J. Mater. Sci. Technol., Vol.25 No.

1, 2009 95
Eect of Oxide Inclusions on Electrochemical Properties
of Aluminium Sacricial Anodes
M. Emamy
1)
, A. Keyvani
1)
, M. Mahta
1)
and J. Campbell
2)
1) School of Metallurgy and Materials, University of Tehran, Tehran, Iran
2) Department of Metallurgy and Materials, University of Birmingham, B15 2TT, UK
[Manuscript received October 25, 2007, in revised form September 3, 2008]
Oxide lms are incorporated into melts by an entrainment process, and are expected to be present in most
metals, but particularly cast Al alloys. The oxides are necessarily present as folded-over double lms (bilms)
that are eectively cracks. Their eect on the electrochemical behaviour of cast Al-5Zn-0.02In sacricial
anodes was studied in 3 wt pct sodium chloride solution using the NACE eciency evaluation. Three methods
were employed to entrain progressive amounts of oxide in the alloy, including the addition of Al-Zn-In maching
chips to the charge, increasing the pouring height, and agitating the melt. The introduction of oxide bilms
in the cast alloy resulted in the deterioration of the electrochemical properties of the sacricial anodes, such
as current capacity and anode eciency, and introduced increasing variability in these properties. The results
suggest that corrosion behaviour is strongly related to the presence of bilms suspended in the liquid alloy
because bilms provide crack paths allowing the corrodant to penetrate deeply into the metal matrix, and
simultaneously provide localized galvanic cells because of the precipitation of Fe rich intermetallic compounds
on their outer surfaces.
KEY WORDS: Aluminium; Sacricial anode; Eciency; Entrainment; Bilm
1. Introduction
Aluminium alloy sacricial anodes are widely used
in cathodic protection technology. Among these al-
loys, Al-Zn-In anodes are common because of their
low polluting eect on the seawater environment com-
pared with Mg-activated Al anodes, and because of
their relatively easy manufacturing techniques com-
pared with Sn-activated aluminium anodes, which re-
quire heat treatment after casting. However, their
valuable properties, due to low specic weight, low
electrode potential and high theoretical current ca-
pacity, are often hindered by the presence of a pas-
sive oxide lm which causes several diculties in their
practical application. The omnipresent oxide on the
metal surface in aqueous environments is the result
of rapid polarization. In addition, localized corrosion
of the alloy occurs in halide-containing environments,
reducing its eciency
[14]
.
The performance of aluminium alloys as sacricial
anodes has been directly related to its electrochem-
ical eciency
[5]
. To achieve good performance, re-
search has focused on the development of aluminium
alloys, whose oxide lm can be broken down. For that
purpose, several studies have been made, including
the eect of alloying additions
[57]
, the eect of cast-
ing parameters
[8]
and microstructure control
[9]
. The
aim has been to achieve a uniform structure together
with a uniform distribution of precipitates in the -
Al matrix, capable of preventing the formation of the
continuous, adherent and protective oxide lm on the
alloy, thus permitting a continued galvanic activity of
the aluminium sacricial anode
[5,10]
.
Alloying elements such as Zn, In, Sn and Ga
are added to achieve active dissolution of aluminium
and thereby obtaining good anode eciency. In
Corresponding author. Assoc. Prof., Ph.D.; E-mail address:
emamy@ut.ac.ir (M. Emamy).
addition to the amount of alloying elements presented
in Al-Zn-In alloys, the distribution of these alloying
elements both in solid solution and segregated form,
and the grain size
[11]
, which depends in turn on the
casting conditions, can all aect the electrochemical
behavior of the anode.
In addition, the anode behaviour would be ex-
pected to be aected considerably by a variety of de-
fects in the casting. The most important of these
are expected to be oxide bilms. These defects arise
principally, but not exclusively, during the pouring of
liquid metal. The entrainment process is an enfolding
process; the oxide on the surface of the liquid is folded
in to the bulk melt, necessarily folding with the top,
dry side of the oxide face to face in the fold. The folds
are often separated by a microscopically thin layer of
air, thus constituting an eective crack in the liquid.
Thus as a necessary consequence of the entrainment
process, all oxide lms in melts are necessarily dou-
ble (giving the name bilm) and necessarily act as
cracks
[12]
.
Thus turbulent pouring can ll the liquid with
cracks. These bilm defects remain in suspension
