Corrosion Science 48 (2006) 42434256

www.elsevier.com/locate/corsci

The activation of aluminium by mercury ions

in non-aggressive media
J.B. Bessone

INIEC-Dto de Ingeniera Qumica, Universidad Nacional del Sur, Av. Alem 1253,
8000 Baha Blanca, Argentina
Received 10 October 2005; accepted 16 March 2006
Available online 16 October 2006

Abstract
The presence of Hg at concentration less than 300 ppm in Al base alloys causes their passivation
breakdown. On alloys used as sacricial anodes, it causes a major lowering (>0.3 V) in their operational potential in chloride media. Mercury as trace constituent in the natural gas stream causes
severe damage to cryogenic heat exchangers. The present paper presents evidences of the mechanism
by which mercury produces its pronounced eect in aqueous non-aggressive media. The work was
carried out using pure (99.99%) aluminium and mercury (II) acetate solutions of dierent concentrations and pH. Open circuit potentialtime responses were obtained. The surface eects were followed
by means of scanning microscopy and EDAX/X-Ray analysis. The results demonstrate that immediately after immersion, the initial air-formed oxide lm underwent a dynamic crackhealing process
at aws in the lm, possible associated to grain boundaries. The subsequent healing process, if any,
depends on the media composition. Thus, in this special case, Hg2+ ions can be directly reduced on
the bare aluminium, reaching a true metallic contact, and initiating surface diusion. This enables
the formation of an amalgam. Aluminium atoms diuse through the liquid mercury and undergo
oxidation at the amalgam/electrolyte interface. This process is responsible for the oxide detachment
(by undermining) and the attack morphology (i.e., wide cavities).
The presence of aggressive anions is not needed to initiate activation.
 2006 Published by Elsevier Ltd.
Keywords: Aluminium activation; Amalgam corrosion; Hg decoration; HgAl attack morphology

Tel./fax: +54 291 459 5182.

E-mail address: jbessone@criba.edu.ar

0010-938X/$ - see front matter  2006 Published by Elsevier Ltd.

doi:10.1016/j.corsci.2006.03.013

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J.B. Bessone / Corrosion Science 48 (2006) 42434256

1. Introduction
Without exception, all the currently successful aluminium sacricial anodes are ternary
(or higher) alloy systems. One component is always one of ve elements, called activators
(Hg, In, Ga, Sn, Bi), that are known to cause a major (>0.3 V) lowering of the operating
potential. The presence of Hg at concentration less than 300 ppm, in Al base alloys, causes
this lowering in the operational potential [1] in chloride media. Increasing eorts have been
done [27] to understand the Al activation process produced by activators elements and
specially those of low melting points [814]. Some of them [1,4,79] presented interesting
results of Al activation produced by Hg and In as alloying elements or electrolyte additives
(Hg2+, In3+, Ga3+) [1012], but no intention to explain the activation mechanism was put
forward. Recently, the electrochemical behaviour of pure Al in the presence of Ga3+ or
when a particle of Ga was mechanically attached to Al, in chloride and acetic acid solutions
and distilled water was studied [14]. Two activation mechanisms were proposed. (i) When a
critical surface concentrations of Ga in liquid state are achieved, a GaAl amalgam is
responsible for the activation process (1.5 V versus SCE). (ii) At higher anodic potentials
(near 1.1 V), and in aggressive media, the presence of solid Ga (saturated amalgam) at the
interface facilitates a chloride adsorption process which depolarised the anodic reaction,
and gives a more localised attack. On the other hand, the same amalgamactivation mechanism was considered to explain the activation of AlZn alloy by In deposition [13].
The release of trace amounts of Hg present in a gas stream, into a cryogenic heat
exchanger used in the gas processing, promotes corrosion of aluminium metal and alloys
used to construct this equipment. Aluminium is widely used in such machinery because of
its heat-transfer properties, high strength-to-weight ratio and ease of fabrication. Aluminium alloys have the highest strength-to-weight characteristic of any commercial metal. The
strength of the various aluminium alloys increases, with little change in ductility, as temperatures drop into the cryogenic range. The primary symptom of mercury corrosion is
loss of mechanical strength in the aected components due to intergranular SCC [15].
The Al alloys containing Hg, either sacricial anodes or opened aluminium cryogenic
units, in presence of moisture, presented a feathers like white loose corrosion products.
Mercury can corrode aluminium basically by a combination of physic and electrochemical mechanism, which can be stress-assisted [16].
Amalgamation (Physic corrosion): Mercury adsorption on bare Al induced localized
reduction in the strength of the atomic bonds of Al producing liquid solutions or alloys
due to atoms-diusion through the HgAl interface. The thin coating of aluminium
oxide formed upon exposure to air, oers some protection, although it contains surface
defects. It is dicult for liquid mercury to penetrate into the metal underneath because
of its surface tension. However, gaseous mercury can penetrate, condensate and initiate
amalgamation. In this process, Hg wetting is the initial and conditioned step. Afterwards, atom-diusion is the control variable, limited by amalgam saturation.
Amalgam corrosion (Electrochemical corrosion): occurs when mercury and aluminium
amalgamate in the presence of moisture
Hg + Al ! Hg(Al)

