resulted in an Fe rich surface55. It was suggested that
Fe enrichment on the Al3Fe surface is detrimental to
cathodic behavior due to the formation of a protective
Fe oxide. The presence of Mn and Si in Al3Fe can
reduce the effect of Fe on both anodic and cathodic
rates. Mazurkiewicz and Piotrowski57 found that
Al2Cu underwent dissolution to form Al and Cu ions
at the open circuit potential and under anodic
polarization in sulfate solutions. Cu ion release was
also found in Rotating Ring-Disk Electrode (RRDE)
experiments on Al2Cu and Al7Cu2Fe at the OCP and
under anodic and cathodic polarization in chloride
solution .
The corrosion potentials for Mg2Si (D) and Al2CuMg
(S) particles in chloride solution are -1.59 and -0.92
V SCE, respectively. Both Mg-containing phases are
active to the matrix and act as anode. They are
susceptible to active dissolution or Mg dealloying

when exposed in acidic solution or chloride solution.


Mg 2Si phase in AA6000 dealloyed in 0.1 M
phosphoric acid and MgO was found on the Mg2Si
particles. Buchheit and coworkers58,60-62 studied the
electrochemical behavior of S (Al2CuMg) phase in
the form of both synthesized bulk and real phases in
AA2024-T3. They found that S phase supported rapid
anodic and cathodic reaction kinetics and selective
dissolution of Mg and Al readily occurred under
anodic and cathodic polarization. Dealloying of active
S phase left Cu-rich remnants, which was cathodic to
the matrix and therefore caused grooving by alkaline
dissolution and then pitting at the dealloyed S phase.
They also proposed that decomposition of Cu-rich
remnants of S phase resulted in Cu release and
redistribution, which further accelerated corrosion of
the Al alloys. This hypothesis has been supported by
RRDE experiments on S particles. The details about
Cu enrichment and redistribution will be reviewed
below. In summary, alloying addition and various
intermetallic particles play an important role in the
corrosion properties of Al alloys.
3.3 Cu Enrichment and Redistribution
The critical role of intermetallic particles in localized
corrosion of Al alloys was described previously. Many
studies revealed that Cu-containing intermetallic
particles govern the corrosion of high strength Al
alloys due to the noble nature of the Cu rich particles.
In chloride environment, Cu-rich particles,
particularly Al2CuMg (S) particles, often lead to Cu
enrichment and redistribution, which in turn is
detrimental to corrosion resistance. Buchheit and
coworkers58,60-62 attributed Cu enrichment in AA2024
to dealloying of S-phase, which accounts to about
60% of total intermetallic particles (Fig. 11). S phase
is susceptible to dealloying in acidic solution or
chloride solution. Selective dissolution of Mg and Al
leaves behind Cu rich sponge remnants. Buchheit
et..al62 further pointed out that Cu redistribution was
attributed to the formation and re deposition of Cu
ions although the corrosion potential of AA2024 is
well below the reversible potential for Cu/Cu2+.
There are two possible explanations for this seemingly
thermodynamic contradiction. They proposed that the
Cu rich sponge remnants undergo physical coarsening,
which results in non faradaical liberation of
mechanically and electrically isolated metallic Cu
clusters.

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TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

Fig.11

: (a) Optical picture and (b) Schematic representing Cu enrichment redistribution during localized corrosion in
AA2024-T3

Metallic Cu clusters suspended in the solution or


isolated in the corrosion product can achieve a
corrosion potential that is not controlled by the alloy
potential. In an aerated solution, metallic Cu is
oxidized into Cu ions. Dissolved Cu2+ ions can drift
around by solution convection and redeposit on the
alloy surface, reducing back to metallic Cu. This
then leads to the localized corrosion in other places.

view point, the curvature effect is thought to be


responsible for the formation of Cu ions rather than
the liberation of metallic Cu clusters. The curvature
of Cu rich clusters on the surface shifts the reduction
potential for Cu in the anodic direction (equation 1),
dramatically when the radius r is very small.

