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Corrosion behaviour of electrochemically joined aluminum and stainless steel

Article in Indian Journal of Chemical Technology · July 2005

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Indian Journal of Chemical Technology
Vol. 12, July 2005, pp. 466-471

Corrosion behaviour of electrochemically joined aluminum and stainless steel

G Sheela, V S Muralidharan & Malathy Pushpavanam*
Central Electrochemical Research Institute, Karaikudi, 630 006, India
Received 17 November 2003; revised received 5 November 2004; accepted 21 March 2005

Two dissimilar metals viz., aluminum and stainless steel (SS) were joined electrochemically by heavy nickel
deposition. Potential-time behavior, Tafel extrapolation method and galvanic coupling experiments were conducted to study
the corrosion behavior of the three individual metals in 5% aqueous sodium chloride acidified with acetic acid, alone and in
combination. The systems behaved differently in simple immersion test and on coupling with each other. In simple
immersion test, nickel and SS were nobler to aluminum. Coupling of aluminum and nickel (bi-metallic) resulted in
dissolution of both metals, the rate of nickel being lower. Potentiodynamic polarization experiments showed that the
aluminum-SS bi-metallic system has the highest corrosion rate than aluminum-Ni or SS-nickel. Aluminum exhibits pitting
type corrosion when coupled to nickel. Experiments with electroplated specimens and SEM analysis confirmed that in
aluminum-nickel couple both metals corrode, the corrosion of nickel being considerably lower. Formation of elemental
nickel on aluminum surface also confirmed the above result.

Keywords: Electrochemical joining, mass loss, corrosion current, galvanic couple, polarization technique
IPC Code: G01N17/02; C23F11/00

Electrochemical joining of dissimilar metals is plating procedures and the strength of the joints were
preferred when two difficult-to-plate metals need to evaluated3. Determining the corrosion behaviour of
be joined. In this context, conventional joining such a tri-metallic joint needed special consideration
methods are not suitable due to metallurgical since each metal will be influencing the corrosion
incompatibility. Since electroplating process can be behaviour of the other. So, corrosion of three different
done at room temperature, problems due to shrinkage metals was studied individually and in combination
stresses and distortions, associated with high with another metal and as three systems together, in a
temperature joining operations, are eliminated1. The similar manner as reported earlier4. This paper
properties of the joints can be tailored to meet specific presents the results of these studies.
requirements and can be used on components of any
size and shape2. Because of these advantages, this Experimental Procedure
method is gaining popularity in aerospace and nuclear Corrosion experiments were conducted in aqueous
programs, for example in heat shields, missile nose 5% sodium chloride electrolyte acidified to pH 3 with
cone protection during reentry, solid motor cases with glacial acetic acid. This solution is universally
propellant gain insulation and nozzle system grown in accepted for accelerated corrosion testing for
place, jet nozzles with fuel partitions grown in place, electroplated nickel5,6 and hence should have strong
linear accelerator structures with copper discs for corrosive effect on nickel. Since, the ultimate aim of
regulating purposes and so on. Large diameter (1 the paper is to evaluate behaviour of the plated
meter) rings of 6061-T6 aluminum alloy have been materials, this solution was chosen for the studies.
joined to AM 363 stainless steel rings and are used for
For open circuit potentials measurements aluminum
commercial production in some countries.
(6061-T6) (Al), stainless steel (AISI type 316) (SS)
In the project on electrochemical joining for space
and nickel (electrolytic) sheet (Ni) specimens of 1
applications, heavy nickel deposition was used to join
inch2 surface area were exposed as individual study
aluminum and stainless steel, adopting suitable pre-
metals in the above medium for 168 h, with potential
monitoring after every 20h and finally estimating the
__________
*For correspondence (E-mail: malathypush@yahoo.com; weight loss of the metals in milligrams/day/square
Fax: (04565) 227779, 227713) decimeter (mdd).
 SHEELA et al.: CORROSION BEHAVIOUR OF ELECTROCHEMICALLY JOINED ALUMINUM 467