Hg(Al) + 6H2 O ! Al2 O3  3H2 O + H2 + Hg

J.B. Bessone / Corrosion Science 48 (2006) 42434256

Hg + Al ! Hg(Al)

4245

The rst step is physic corrosion, followed by the electrochemical oxidation of Al and
water reduction. It produces a hydrated alumina, hydrogen gas and free mercury. The
reaction is self-propagating as long as moisture is still present. The protective aluminium
oxide coating can be attacked if the surface tension is suciently lowered. Penetration into
the aluminium structure can be fairly rapid, but not as rapid as LME corrosion.
Liquid metal embrittlement (LME): Mercury embrittles both pure and alloyed Al
[1720]. Under applied or residual positive stress, SCC of aluminium by liquid mercury
occurs through rapid dissolution and weakening of the intergranular crystalline boundaries by the amalgamation processes described above. The corrosion spreads along the
grain boundary interface, because it concentrate the stress and nd a weaker bonding of
their atoms, resulting in characterized longitudinal cracks and faults transporting the
mercury deeper into the metal structure. The unusual aspect of LME is that the cracking can occur very quickly and that the stress required is very low.
Galvanic corrosion: occurs when Hg2+ ions are in contact with metallic Al in aqueous
solution. Galvanic corrosion from mercury deposits can even develop on steel in corrosive environments, accelerating acid dissolution and aggravating localized corrosion
eects.These mechanisms appears related because all of them need Hg wetting as an initial step. Once initiated, each one responds to a dierent control. Thus, the rst one is
under atom-diusion control; the second one is under electrochemical control; the third
one under the applied or residual positive stress and the last one is a particular electrochemical case, between Hg2+ ions and metallic Al.
Normally the eect of Hg has been studied when it is present in the Al base alloy, and in
aggressive media [4,21]. On the other hand, Valand and Nilsson [2224] through an elegant
method, studied the electrochemical behaviour of pure Al and AlSn alloy in Na-acetate
buer solutions, where a cathodic reaction, potential independent, was considered to take
place at cracked aws present in the oxide. In our case, Hg2+ ions are added to the same
non-aggressive electrolyte (acetate solutions). Thus, variables such as the Hg2+ ions concentration and solution pH are better analyzed in the initiation of the Al activation mechanism. It is intended to assess, in the rst instance, if reduced Hg per se, is capable of
producing an Al active state, and the mechanism by which this process occurs. The Al
active state is reached when the Al oxidation reaction is suciently depolarised. This eect
will appear if the Al oxide lm is destroyed or avoided. Earlier evidences of Hg2+ ions on
Al are found on the stripping process used by Furneaux et al. [25] to isolate the anodic
oxide lm previously formed on Al for its study on TEM. The oxide lms of dierent
thickness, were cut and introduced in a mercuric chloride solution. After few seconds,
the lm was detached and appeared oating on the solution. This procedure does not permit to analyse the activation mechanism. Therefore, to produce a systematic study on this
issue, a pure Al electrode, following always the same procedure, was polished and left to
air to form an spontaneous oxide lm, of several molecular layers which in 25 h reached a
thickness [26].
2050 A
No matter the degree of purity claimed by any special technique employed in producing
a pure metal, even though an ideal homogeneous system is dicult to obtain. Impurity
segregates (Cu, Fe, Si), non-metal inclusions, second-phase particles or intermetallic compounds (FeAl3) are present at the grain boundaries or within the matrix itself. Alterna-