E Cu = E Cu

63-64

Sieradzki and coworkers


proposed a different
viewpoint that Cu ions are formed directly from Cu
rich sponge remnants on the alloy surface. In this

2 Cu Cu
nFr

(1)

where E Cu is the potential of the Cu rich remnant,


E Cu is the reversible potential for Cu, n is

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2 equiv/mol, F is faradays constant (96487 C/equiv),


9Cu is the molar volume of Cu, r is the radius of
the surface curvature and ICu is the surface energy
of Cu.
The formation of Cu ion is possible at the alloy
corrosion potential when the radius is about 40 nm.
Besides the Cu enrichment and redistribution from
the S phase, other arguments have been made to
explain Cu surface enrichment, which do not require
any Cu oxidation or long-range redistribution of Cu
from the S phase. An argument is that Cu on the
surface around the intermetallics comes from the
surrounding matrix 65.According to this viewpoint,
the active intermetallic particles such as the S phase
rapidly dealloy leaving behind the porous Cu rich
remnants, which act as local cathodic sites. The
oxygen reduction reaction occurring at these cathodic
sites increases local pH to alkaline. In local alkaline
solution, adjacent Al matrix around intermetallics
dissolves also leaving behind Cu, which is originally
in the Al matrix. Cu enrichment from both S phase
dealloying and matrix dealloying is possible. Cu
enrichment and redistribution from the S phase is
dominant when AA2024-T3 is immersed in chloride
solution for a short time, whereas, matrix dealloying
contributes to Cu enrichment and redistribution more
than S phase delloying after long time immersion.

4. PITTING MECHANISM IN Al-Cu


ALLOYS
Although the addition of copper increases the strength
of aluminium it dramatically decreases the corrosion
resistance of the metal to seawater. Copper has a
limited solubility in aluminium (2wt%) and unless
the liquid metal is rapidly cooled, copper will not be
uniformly distributed throughout the grains of the
aluminium phase 66. If precipitation hardening
(increase in hardness of the metal due to the
precipitation of the CuAl2 inter-metallic phase) occurs,
the areas around the grain boundaries become depleted
in copper and as such become more anodic (more
reactive) than the rest of the grain. Under these
conditions the metal is subject to inter-granular
corrosion. In the absence of complicating factors the
more reactive metal or Corrosion potentials for a
solution containing 53g 1 1 NaCl, 3g 1-1 H202
from65 metal phase will have a more negative

Table 1
Solid solution or
constituent

Ecorr, the corrosion


potential
Volts rel. N.H.E.,
25C

Cu

+007 noble

Al + 4% Cu in solid solution -036


CuAl2

-040

Al + 2% Cu in solid solution -042


Al

-052

active

corrosion potential (see Table 1). The difference of


100mV in the Ecorr values for pure aluminium and
aluminium with 2% copper in solid solution is quite
large and can lead to markedly different corrosion
rates across the different phases in a sheet of metal.
The copper corrosion products were formed by the
oxidation of the CuAl2 units in the metal structure.
A very com-mon mineral formed during the corrosion
of copper in seawater (pH 82) is cuprous oxide
(Cu2O). Under the same conditions an aluminium
oxide (Al203) will form as aluminium corrodes.
Because of the more reactive nature of aluminium
compared with copper, Cu20 or any other copper
mineral can be converted back to the metal by reaction
with aluminium metal,
2A1 + 3Cu20 A1203 + 6Cu

(2)

The formal cell potential for the above reaction is


+198 volts and so the process is spontaneous.
Examination of the Pourbaix diagram (Fig. 12)
(Eh vs pH) for copper in seawater 67 and for
aluminium 68 shows that none of the copper corrosion
products can co-exist in contact with aluminium metal
under equilib-rium conditions. In the light of this it
is not surprising to find that copper deposits on parts
of the aluminium surface.
In the pitting of aluminium (Fig. 13) the deposited
copper acts as a cathodic site for the facile reduction
of oxygen 69, viz.
02 + 2H20 + 4e 40H

(3)