for long periods in Al melts because of their nearly
neutral buoyancy, and can be created in high den-
sities with poor melt handling and poor casting
techniques
[12]
. The outer surface of the bilm are
those interfaces that have grown atom-by-atom dur-
ing the oxidation of the melt surface, and so, of course,
are in excellent atomic contact with the matrix alloy.
This curious structure of the bilm, with its unbonded
internal interface and atomically cohered external in-
terfaces gives the defect its unique properties.
The outer surfaces constitute favoured substrates
for the precipitation and grown of many inclusions
and intermetallics during the freezing of the alloy, par-
ticularly Fe-rich and Cu-rich phases
[12,13]
.
In their turn, the bilms assist to initiate a retinue
of well-known casting defects such as shrinkage cavi-
96 J. Mater. Sci. Technol., Vol.25 No.1, 2009
Table 1 Chemical composition of the alloy used as sacricial anode (wt pct)
Zn In Fe Cu Ti Pb Si Al
4.994 0.022 0.152 0.005 0.002 0.040 0.070 Bal.
ties, gas porosity, cracks and hot tears in solidied
castings
[14]
. The tangled network of oxide lms con-
stitutes cracks of convoluted morphology (quite unlike
cracks caused by stress) that can signicantly reduce
strength. The folded nature of oxide bilms allow
them to re-open, becoming extensive planar cracks or
even pores when the oxide bilms are subjected to
the internal pressure of hydrogen gas, or the external
reduction in pressure due to shrinkage.
The bilms described above result from turbulence
form in the few milliseconds of the surface folding
and are submerged. Therefore they have little time
to thicken. Such thin bilms are called new bilms
and may be only a few nanometres thick (even though
they may have extensive area of course).
In contrast, charge material added to the crucible
to eventually make up the melt, becomes heavily ox-
idised before it melts, and these oxide skins can, of
course, become incorporated into the melt. These are
generally thick oxide lms, generally known as old
oxides that can be any thickness up to several millime-
tres. They may be folded over to created totally old
bilms. However, more usually, it is to be expected
that the act of passing through the melt surface to
be incorporated in the bulk melt will wrap the thin
new lm on the liquid surface around the old piece of
lm as it is submerged. In this way, it will create an
asymmetrical bilm consisting of one half of old thick
lm, and one half of new thin lm.
It is wide experience in the Al casting industry
that the addition of a substantial content of machin-
ing swarf or chips to a charge results in enhanced ox-
ides in the melt. Thus this attested oxide addition
technique was employed in this work.
Turning now to consider those oxides introduced
during pouring, where the speed of the falling melt
naturally increases with increasing height. A fall
of over 12.5 mm is, in theory, sucient to generate
enough energy to entrain lms
[12]
. However, in sim-
ple practical pouring experiments, Turner
[15]
showed
that 80 mm of fall was required to entrain bubbles of
air. Bubbles are known to create copious oxide lms
as a result of the creation of the oxide trails (bub-
ble trails) that they leave in their wake as they oat
up to the surface
[16]
. It is well known in the casting
industry that even greater fall heights lead to consid-
erable metal losses because of the creation of dross.
Thus increasing fall height appears to be another well-
attested technique for the increase of oxides in a melt.
This simple technique was also used to provide melts
with progressively increasing bilm content.
The bilms formed during agitation of the surface
of the melt, and especially during nal pouring into
the mould are expected to be uniformly thin. Even so,
the presence of the thin side to the older lms gener-
ated from the charge materials means in practice that
both young and mixed young/old bilms will proba-
bly behave similarly. Thus all three techniques used
to enhance the oxide content of melts are expected to
result in similar defects, and therefore produce similar
changes in the behaviour of the alloy.
2. Experimental
The chemical composition of the ternary Al-5%Zn-
0.02In sacricial anode material is shown in Table 1.
All fteen melts studied in the three main groups were
based on this composition. Only the casting parame-
ters were varied.
The alloy ingots were cut, dried, weighed and
melted in a 1 kg of clay-graphite crucible in an elec-
trical resistance furnace. The temperature was care-
fully controlled and monitored using a K-type thermo-
couple. When the melt reached the temperatures of
750