In a separate experiment, the metals were coupled

as Al-Ni, SS-Ni, and SS-Al and their mixed potentials
with time and weight loss were estimated as above.
Galvanic current prevailing between the two
coupled metals and three coupled metals (each 1 inch2
exposed area) were monitored using a Zero
Resistance Ammeter (ZRA) in the same electrolyte
and the experiments were conducted for 168 h. The
potential and current values were recorded.
For corrosion current density determinations, an
electrochemical analyzer (Ecochemie auto lab 100
Potentiostat/galvanostat, Netherlands) was used. The
individual metals in the above test medium were
polarized from the open circuit potential (OCP) by
about 200 mV on cathodic as well as anodic side at
the rate of 10 mV/sec. A platinum foil and SCE were
used as the auxiliary and reference electrodes
respectively. The linear segments of the anodic and
cathodic branches were extrapolated to OCP and from
the Tafel slopes of the individual metals the corrosion
current density icorr and corrosion potentials Ecorr were
estimated.
In the same way, the above values were determined
also for the bimetallic system in which 1 cm2 of each
electrode (total 2 cm2 exposed area) was externally
connected in the above test medium and treated as the
working electrode.
Experiments were conducted to determine the icorr
and Ecorr values in the above medium on nickel
electroplated aluminum/stainless steel exposing 0.5
cm2 each of nickel plated portion and the unplated
portion on aluminum or stainless steel. Finally, the
three metal systems viz., electrochemically joined SS
and aluminum flats with nickel were treated as
working electrodes and tested for their corrosion
behaviour.
Fig. 1⎯Schematic diagram for the circuits used for the study (1)
All experiments were conducted under quiescent immersion (2) galvanic coupling study of bi and trimetallic
condition and at room temperature. The schematic systems (3) potentiodynamic polarization study of single and
diagram of the circuits used in this study is shown in bimetallic system (4) potentiodynamic polarization study of
Fig. 1. plated systems.
The corroded specimens were examined for their
surface topography using Scanning Electron of 168 h, nickel exhibited highest corrosion rate
Microscope, to confirm the findings. followed by aluminum. SS was found to possess least
corrosion rate (Table 1).
Open circuit potentials of bimetallic couples were
Results followed for 168 h. Aluminum-nickel, and aluminum-
In the open circuit potentials measurements of SS when immersed together showed almost the same
aluminum, SS and nickel in 5% NaCl solution behaviour. Their mixed potentials were in the range of
acidified with acetic acid (pH 3.0), aluminum –750 to –800mV whereas nickel-SS system exhibited
exhibited the least potential among the three followed the mixed potential of –0.27 at the time of start but
by nickel. SS exhibited the highest values. At the end decreased to –300mV in 35 h and got stabilized
468 INDIAN J. CHEM. TECHNOL., JULY 2005