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J.B. Bessone / Corrosion Science 48 (2006) 42434256

tively, dierent surface treatments either mechanical or chemical, render various surface
irregularities. Scratch lines, surface cavities, sheared edges and emergent dislocations give
rise to macroscopic and microscopic surface heterogeneities [27,28]. Regions of localized
impurity segregation shield the Al substrate during oxidation, producing awed regions
in the lm or regions of impure lm. Tensile or compressive stress arising from the undulating metal surface is also likely to lead to localized stress release by oxide cracking during
oxide lm growth. It might be followed by healing of the lm, leaving a aw in the oxide.
These latter types of aws were earlier regarded as mechanical aws, which were
thought to be predominant in air-formed lms [27]. Those aws associate with secondphase precipitates particles or impurities were regarded as residual aws. Bare Al can
be revealed by means of a mechanical breakdown of the oxide present at the base of ows
[26,29] or by its localized dissolution [30,31]. The former case is expected to be caused by
the relief of stresses present in the oxide and those derived from the substrate, particularly
when the specimen is immersed in aqueous solutions [32]. Thus crackhealing (CH)
events are expected to occur continuously. Whether they develop into active sites or
repassivate will depend upon local electrochemistry and chemistry which in turn depend
upon solution composition and pH and alloy composition.
2. Experimental details
Sheet electrodes of 1 cm2 and 1 mm thick were made from pure Al (99.99%), (with
5 ppm of Si, 4 ppm of Fe and 3 ppm of Cu). They were polished with 1000 emery paper
followed by 1 and 0.3 lm grit alumina suspensions and then cleaned with triply distilled
water. Then they were electropolished and left for 2 h in a CaSO4 desiccator where a thin
air formed lm was developed. A grade mercury (II) acetate solution prepared with triply
distilled water were used. Free corrosion potentials readings were taken through a Hg/
HgSO4 reference electrode, using a Solartron 7060 digital voltmeter. All potentials in this
work are referred to SCE. The corrosion products attached to the Al specimens were
removed, when required, by immersing in a chromicphosphoric mixture, at 70 C for
1 h. The CrP mixture composition was: 25 g/l CrO3 + 30 ml/l H3PO4 (SP = 1.75, 88%
min). No appreciable substrate damage is observed, when comparing an Al specimen
before and after treatment in the CrP mixture operated under theses conditions [33]. A
dual stage ISI DS 130 SEM and EDAX 9600 energy dispersive X-ray analyzer were used
to examine the electrode surface characteristics.
3. Results and discussion
3.1. The aluminiummercury ions system
The Hg2+ ions source is obtained from an Hg (II) acetate salt (Hg(C2O2H3)2), due to
the non-aggressiveness of the acetate anion [34] (i.e., the corrosion c.d. in 0.1 N Na-acetate
solution remains below 102 A/m2), and the relatively soluble mercuric salt [35]. Thus, the
eect found, if any, can only be ascribed to the presence of Hg2+ ions. As a rst approach
in the study of the Al/Hg2+ ions system, the potentialtime (Et) response of an Al specimen immersed in a 103 M Hg (II) acetate solution, pH = 4.2, is followed. Fig. 1 shows
that three dierent regions can be distinguished: (a) an initial region, where the potential
rises to a maximum and then slowly decreases, identied as the decoration region; (b) a

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Fig. 1. Potentialtime response of Al activation process by Hg. Al in 103 M Hg (II) acetate solution, pH = 4.2.

second region, where the potential is sharply shifted towards a very negative value, after
nearly 11 min, called the activation region; (c) a nal region, called attack development,
where the potential remains approximately constant. Each of these regions is subsequently
analysed. To begin with, the decoration region is studied, where a passive state seems to
remain over the macroscopic aluminium surface.
3.2. Mercury decoration on aluminium
The Hg decoration on Al was examined by immersing an Al specimen in a 101 M Hg
(II) acetate solution, pH = 3.4. The standard electrochemical potential of the couple Hg/
Hg2+ is +560 mV [35]. Whilst for the Al/Al3+ couple it is 1901 mV. In the working conditions initially used, a strong driving force arises between the Al oxidation and Hg2+ ions
reduction. The Al oxidation reaction takes place mainly to heal the cracked aws. This
reaction will displace the Hg2+ ions from the solution, reducing them at preferential cathodic sites according to:
Al ! Al3 + 3e
Al

+ 3H2 O ! Al(OH)3 + 3H

Hg2 + 2e ! Hg

5
6

Therefore, if Hg-containing particles are identied, it is likely that they correspond to

metallic Hg. The X-ray analysis (Hg Lx X-ray energy) and EDX spectrum performed on
the particles, demonstrated the presence of Hg species. During this experiment, the same
specimen was retired and observed by SEM at 10 s, 1 min and 6 min. The nal state is
shown in Fig. 2(a). This experimental sequence demonstrated that the Hg droplets
increased in number and size. This increasing population density of Hg droplets also suggests that a dynamic crackrepassivation process is taking place at the base of the oxide
aws. During this successive decoration process, the Et response was followed. Initially