C (1382

F), it was thoroughly skimmed. After-

wards the melt was homogenized by manual stirring
with graphite rods for about 20 s.
To study the eect of oxide impurities, three ar-
ticial methods of oxide entrapment were used: (1)
addition of Al-Zn-In chips with an average diameter
of 0.53 mm up to 60 wt pct, (2) increasing the pour-
ing height from 30 to 480 mm and (3) melt agitation
carried out using mechanical stirring action by means
of a graphite impeller rotating at 4 Hz (250 r/min)
for dierent times between 20 and 300 s.
The surface oxides were nally skimmed prior
to pouring the molten metal into a small cast iron
mould with 60 mm height and a cross section area of
25 mm25 mm.
Samples were sectioned transversely at 25 mm
above the bottom of each casting and cleaned by
50 g/l NaOH solution and afterwards by 65% HNO
3
and then washed with acetone, dried and nally
weighed to 10
4
g in accuracy. Accelerated disso-
lution tests at current density of 6 A/m
2
in 0.5 mol/L
NaCl solution (the standard electrolyte according
to ASTM-D1141-52) were performed over 14 days
to determine the anode current capacity and po-
tential variation vs time according to the NACE
standard method TM0190-98
[17]
. Some of the tests
were repeated to check reproducibility. The poten-
tial values were measured with a standard saturated
calomel electrode (SCE). After the test, specimens
were cleaned from corrosion products in a solution
of 41 ml H
3
PO
4
+28 g Cr
2
O
3
+1.4 l distilled water at
80

C for about 5 min. The samples were nally dried

and weighed again. The current capacity and anode
eciency evaluated according to the ASTM G97 stan-
dard can be expressed as:
Current capacity, C.C.

Ah
Kg

Q
W

1000 (1)
Anode eciency =

C.C
2981.5

100 (2)
where, C.C. is current capacity, Q is quantity of the
total charge passed through the electrochemical cir-
cuit, W is total weight loss and 2981.5 is the the-
oretical current capacity of aluminium according to
J. Mater. Sci. Technol., Vol.25 No.1, 2009 97
Fig. 1 Surface turbulence leading to the entrainment of
the surface oxide as a bilm (AB), and the addi-
tion of a machining chip (C) entraining a wrap-
ping of young lm around machining chips (D,
E) as they are added to the melt; their old oxide
(shaded) being surrounded by a layer of air and a
young oxide to form an asymmetrical bilm
Faraday