Noble impurities such as Al3Fe act in a similar


fashion. Chloride ions are known to be absorbed

603

TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

There is an equilibrium between the formation of


aluminium oxide and AlCl3, at the interfacial region
(the area between the metal and the corrosive medium)
viz.
A12O3 + 6H+ + 6Cl-
2AlCl3 aq + 3H2O (7)
When aluminium chloride is formed a pit develops
and when alumina (Al2O3) forms the pit will passivate.
The chloride ions directly affect the corrosion
potential of aluminium in fresh water. The higher
the chloride ion concentration the more negative is
the corrosion potential and the faster the metal will
corrode (in the absence of complicating factors).
Chloride ions accelerate the corrosion process but
whether this is due to oxide film breakdown or
assisting the anodic reaction, is not known. To be
effective in arresting further corrosion the treatment
process must remove the re-deposited copper from
the remaining metal surface and also remove chloride
ions.
Fig. 12 : Potential pH diagram for the system Cu NH3 Cl
H2O Al. The diagram is based on data from [68]
and [74]. Region 1 is the stability domain for
Cu(NH3)12+ region 2 for Cu(NH3)22+ and region
3 for Cu(NH3)32+. Solution conditions are NH3 =
NH4 = 025M, Cl = 2 X 10-3M, Al = 10-6M,
CU = 1 X 10 4M.

onto aluminium 70 and as little as 15ppm chloride


can initiate pit growth due to breakdown of the
protective oxide film 71.
The anodic reaction occurs at the bottom of the pit
Al Al3+ + 3e

(4)

and the aluminium ions migrate towards the


inter-facial region where hydrolysis occurs,
Al3+ + 3H20 Al(OH)3 + 3H+

(5)

which makes the pit acidic. Chloride ions migrate


into the pit to form aluminium chloride (A1Cl3) which
dissolves in the solution. Because of the low pH the
aluminium may also corrode with the evolution of
hydrogen .
2A1 + 6H+ 3H2 + 2A13+

(6)

There is a critical bulk chloride concentration needed


to keep the pit propagating (16M) which is higher
than normal seawater (057M)

5. CORROSION OF WELDS
Welding is an important method of fabrication and
leads to physical, chemical and metallurgical changes
in aluminium alloys. One of the reasons for the
chemical changes in the welds is due to the different
chemical compositions of the filler materials used.
Weld thermal cycle also causes microstructural changes
in the weld metal and heat affected zone (HAZ).
These alloys after welding will be subjected to either
postweld natural aging (T-4) or post weld artificial
aging (T-6). AA6061 and AA2014 alloys are
subjected to single step aging while 7020 alloys is
subjected to two step aging. Though artificial aging
results in higher strength values compared to natural
aging, some times natural aging is preferred from
the viewpoint of toughness.
Though literature on the corrosion behaviour of
aluminium alloys is available, the same cannot be
said of their welded counterparts presumably in view
of the chemical and microstructural changes caused
by welding. The literature survey also indicated that
there were no detailed and comparative studies
available on corrosion behavior of welds of heat
treatable aluminium alloys with respect to changes in
welding and heat treatment conditions.

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SRINIVASA RAO AND PRASAD RAO : PITTING CORROSION OF HEAT-TREATABLE ALUMINIUM


ALLOYS AND WELDS

When localized corrosion does occur in aluminum


welds, it may take the form of preferential attack of
the weld bead, pitting, intergranular attack or
exfoliation may occur in a HAZ a short distance
from weld bead. Welds in Al-Mg-Si alloys (AA6061)
generally have a good resistance to atmospheric
corrosion, but in specifically corrosive environments
like seawater localized corrosion may occur. Welds
in Al-Cu alloys (AA2014, AA2219, AA2026), AlZn-Mg-Cu alloys (AA7075) and Al-Zn-Mg alloys
(7039) have less corrosion resistance, due to
metallurgical changes in the HAZ. Reheat treatment
of the welded part might restore the original corrosion
resistance, but this is rarely possible.

a knife-edge attack parallel to at some distance from


weld.