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J.B. Bessone / Corrosion Science 48 (2006) 42434256

Fig. 2. SEM Micrographs after the successive Hg decoration on an electropolished Al specimen. Al immersed in
101 M Hg (II) acetate solution for 6 min. (a) Hg population density = 3.0 109 m2, 290. (b) Hg drop at high
magnication (22 K) showing the narrow tail.

the potential rose to +100 mV and remained constant throughout the experiment. The
passive state was sustained, as demonstrated by the potential subsequently measured in
a 0.5 M Na2SO4 solution (230 mV). The reason for this procedure is given in Section
3.5. The relatively noble potential attained during the decoration can only be explained
by accepting the formation of a strong polarising couple Hg/Hg2+. This anodic polarisation will favour the oxide cracking at the base of aws by increasing the electrostriction
pressure at them [32]. This polarising eect also implies that an electronic contact between
Hg and Al has been reached when Hg was reduced. As seen later, this contact is the initiation of the Al activation process. Therefore, two probable situations may co-exist to
maintain a passive decoration state. Firstly, the Hg2+ ions are reduced on pre-existing
cathodic impurities (Fe, Cu) present in the air-formed lm, which avoid the requirement
of a direct Hg contact with the bare Al. This establishes a good electronic contact through
which the Hg/Hg2+ couple polarises the whole specimen. Secondly, Hg2+ ions are reduced
within a cracked aw, which immediately after restored the oxide lm around the HgAl
avoiding activation and further Hg surface diusion by the increased Hg surface tension
on that oxide lm. Thus, Hg can be detached from the Al contact by this crackrepassivation process, as was suggested by Reboul et al. [8]. At high magnication (22 K) each
Hg drop showed a narrow tail-like feature (Fig. 2(b)), which is interpreted as an Hg
decorated channel through an oxide crack, facilitating the electronic conduction. EDX
analysis could not detect the presence of cathodic impurities (Cu, Fe) within the Hg
channel. Therefore, the likely narrow Hg tail observed may correspond to any of the
cases mentioned. Thus, two possible situations may arise: (a) Hg2+ ions reduced on a

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4249

preferential cathode (related possible to a surface impurity) where the anodic site is located
in another cracked aw; (b) Hg2+ ions reduced at cathodic sites present in the same
cracked aw, not related here to a cathodic impurity. The corresponding healing process
of the cracked aw is controlled by the bulk pH, as discussed in Section 3.4.
3.3. Activation process
The extremely negative potential attained in Fig. 1, after nearly 11 min, was ascribed to
the development of an active state, where the Al surface is partly free of its oxide lm.
According to Eqs. (4) and (5), by lowering the bulk pH, it is possible to hinder or retard
the crack healing process, which gives further insight into the nature of this process. Therefore, the same experiment as in Fig. 1 was repeated, but at pH = 1.9. After 4 min, the corrosion potential was shifted to a very negative value (1.570 mV). Immediately after
reaching this potential, the specimen was removed from the solution, and gently washed
prior to scanning electron microscopy. Fig. 3(a) shows a discrete Hg droplet distribution
over the surface, similar to the previous ndings in the decoration process (Fig. 2(a)).

Fig. 3. SEM Micrographs of an Al specimen after being activated in 103 M Hg (II) acetate solution at pH = 1.9.
(a) General view showing the Hg decoration distribution and some localised attack (holes) in the oxide lm. (b)
Hg drops distribution around holes in the oxide lm. (c) Spongy Al(OH)3 development in localised attacked areas
following the same Hg distribution as in Fig. 6(b).

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J.B. Bessone / Corrosion Science 48 (2006) 42434256