s law
[18]
. These experiments also allow deter-
mination of the coupled potential, which corresponds
to the average of the potentials recorded each day.
Microstructural studies were made on polished
sample surfaces by optical microscopy and Cam-
Scan MV2300 scanning electron microscopy (SEM)
equipped with energy dispersive X-ray analysis
(EDX).
3. Results and Discussion
The inuence of oxide entrainment by various
processes, i.e. increasing the pouring height, scrap
addition and nally surface turbulence, on the anode
eciency and current capacity of Al-5Zn-0.02In sac-
ricial anode in the accelerated dissolution tests, are
shown in Fig. 1. It is seen that in all cases oxide inclu-
sions in the Al anode reduce both the current capacity
and anode eciency.
Under the conditions of this study, the eects of
each of the three oxide addition techniques result in
similar behaviour. This is interesting, and not entirely
to be expected. It is true that each technique would
be expected to result in a progressive increase in ox-
ides, and some progressive response of the corrosion
reaction. However, in each case, the fall in current
capacity occurs approximately linearly, and by a non-
trivial amount, approximately 16%.
Also, of course, the linear behaviour indicates that
even more reduction occurred with more added ox-
ides. Thus the eect of oxides can be clearly sub-
stantial. Since oxides have rarely been monitored in
many engineering alloys, and the importance of their
eect on the mechanical properties of Al casting alloys
has only recently been appreciated, this discovery is
a source of concern.
A detail of the response of the potential to the
height of fall of the melt in Fig. 1 is signicant. The
small threshold of approximately 80 mm required be-
fore any signicant impact on the potential variation
in Fig. 1 once again corroborates the expectation that
oxides are being entrained in the melt by increasing
the fall of metal. The head height of 80 mm exactly
agrees with the observations by Turner
[15]
that bub-
bles are only entrained above this height, and the ob-
servations by Divandari and Campbell
[16]
that bub-
bles in Al melts always result in bubble trails con-
sisting of collapsed tubes of oxide, eectively creating
Fig. 2 Current capacity and eciency values of anodes
with dierent methods of oxide incorporation
long bilms in the melt.
The potential variation vs time curves are shown
in Fig. 2 illustrating changes of the operating po-
tential with time. Non-uniform dissolution process
has been previously observed in alloys with columnar
structure and over-grain-rened Al-Zn-In anodes
[11]
.
However, these conditions do not appear to be applied
in this case. The eects in this study are almost cer-
tainly directly related to the concentration of oxides
present. The addition of oxides by all three methods
intensies the potential dierences between anodes,
and leads to the increase of the potential instability.
This uctuation in the potential with time (Fig. 3)
is associated with the non-uniform corrosion of the an-
ode, especially pitting as seen in Fig. 4, and possibly
associated with the penetration of the electrolyte into
the bilms, and the arrival of the electrolyte at sites
of intermetallic precipitates at random locations on
the bilms. The precipitates, often being high in Fe
and/or Cu will be act as eective corrosion couples.
The typical EDX result in Table 2 indicates a signif-
icant level of Fe in association with an oxide bilm.
Iron-rich intermetallics are precipitates on the outer
surfaces of young bilms (and the old oxide lms from
the chips will be associated with a young oxide as a
result of the entrainment mechanism). The random
siting of intermetallics may explain the random uc-
tuations of potential observed. The corrodant will
98 J. Mater. Sci. Technol., Vol.25 No.1, 2009
Fig. 3 Potential variations vs time plots of aluminum anodes with dierent: (a) weight percent of Al-Zn-In scraps,
(b) pouring height and (c) stirring (agitation) time
Table 2 EDX results of the oxide inclusions
Element/at. pct
Figure Condition
Al O Fe Zn
5 Scrap addition 79.45 16.04 1.22 3.29
6 Pouring height 61.33 38.67
J. Mater. Sci. Technol., Vol.25 No.1, 2009 99
Fig. 4 Optical images of corroded Al-Zn-In anodes after 14 days using dierent entrainment techniques, showing
localized attack
Fig. 5 Eect of dierent methods of oxide entrainment on the average potential uctuations with standard devi-
ation
Fig. 6 X-ray mapping of elements distribution in a bilm crack accompanied by old oxides, an open path for the
entry of corrodant, incorporated by scrap addition (60 wt pct) and EDX microanalysis obtained from the
arrowed old oxide inclusion (a)
100 J. Mater. Sci. Technol., Vol.25 No.1, 2009
Fig. 7 Secondary electron image of aluminum oxide in-