Some of the heat treatable alloys particularly those


containing substantial amounts of copper and zinc,
may have their resistance to corrosion lowered by the
heat of welding. These alloys exhibit grain boundary
precipitation in the HAZ and of this zone is normally
anodic to the remainder of the weldment. In a
corrosive environment selective corrosion on the grain
boundaries may take place and in the presence of
stress this corrosion can proceed more rapidly. Post
weld heat treatment provides a more homogeneous
microstructure and improves the corrosion resistance
of these alloys. Welds in Al-Zn-Mg alloy were seen
to be attacked preferentially in an area adjacent to
the weld bead when exposed to a corrosive environment
in the as welded condition. Post weld aging for a
sufficient at a high enough temperature eliminated
this preferential attack. Insufficient aging resulted in

In the Aluminium-copper alloys, the heat-affected


zone (HAZ) becomes cathodic, where as in aluminumzinc alloys, it becomes anodic to the remainder of
the weldment The corrosion potentials across the weld
zone for a 5xxx, 2xxx and 7xxx series weldment are
shown in Fig. 14.These differences in potential can
lead to localized corrosion as demonstrated by
corrosion of the alloy 7005 shown in Fig. 15. The
HAZ in the 5xxx alloy is mildly cathodic, where as
the 2xxx alloy exihibits a greater cathodic potential.
The 7xxx series HAZ is anodic to the unaffected
material and would be of great concern. Selection of
proper filler wire is important to avoid cracking during
welding and to optimize corrosion resistance. When
the solution potential of the filler is same as that of
the base metal (4043 for 6061-T6 alloy), optimum
corrosion resistance is obtained. In some cases,

Gas tungsten arc welding (GTAW) and Gas Metal


Arc Welding (GMAW) processes are widely used for
joining aluminium alloys for various applications like
aerospace, defence and automotive industries. The
resistance to corrosion of aluminium alloy welds is
affected by the alloy being welded and by the filler
alloy and the technique used. Galvanic cells that cause
corrosion can be created because of the corrosion
potential differences among the base metal, the filler
metal and the heat-affected regions where
microstructural changes have been produced.

Fig. 13 : Schematic diagram showing pitting corrosion in aluminium

605

TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

Fig. 14 : Effect of the heat of welding on microstructure, hardness and corrosion potential of welds of three aluminium
alloys. (a) Alloy 5456-H3 with 5356 filler (b) Alloy 2219-T87 base metal with 2319 filler (c) Alloy 7039-T6 base
metal with 5183 filler

intermetallic phase formed by the base metal and


filler wire determines the final corrosion resistance
of the weld, for example magnesium silicide formed
during welding 5xxx alloy with 4043 filler can be
highly anodic to all other parts of the weldment 72.
In general, the welding procedure that has the least

influence on microstructure has the least chance of


reducing the corrosion resistance of aluminium
weldments. The alloy with the more negative potential
in the weldment will attempt to protect the other
part. Thus if the weld metal is anodic to the base
metal (as 5356 weld in 6061-T6), the small weld can
be attacked preferentially to protect the larger surface
area of the base metal.

606

SRINIVASA RAO AND PRASAD RAO : PITTING CORROSION OF HEAT-TREATABLE ALUMINIUM


ALLOYS AND WELDS

Fig. 15 : Welded Jiont of alloy 7005 with 5356 filler after


a one year exposure to sea water (a) As welded
joint showing severe localized corrosion in HAZ
(b) Post weld aged effect. Corrosion potentials
measured in 53g/l NaCl plus 3g/l H2O2 versus
SCE.

Unpublished work of the authors on age-hardneble


Al-alloys (AA2014,AA6061,AA7020) deposited with
Al-5% Si (AA4043) and Al-5%Mg (AA5356) fillers
showed a strong dependence of corrosion behaviour
on the chemical and metallurgical changes of Alalloy welds due to welding and post weld heat
treatments.

Conventional Continuous current welding (CCW)


technique of gas tungsten arc welding (CCTIG) limits
the use of base metal property like strength and
corrosion resistance73. Due to steep thermal gradients,
characteristic of CCW, the segregation of elements
and liquid film formation at the grain boundaries
leads to hot cracking in the fusion zone and poor
corrosion resistance. Combination of pulsed current
and magnetic arc oscillation technique using AC TIG
process will improve the hot cracking resistance,
reduce the grain size and micro segregation, and hence
improve corrosion resistance of fusion zone. The
intermetallic phases like CuAl2 in AA2219 and Mg2Si
in AA 6061 Al-alloys are harmful with respect to
weldability and corrosion resistance. These
intermetallic particles induce liquation in the partial
melted zone(PMZ) of the weldment leading to
cracking and galvanic coupling effect of these phases
with the surrounding matrix results in poor corrosion
resistance. Recently, Huang and Kou75 studied the
liquation mechanisms in AA2219, 6061, 2014 and
7075 alloys and suggested that proper care has to be
taken in selecting parameters and filler during GMA
and GTA welding of Al-alloys to avoid liquation
cracking. It is difficult to avoid the PMZ in Alalloys completely, but can be minimized by

Fig. 16 : PMZ areas of GTA Welds of 2219-T6 after Corrosion Testing.