Particularly, some of the Hg droplets are in the vicinity of holes in the oxide lm
(Fig. 3(b)), which appear covered with corrosion products, possibly Al(OH)3 gel. This is
more evident in Fig. 3(c), where, following the same Hg distribution, the Al hydroxide
gel appears in a large quantity, from a feather forming reaction, even detaching some
Hg droplets.
To initiate the activation process, the reduced Hg must wet the bare Al. Eective wetting, which is the establishment of a true interface between the liquid metal and the solid
metal, is reached when the interfacial energy dierence (surface tension) between the Al
oxide/Hg interfaces is lowered suciently to match that of the bare Al/Hg interface. Wetting will occur when the Al oxide builds up is avoided. The surface tension can be measured through the contact angle between the liquid and the oxide, Fig. 4. If it is
suciently acute, within a cracked aw where Hg has been reduced, the capillary action
will predominate on the Hg surface tension and it will wet the bare Al [36]. The low bulk
pH and/or the local acidication produced by the Al3+ ion hydrolysis reaction (Eq. (5))
will increase the Al hydroxide solubility [35], retarding the repassivation of the cracked
aw, that is, the hydrated alumina build up within the crack. This eect will favour the
Hg wetting of the bare Al, oering a more acute contact angle. On the other hand, if
the oxide lm adjacent to the Hg drop is restored, due to favourable media conditions
within the cracked aw (high pH), this angle will change, favouring now the detachment
of Hg from the Al. A complete restoring of the oxide lm beneath the Hg drop is also possible. This could be the situation attained during the Hg decoration (Fig. 2(a)) or when the
bare Al, after being in contact with Hg, is left at air (Fig. 3(a)(c)) where a repassivation
process is favoured, as explained later in this section.
When Hg enters into a metallic contact with the bare Al, an amalgam will be formed.
The Al solubility in Hg is extremely low at room temperature (0.003 wt.% of Al), as given
by the AlHg phase diagram [37].
The dilute solution of Al in the Hg seems to be incapable of creating a self-protective Al
oxide lm at the amalgam/solution interface and, as a result, an active state is developed,
which is manifested by the very negative potential recorded. Heyrovsky [38] found that the
Al liquid amalgam potential must be very near to that of active Al (Al free of oxide lm).
The Al volume diusion into the Hg brings Al at the amalgam/electrolyte interface, where
it is now oxidised. Thus, the initial cathodic areas where Hg was reduced, are converted
into anodic ones, as shown schematically in Fig. 3, following these reactions:

Fig. 4. Schematic representation of the Al activation process produced by Hg.

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4251

Fig. 5. Schematic representation of the Hg wetting process on Al within a cracked aw leading to an active or
passive state. (a) Eqs. (1)(3) in neutral media Hg decoration or crack repassivation is produced. (b) Eqs. (1)(3)
at low pH Crack activation by Hg is produced.

Hg + Al ! Hg  Al (amalgam)

Hg  Al ! Al3 + 3e + Hg

The Hg droplet distribution observed in Fig. 3(b) and (c) can now be explained, considering that within a cracked aw, its central area becomes initially the anodic one, surrounded by a cathodic area, where Hg2+ ions are reduced (Fig. 5).
As Al is oxidised and comes out from the amalgam, it is replaced by Al coming from the
substrate. Although the amount of Al present in the amalgam is expected to be extremely
low, on average, this situation can still be maintained if a fast oxidation takes place at the
amalgam/electrolyte interface. The possible kinetic control in this process could be given
then by the Al volume diusion through the Hg or by the Al3+ ions ux towards the bulk
of the solution. This latter step will depend upon the Al compound solubility and its diffusion rate, away from the reactive interface. This process consumes Al. The lateral Al
consumption facilitates the Hg surface diusion. This eect proceeds to detach the oxide
lm, increasing the amalgamated area.
The Al(OH)3 gel which appears to cover the Hg droplets (Fig. 3(b)) and the feather
forming reaction observed in Fig. 3(c) can now be explained by considering the reactions
produced on the wet amalgamated surface when it is removed from the solution. The Al
oxidation reduces H+ or O2, in a reduced volume of solution increasing its pH value, facilitating the formation of Al(OH)3, which is observed as a white spongy corrosion product.
The exothermic hydrolysis reaction given by the reaction of Al3+ ion with water [35],
speeded up the natural drying process:
Al3 + 3H2 O ! Al(OH)3 + 3H +
DH 1406:7 kcal:=gr mol

9
10

As the amalgamated surface dries, the feather forming reaction rate decreases, until it
nearly stops, because the cathodic reaction rate decreases (water content is reduced, and so
does the reduction rate of protons and oxygen). Afterwards the feather forming reaction is
maintained at a slow rate, given by the ambient humidity or moisture and the slow O2 diffusion towards the reactive interface. The hydrated alumina restored by this process
increases the Hg surface tension. Thus, the Hg will be detached from the reactive interface,
as in the case observed in Fig. 3(b). Also, the feather forming reaction will detach Hg droplets, which appears eectively within the Al hydroxide (Fig. 3(c)). The attack morphology
observed in Fig. 3(b), where a hole in the oxide seems to be formed, is the consequence of
an initial cracked aw activated by the reduced Hg, that was repassivated at air.