around this value. This suggested that in aluminum- Table 1⎯ Open circuit potentials of various systems in acidified
nickel and aluminum-SS systems, aluminum 5% sodium chloride
dissolved in preference and controlled the mixed
System Open circuit potential Corrosion rate
potential value whereas in SS-nickel system, nickel (mV Vs SCE) (mdd)
dissolved preferentially. Start Potential
potential after 168 h
In aluminum-nickel system, nickel showed a
negative value for mass gain, which can be taken as Nickel -240 -335 75.53
no loss whereas aluminum exhibited a corrosion rate SS -70 -155 0.433
of 70.87 mdd. This suggested that in aluminum-nickel Aluminum -770 -865 21.48
system aluminum acted anodically (Table 1). In SS-nickel -27 -357 Ni 45.4; SS –2.66
Aluminum-nickel -756 -796 Al 70.87; Ni –5.98
presence of SS, aluminum experienced corrosion rate SS-aluminum -754 -784 Al 116.3; SS –5.76
of 116.3 mdd and SS a negative value that can be
assumed as no loss. In SS-nickel system nickel Table 2⎯ Galvanic behaviour of various systems coupled to
dissolved with a corrosion rate of 45.4 mdd and SS nickel in acidified 5% sodium chloride
experienced negative rate that can be taken as no loss. System Potential (mV Vs SCE) Corrosion rate (mdd)
Surface examinations of the nickel surface indicated Initial Final
pitting7 and that of aluminum surface, uniform
dissolution (Fig. 2). SS-nickel 33 -414 Ni 53.4; SS –0.89
Aluminum-nickel -661 -1279 Ni 468.66; Al 343.08
Figure 3 presents the variation of mixed potential
values versus SCE and galvanic current of the
aluminum-nickel couple (aluminum connected as
anode and nickel as cathode) with time. The mixed
potential, which was –0.66V at the start gradually
decreased with time and reached –1.52V in 75 h and
then showed oscillations representing onset of
passivity followed by trans-passivity. In a Zero
Resistance Ammeter (ZRA), to measure absolute
current values the resistance of the system must be
reduced to a minimum and this imposes some
potential on the electrodes. Hence the measured
galvanic potential would not be the correct one for Fig. 2⎯SEM micrograph showing corrosion of aluminum after
drawing any conclusion. The galvanic current, which immersion test.
registered a slightly positive value at the start,
decreased gradually, reached a negative value with a
rapid decrease after 130 h. Both nickel and aluminum
were found to experience corrosion rates of 468.66
and 343.08 mdd respectively (Table 2). When the
current density prevailed at each electrode was
calculated using this value, it was observed that the
average current density at aluminum was around
3 mA/cm2 and that at nickel was around 0.178
mA/cm2.
When nickel was coupled to SS, the mixed
potential that was positive at the start, progressively
decreased with time and reached –0.41V at the end of
168 h, which corresponds to the open circuit potential
of nickel suggesting a gradual increase in dissolution Fig. 3⎯Galvanic current and potential measurements for
of nickel (Fig. 4). This was confirmed by corrosion Aluminum versus Nickel in acidified 5% sodium chloride.(□)
rate measurements given in Table 2. Potential (•) Current.
 SHEELA et al.: CORROSION BEHAVIOUR OF ELECTROCHEMICALLY JOINED ALUMINUM 469

Fig. 4⎯Galvanic current and potential measurements for SS

versus Nickel in acidified 5% sodium chloride. (□) Potential (•)
Current.

Table 3⎯Parameters derived from polarization curves for the

corrosion of various systems in acidified 5% NaCl

System Ecorr Tafel slopes Corrosion

mV vs SCE mV/decade current density
Anodic Cathodic μA/cm2

SS -417 40 40 0.35
Nickel -425 50 40 15.0 Fig. 5⎯Potentiodynamic polarization behaviour of (a) Al (b)
Aluminum -795 50 50 900 Nickel (c) SS in the above medium with Platinum counter
Aluminum- -770 30 30 870 electrode, Scan rate 10mV/s.
nickel
Aluminum-SS -785 30 30 1250
Nickel-SS -420 50 40 8

Figure 5a-c presents the potentiodynamic

polarization curves for aluminum, nickel and SS in
acidified 5% NaCl solution (against platinum counter
electrode). Aluminum exhibited highest corrosion
current density followed by nickel and SS (Table 3).
The potentiodynamic polarization curves for
bimetallic systems are given in Fig. 6a-c (against
platinum counter electrode). Aluminum-SS couple
showed highest corrosion current density.
Aluminum-nickel couple exhibited moderate, while
SS-nickel couple the least corrosion current density.
The corrosion potentials recorded for Al-SS and Al-
Ni couples corresponded to that of aluminum while
for Ni-SS couple it was nearer to that of nickel
(Table 3).
Figure 7a-c presents the polarization curves for
electroplated nickel with other metallic couples.
Nickel plated aluminum exhibited a corrosion current
density of 70 µA/cm2 while nickel plated SS offered Fig. 6⎯Potentiodynamic polarization behaviour of (a) SS-Ni (b)
more than ten times less corrosion current density. Al-Ni (c) SS-Al in the above medium with Platinum counter
When aluminum and SS were joined by heavy nickel electrode, Scan rate 10 mV/s.
470 INDIAN J. CHEM. TECHNOL., JULY 2005