corporated by increasing the pouring height to
360 mm (prior to chemical attack)
arrive at such locations at random times to create a
temporary cathodic potential against the aluminium
matrix, behaving as a cathode while the localized cor-
rosion cell remains active.
With regard to the increasingly nonuniform corro-
sion of the anode with increasing levels of oxide, if suf-
cient oxides could be introduced, uniformity might
return. This might explain some of the irregularity of
the response evident in Fig. 4.
Increasing the usage rate of foundry returned ma-
terials causes an increase in the amount of old oxides
incorporated into the melt and the possibility of their
inclusion in the cast alloy. This situation was simu-
lated in this work by the incorporation of machining
chips of the alloy into the melt charge. Figure 6 shows
the X-ray elements distribution of Al sacricial anode
obtained by the maximum addition (60 wt pct) of
chips. The low oxygen counts in Fig. 6 almost cer-
tainly the result from the dilution of the count with
matrix signals because the oxide lm is relatively thin.
However, as an old oxide, it is just thick enough
to provide some detectable X-ray response. Interest-
ingly, Table 2 illustrates that this bilm was associ-
ated with approximately 10 times of the matrix iron
content, as expected from the bilm being a favoured
substrate for iron precipitation.
Figure 7 shows the SEM image of a sample poured
from the greatest height (360 mm) indicating typical
crack-like oxide bilms coupled with shrinkage pores.
These have led to localized corrosion of the anode.
The chemical composition of the oxide particle ob-
served in this image obtained from X-ray microanaly-
sis is listed in Table 2, indicating that the particle
is almost certainly alumina. This is unlikely to be
formed during casting or solidication. It is just pos-
sible that it may have originated as a very old oxide
from the melting furnace. However, it is more likely
to be an artifact of the metallographic preparation in-
volving alumina grinding and polishing media. It is
important that the majority of the oxides introduced
during melting and casting are in the form of lms,
not particles.
Figure 8 shows X-ray mapping of a sample of alloy
with 360 s melt agitation. The oxygen gure shows
an absence of any signicant numbers of counts. This
response is typical of a new lm that may be only
nanometres thick.
It seems clear that this study has revealed the ac-
tion of bilms to be critical in chemical dissolution
of metals. Not only do the crack-like nature of the
bilms provide a route into the interior of the ma-
terial, but the presence of iron-rich and other inter-
metallics precipitated onto the outer surfaces of the
bilms (and therefore separated from the penetrating
corrodant by only nanometres of fragile and probably
fractured oxide lm) provide excellent corrosion cou-
ples to enhance pitting corrosion attack. A schematic
illustration is outlined in Fig. 9.
Fig. 8 X-ray mapping of elements distribution in an oxide bilm in shrinkage porosities, incorporated by melt
agitation (360 s)
J. Mater. Sci. Technol., Vol.25 No.1, 2009 101
Fig. 9 Schematic representation of new oxide defects in
deterioration of anode eciency. Black particles
are Fe-rich intermetallics. Successive dissolution
and propagation of the corrodant is depicted by
successive contours, illustrating the nal stages of
fragmentation of the anode associated with the
fall in anode eciency
4. Conclusions
(1) Casting conditions have a major inuence on
anode performance and can aect the quality of gen-
erated anodes. Oxides originating from the melt, or
introduced by the surface turbulence from pouring or
agitation of the melt, all have similar non-desirable
eects on the current capacity and eciency of Al-
Zn-In anodes.
(2) Presence of high densities of double oxide lms
(bilms), acting as cracks, which provide open path-
ways for the entry of corrodant into the interior of the
alloy, not only reduces the current capacity but also
leads to macroscopic fragmentation of the anode. In
addition, of course, the anode eciency deteriorates
appreciably.
Postscript
Recent work has revealed that bilms are unfortu-
nately prolic in many of our currently available engineer-
ing metals, but can be largely avoided by careful melt
preparation and good design of the melt handling and
casting processes
[19]
. This includes, if possible, the avoid-
ance of pouring of the melt, or pouring via carefully de-
signed plumbing systems, or the counter-gravity lling of
moulds. It follows from this study that alloys cast using
appropriate casting technology can be expected to have
signicantly enhanced corrosion rsistance
[12]
.
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