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J.B. Bessone / Corrosion Science 48 (2006) 42434256

The fact that the initiation of the activation process is associated with the direct metallic
contact between the reduced Hg and the bare Al is supported by the following results. Hg
drops placed on an Al specimen carrying its air formed oxide, were incapable of activating
the Al surface, during the 2 h run. The oxide lm prevented the HgAl metallic contact.
Then, the same specimen with the Hg drops was immersed in 3% NaCl solution, and
no Hg activation took place during the 1 h test. The corrosion potential was established
by the pitting potential (oscillating between 640 and 800 mV) [39]. After removal of
the specimen from the solution, no feather forming reaction appeared. This result suggests
that although an active area is developed (within a pit) if no Hg2+ ions are present in the
solution, there is no possibility of bringing Hg into contact with the bare Al.
3.4. Comparison between the Hg2+ ions concentration and bulk pH
The initiation of the activation process shown is likely to depend on the media composition. In this respect, the Hg2+ ions concentration and the bulk pH eect were studied.
Therefore, several Hg (II) acetate solutions, of dierent concentration and pH were prepared. In preparing the solution, a bulk pH was established, by the buer action exerted
by the acetate anion (pK acetic acid = 4.75 [10]) and the acidication produced by the
Hg2+ ions hydrolysis reaction. The pH value could not be increased deliberately, because
Hg hydroxide will precipitate [40]. However, it may be decreased by adjustment with
HNO3, without altering the initial Hg2+ ion concentration, although its buer properties
2+
are lost. Additionally, NO
ions [35], thus avoid3 anions form a soluble salt with the Hg

ing precipitation. Within the working conditions used, NO3 anions behaved as a relatively
inert anion to Al, rather than promoting any active state [40].
The Al specimens were placed in the respective solutions and their Et responses were
followed. Their passive state was continuously checked, every minute in a 0.5 M Na2SO4
solution because the Hg2+/Hg polarising couple could mask an active state, which is discussed in Section 3.5. The active state was considered to be reached when the measured
potential in the sulphate solution was more negative than 1100 mV.
Table 1 shows the results obtained during this set of experiments.
Comparing the activation time required, at the same Hg2+ ions concentration, it suggests that at lower pH values, the healing process at the cracked aws is retarded or hindered. Conversely, changes in the Hg2+ ion concentration only show slight dierences in
the activation time (101 M: 9 min and 103 M: 11 min). In fact, it is more eective to hinder the healing process by the low pH than to increase the likely cracking rate by a stronger polarising couple (Hg/Hg2+). Although higher Hg2+ ions concentration will increase
the possibilities for Hg2+ ions to be reduced into the bare Al, developed at a cracked aw,
Table 1
Activation time for dierent Hg2+ ions concentration and pH
Hg2+ conc. (M)

pH

Activation
time (min)

Final passive potential tested

in 0.5 M Na2SO4 pH = 5.95 (mV)

101
101
102
103
103

3.40
2.00
3.65
4.20
1.90

9
3
11
11
4

230
300
240
360
415

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4253

only a small number of active sites are required to shift the corrosion potential to an extremely low value. This eect was conrmed in the present work and is also supported by
Reboul et al. [8].
3.5. Evans type diagram for the system Al/Hg2+ ions
It has been noticed that at higher Hg2+ ions concentrations it is possible to continue
reading a very noble potential (+100 mV or more), whilst testing in sulphate solution
shows a very active potential. The explanation can be given through an Evans type diagram, Fig. 6. Initially, upon immersion, Hg2+ ions are reduced, decorating the cathodic
impurities, and forming the Hg/Hg2+ couple, which will polarise the still passive Al surface
to Ecorr1. If Hg2+ ions activity is decreased by their reduction, the polarising couple will
reduce its potential. This seems to be the explanation for the potential decay observed
within the decoration region in Fig. 1. Once the active state has been reached, the potential
measured can show a very positive or negative value, depending upon the Hg2+ ions concentration still remaining at the reactive interface (Ecorr2 or Ecorr3).
These dierent potentials will aect the Al oxidation rate. At higher Hg2+ ions concentration, the Hg/Hg2+ couple will be maintained for a longer time, producing a high Al oxidation rate (Icorr2). When the Hg2+ ions concentration have been completely reduced, the
Hg2+ polarising eect completely disappear, and the Al oxidation rate is now reduced,
mainly supported by the proton reduction (Icorr3), which is now possible at that potential.
3.6. Attack development
The activation process which ultimately develops into the attack is characteristic of Al
sacricial anodes containing Hg [8] as opposed to the usually observed discrete pitting of

Fig. 6. Evans type diagram for the Al/Hg System in aqueous media (1) Al/Al3+ + (oxide); (2) Al/Al Hg/Al3+;
(3) Hg2+/Hg; (4) H+/H2.