607

TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

controlling the welding parameters and selecting proper


filler wire suitable for the base metal composition
and thermal temper. Recent unpublished work of the
authors proved that PMZ is a strong function of
prior thermal temper of the Al-alloy like T-4, T-6
and T-87.Similarly it was also found that width of
the PMZ is less in pulsed current (PC) GTA welding
compared to that of continuous current (CC) GTA
welding of Al-alloys. Improvement in corrosion
resistance in Pulsed GTA welds of 2219 and 6061
alloys has been attributed to the decrease in segregation
and refinement of eutectic network of the weld metal.
Corrosion studies on Heat Affected Zones with PMZs
in CC and PC GTA welds of AA2219 (T6 and T87)
and AA6061 (T4 and T6) indicated the significant
influence of prior welding technique and prior thermal
temper. HAZs of PC GTA welds of 2219-T87 and
6061-T4 are found be having higher corrosion
resistance when compared to that of T-6 temper.
Corrosion damage is extensive in the PMZ area of
the HAZ due to grain boundary eutectic enrichment
and segregation of alloying elements during welding
and this is evident from the optical microscopy and
scanning electron microscopy studies on GTA welds
of 2219-T6 alloy (Fig. 16). Authors76 recently made
an attempt to study the effect of prior copper removal
treatment on the corrosion resistance of the CC GTA
Welds of 2219-T6 and uniform pitting potential has
been achieved in all three zones of the weldment.
To summarize welding will have a strong influence
on the pitting corrosion of heat-treatable Al-alloys,
mainly microstructural changes in heat affected zone
and partially melted zone might lead to non-uniform
pitting potential across the weldment. Proper care
has to be taken in the selection of welding technique
and the filler wire, depending on the base metal
history of the Al-alloy.

number of metastable pits and the current spikes


increase with increasing applied potential below
pitting potential and the chloride concentration.
The potential distribution in pits is considered to
be another important factor to stabilize pit growth
and a pit must maintain a minimum current
density for stabilized growth.
2.

Pitting potential ( EP) and Repassivation potential


( ER) can be used to evaluate the susceptibility
to pitting corrosion of aluminium alloys and
recently Electrochemical Impedance Spectroscopy
(EIS) has been recognized as the accurate method
of determining the corrosion resistance of
aluminium alloys in solutions containing
aggressive halide ions.

3.

The role of alloying elements was to mainly


change the surface over potential and shifting
the repassivation potential. Intermetallic particles
weaken the passive film and are sites for pit
nucleation. Cathodic intermetallics produce a
galvanic cell with aluminium matrix and act as
cathode for the oxygen reduction.These particles
selectively dissolve and remnants from the
particles dissolution- metallic Cu, Fe are still
more cathodic than the intermetallics. High pH
local environment is established at these particles,
which causes grooving of the surrounding almatrix by alkaline dissolution.

4.

Copper enrichment and re-distribution is the root


cause of pitting in aluminium-copper alloys.
Chloride ions which accelerate the corrosion
process may be attributed to oxide film break
down or assisting the anodic reaction.

5.

Pitting corrosion resistance of heat-treatable


aluminium alloy welds depend strongly on
welding technique and the prior thermal temper.
Partially melted zone of the Al-alloy welds is
severely damaged by corrosion and is attributed
to the grain boundary eutectic enrichment and
segregation.

6. CONCLUSIONS
1.

In general, pitting corrosion involves three stages:


pitting initiation, metastable pitting, and pitting
growth. Three main models of pit initiation are
i) adsorption mechanism ii) penetration
mechanism and iii) film breaking mechanism
and these models address important aspects of
pit initiation such as aggressive ion adsorption,
ion penetration and migration, and stress-induced
breakdown of passive film respectively. The

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