electro deposition, the corrosion current density Table 4⎯Parameters derived from E-logi curves for the corrosion
recorded was 150 µA/cm2 (Table 4). of various plated systems in acidified 5% NaCl
The nickel-plated aluminum surface showed
System Ecorr, mV Tafel slopes Icorr
corroded portions of both the metals. Pitting and non- vs SCE mV/dec μA/cm2
uniform etching along with the precipitation of Anodic Cathodic
elemental nickel was observed on aluminum while
uniform corrosion with corrosion products are Ni deposited SS -250 59 59 6
observed on nickel (Fig. 8a & b). Ni deposited Al -750 39 46 70
Al-SS (joined) by nickel -740 52 30 150
deposit
Discussion
It is well known that when couples/joints of
galvanically dissimilar metals are exposed to a
corroding medium, the nobler metal gets cathodically
protected at the expense of the baser member
provided their corrosion potentials are sufficiently
apart. Associated cathodic current polarizes both
members. Their compromise potential is governed
predominantly by anodically dissolving baser member
of the coupled joint. However, concentrations of ionic
species in contact with the surfaces of bi/tri-metallic
couples exposed to corrosive medium, polarization

Fig. 8⎯SEM micrographs of (a) nickel-plated Al showing

corrosion products on both metals; pitting type corrosion in
aluminum and precipitated elemental nickel; (b) nickel-plated
aluminum showing non-uniform etching and nickel corrosion
products.

behaviour of the concerned metals, as well as

associated IR drop etc, also contribute to the overall
compromise potential and corrosion rate. Preferential
greater corrosion rate of the anodic member includes
contributions from the factor of associated activation
and concentration polarization and also of the nature
of the thin-filmed cathodic surface8, 9.
Results obtained in immersion tests as single metal
Fig. 7⎯Potentiodynamic polarization behaviour of nickel-plated
as well as in combination indicate that aluminum is
(a) SS (b) Al (C) SS-Al joined by nickel with platinum counter the most reactive metal of the three and SS is the
electrode, Scan rate 10 mV/s. least. Even in presence of another metal like SS or
 SHEELA et al.: CORROSION BEHAVIOUR OF ELECTROCHEMICALLY JOINED ALUMINUM 471

nickel, aluminum functions as the anodic material and confirmed by the presence of elemental nickel on
undergoes weight loss which is more in presence of aluminum surface after the test. SEM micrographs of
SS than nickel. This can be understood by the the surface of a tri-metallic system of aluminum-SS
difference in their open circuit potentials, which is joined by heavy nickel electro-deposition further
more between aluminum and SS than Al and nickel. support this behaviour.
In galvanic coupling experiment, aluminum- nickel
couple showed mixed potential which corresponds to Conclusion
aluminum but showed oscillations. The current The corrosion studies of aluminum, SS and nickel
registered was very low initially and showed a steep in acidified sodium chloride solution as individual,
increase after 130 h. This suggested that when bimetallic and trimetallic systems indicated that in
aluminum and nickel are coupled, the mixed potential nickel-SS and aluminum SS couples SS remains
at the initial stages was not sufficient to protect nickel protected allowing nickel or aluminum to corrode.
so that both metals underwent dissolution till a value Aluminum-nickel couple also showed dissolution of
sufficient to protect nickel cathodically is reached. aluminum in immersion as well as potentiodynamic
Black smut of elemental nickel formed on aluminum polarization tests. However, galvanic coupling
after the experiments confirmed the dissolution of experiments followed by weight loss measurements
both metals. In the case of SS-nickel the potentials are indicated noticeable but less significant corrosion of
well separated so that nickel alone showed nickel also along with aluminum indicating that in
dissolution. this test media the protection offered by aluminum to
In potentiodynamic polarization studies in acidified nickel is marginal. The results are confirmed by
5% NaCl solutions, at pH 3 the most common surface examination also.
cathodic reaction is hydrogen evolution. In a
quiescent electrolyte, the hydrogen evolution is under Acknowledgement
diffusion control and the corrosion of a metal is The authors wish to record their sincere thanks to
mainly decided by its anodic reaction. the Director, Central Electrochemical Research
In aluminum-SS couple, though both are oxide- Institute, Karaikudi for his kind support and
forming materials, the film on SS is more strong encouragement. Thanks are due to Indian Space
making aluminum to corrode faster. In aluminum-Ni Research Organization, Bangalore for funding this
couple, the observations in open circuit potential study.
measurements do not agree with those of galvanic
coupling where both metals exhibited weight loss. It
could be inferred that in immersion testing, the metals References
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