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J.B. Bessone / Corrosion Science 48 (2006) 42434256

Fig. 7. SEM Micrographs of an Al specimen after 15 min of being activated in 103 M Hg (II) acetate solution,
pH = 4.2. (a) (250) Shows the characteristic feathering at air produced by an Hg pool, surrounded by darker
areas where the Hg attack has begun. (b) (2.0 K) Shows the typical wide cavity, where its feathering has fallen
away, and the remaining corrosion product presents a mud structure.

Al in chloride media. To analyse this process, an Al specimen was immersed in Hg (II)

acetate (103 M; pH = 4.2), and after reaching an active state (1525 mV), it was left
immersed for a further 10 min. Subsequently the specimen was dried in air and examined
in the SEM (Fig. 7(a) and (b)).
The former shows the characteristic feather formation in air, and also smaller dark
spots associated with damaged areas, which may correspond to an initial stage of attack.

Fig. 8. SEM Micrographs of the same Al specimen examined in Fig. 7(a) and (b), but after cleaning in CrP
mixture. (a) Shows the preferential surface paths followed by Hg in its surface diusion (85). (b) Details of
surface paths (485).

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4255

The latter presents the typical wide cavity, were the masking corrosion products had fallen
away. Once Hg wets the bare Al, at the initial cathodic sites present in the cracked aws
(see Fig. 3), its surface diusion is now possible [36], ultimately enabling it to cover the
whole cracked area producing a Hg pool, avoiding the repassivation of the bare Al.
The amalgamation process (volume diusion of Al in Hg) will help the Hg surface spread
by consuming Al laterally and supercially (not as in a localised pitting reaction) and so
weakening the oxidemetal bonding forces. Thus, the oxide lm will be undermined and
detached from the Al surface. As Hg spreads over the surface, from an initial Hg pool,
a circular attack development is expected, as shown by Fig. 7(b), forming a wide cavity.
Re-examination after cleaning the specimen in a chromicphosphoric mixture, showed
the attack propagation from an initial Hg pool (Fig. 8(a) and (b)). Preferential Hg surface
diusion paths appeared, initially following a radial direction. From them a further lateral
Hg diusion is expected, which will increase the attack, enlarging the circular attacked
area.
4. Conclusions
(a) The Hg decoration and activation processes support the presence of a dynamic
crackhealing process through the defective air formed oxide. Thus, bare Al is
brought into contact with the aqueous media.
(b) Hg2+ ions galvanically reduced at the bare Al, form an amalgam that initiates the
activation process, detaching the passive lm by consuming Al in its surface diusion. The subsequent Al oxidation takes place mainly at the amalgam/electrolyte
interface.
(c) Lowering the bulk pH, the initiation of this activation process is enhanced, by hindering the repassivation of the cracked aws at the oxide lm. Thus, the eective
wetting between Hg and Al is facilitated.
(d) The amalgam surface diusion covers the whole cracked area, producing a Hg pool.
The amalgam generates a homogeneous surface dissolution beneath it, by equalising
the reactiveness of all Al surface atoms. This process accounts for the attack morphology and anodic eciency of the sacricial anode, i.e. the relatively smooth wide
cavities produced.

Acknowledgements
The Secretara de Ciencia y TecnicaUNS (PGI 24/M093/04) and the Consejo Nacional de Investigaciones Cientcas y Tecnicas (CONICETPIP02143/00) are gratefully
acknowledged for the nancial support. Also, helpful discussions maintained with Drs.
Vic Ashworth, George Thompson and David Scantlebury, from UMIST Sta is greatly
appreciated.
References
[1] J.T. Reading, J.J. Newport, Mater. Protect. 5 (1966) 15.
[2] R.A. Hine, M.W. Wei, Mater. Protect. 3 (1964) 49.
[3] T. Sakano, K. Toda, M. Hanada, Mater. Protect. 5 (1966) 45.

4256
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]

[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]

J.B. Bessone / Corrosion Science 48 (2006) 42434256

C.F. Schrieber, J.T. Reading, Mater. Protect. 6 (1967) 33.

D.S. Keir, M.J. Pryor, P.R. Sperry, J. Electrochem. Soc. 116 (1967) 777.
B.M. Ponchel, R.L. Horst, Mater. Protect. 7 (1968) 38.
T.J. Lennox Jr., R.E. Groover, M.H. Peterson, Mater. Prot. Perform. 10 (1971) 39.
M.C. Reboul, M.C. Delatte, Mater. Perform. 19 (1980) 35.
P. Gimenez, D.I. Thesis, 1982, Grenoble.
G. Burri, W. Luedi, O. Haas, J. Electrochem. Soc. 136 (1989) 2167.
J.F. Equey, S. Muller, J. Desilvestro, O. Haas, J. Electrochem. Soc. 139 (1992) 1499.
F. Holzer, S. Muller, J. Desilvestro, O. Haas, J. Appl. Electrochem. 23 (1993) 125.
J.B. Bessone, D.O. Flamini, S.B. Saidman, Corros. Sci. 47 (2005) 95.
D.O. Flamini, S.B. Saidman, J.B. Bessone, Corros. Sci., in press.
R.D. Kane, S.M. Wilhelm, Combatting Liquid Metal Attack by Mercury in Ethylene and Cryogenic Gas
Plants, Results of Joint Industry-Sponsored Research Program Final Report, InterCorr International, Inc.,
Houston TX, 1992.
S.M. Wilhelm, A. McArthur, R.D. Kane, in: Proceedings of the Gas Processors Association 73th Annual
Meeting, 1994, pp. 62.
D.A. Wheeler, R.G. Hoagland, J.P. Hirth, Scr. Metall. 22 (1988) 533.
D.A. Wheeler, R.G. Hoagland, J.P. Hirth, Corrosion 45 (1989) 207.
J.A. Kapp, in: M.H. Kamdar (Ed.), Embrittlement by Liquid and Solid Metals, TMS/AIME, 1984, pp. 117
131.
X.M. Liu, Y.J. Su, L.J. Qiao, W.Y. Chu, Corrosion 55 (1999) 851.
A.H. Al-Saar, V. Ashworth, W.A. Grant, R.P.M. Procter, Corros. Sci. 18 (1978) 687.
T. Valand, G. Nilsson, Corros. Sci. 16 (1976) 591.
T. Valand, G. Nilsson, Corros. Sci. 17 (1977) 931.
degard, T. Valand, Electrochim. Acta 29 (1984) 579.
T. Hurlen, H. Lian, O.S. O
R.C. Fourneaux, G.E. Thompson, G.C. Wood, Corros. Sci. 19 (1979) 63.
M.J. Pryor, in: R.W. Staehele, B.F. Brown, J. Kruger, A. Agarwal, (Eds.), in: Proc. Conf. of Localised
Corrosion, NACE III, 1974, pp. 2.
J.A. Richardson, G.C. Wood, Corros. Sci. 10 (1970) 313.
G.C. Wood, W.H. Sutton, J.A. Richardson, T.N.K. Riley, A.G. Malherbe, in: R.W. Staehele, B.F. Brown,
J. Kruger, A. Agarwal (Eds.), in: Proc. Conf. of Localised Corrosion, NACE III, 1974, pp. 526.
K.J. Vetter, H.H. Strehblow, in: R.W. Staehele, B.F. Brown, J. Kruger, A. Agarwal (Eds.), in: Proc. Conf. of
Localised Corrosion, NACE III, 1974, pp. 240.
Z.A. Foroulis, M.J. Thubrikar, J. Electrochem. Soc. 122 (1975) 1296.
M. Janik-Czachor, J. Electrochem. Soc. 128 (1981) 513 C.
N. Sato, Electrochim. Acta 16 (1971) 1683.
J.B. Bessone, R.A. Suarez Baldo, S.M. de De Micheli, Corrosion 37 (1981) 533.
K.F. Lorking, J.E.D. Mayne, J. Appl. Chem. 11 (1961) 170.
CRC Handbook of Chemistry and Physics, 61st ed., CRC Press Inc., 1980.
W. Rostaker, J.M. McCaughey, H. Markus, Embrittlement by Liquid Metals, Reinhold Pub. Co., New
York, 1960.
L.F. Mondolfo, Aluminium Alloys Structure and Properties, John Wiley Ed., 1976.
J. Heirovsky, J. Chem. Soc. 117 (1920) 27.
J.R. Galvele, S.M. de De Micheli, Corros. Sci. 10 (1970) 795.
G. Charlot, Qualitative inorganic Analysis, John Wiley and Sons Inc., 1954.