Portugaliae Electrochimica Acta 2017, 35(3), 179-186 PORTUGALIAE

ELECTROCHIMICA
DOI: 10.4152/pea.201703179 ACTA
ISSN 1647-1571

Corrosion of a Ni-Al Composite Coating in 2 M NaCl Solution

Ikenna B. Onyeachu,a Demian I. Njoku,b Emeka E. Oguzie,b,* and X. Pengc

a
Department of Chemistry, Edo University Iyamho, Edo State, Nigeria
b
Electrochemistry and Material Science Research Unit (EMRU), Department of Chemistry,
Federal University of Technology Owerri, Imo State, Nigeria
c
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese
Academy of Science, 62 Wencui Road, Shenyang 110016, China

Received August 20, 2016; accepted November 21, 2016

Abstract
A Ni-Al composite was electrodeposited on a Ni substrate, and its corrosion behavior
was observed in 2 M NaCl solution, compared with a pure Ni coating. The Al particles
increased the porosity of the composite and encouraged charge percolation, both at the
corrosion product layer-solution interface and at the substrate–solution interface, based
on EIS characterization. This phenomenon greatly decreased the corrosion potential,
and increased both cathodic and anodic current densities in the active region, as well as
the passive current density in the passive potential range, during polarization of the
composite. Although a continuous Al3+ ions supply to the passivation front was
suspected, based on the longer passivation potential of the Ni-Al composite, the
simultaneous consumption of the Al products by the chloride ions is the reason for
serious cracking and localized collapse of the composite corrosion layer, as confirmed
by SEM. This conferred lower corrosion resistance on the Ni–Al composite, compared
to the pure Ni coating, in the 2 M NaCl solution.

Keywords: Ni–Al composite, passive layer, EIS, SEM, corrosion resistance.

Introduction
The reinforcement of the pure nickel (Ni) coating with micrometer or
nanometer–size second phase particles, to form a Ni matrix composite, is a
veritable approach to improve the material and corrosion characteristics of the Ni
coating [1-7]. A Ni-Al composite consists of a Ni coating reinforced with an
aluminum (Al) particle. The electrodeposition of a Ni-Al composite commonly
involves the deliberate loading of a Ni deposition bath with a given amount of Al
particles, so that, assisted by a means of agitation, the Ni2+ ion adsorbs on the
particle and transports it to the substrate, where it becomes entrapped during the
Ni2+ reduction [8, 9]. Upon annealing treatment of the electrodeposited Ni-Al

*
Corresponding author. E-mail address: [email protected]
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composite, the Al particle usually reacts with the Ni matrix, and the process is an
important step towards the fabrication of an γ/-Ni3Al intermetallic ultrafine-grain,
a potential structural material well known for its low density, high strength at
elevated temperature and higher resistance to high temperature oxidation [10-12]
and electrochemical corrosion [13], compared with the polycrystalline γ/-Ni3Al
counterpart.
Despite refining the Ni grain size and morphology, which is important for
increased corrosion resistance, it is expected that the Al particle in a Ni-Al
composite could also augment the Ni corrosion resistance by enriching the Ni
corrosion product layer with Al2O3. The formation of Al2O3 is fundamental for
the high corrosion resistance of many materials containing Al. Nevertheless, in
aqueous solutions containing chloride ions, Al2O3 itself can be stealthily
destroyed through its transformation into soluble chloride complexes [14-16]. In
a previous work [17], we complemented electrochemical techniques with surface
probe and depth profiling techniques, and reported that, due to the ability of the
Al2O3 to acquire surface hydration and become gradually transformed into the
less protective Al(OH)3, an incubation time was required for the formation of a
well-developed Al2O3 layer, which increased the corrosion resistance of a Ni-Al
composite coating, compared to a pure Ni coating, in a neutral 3.5% NaCl
solution. Conversely, the Al2O3 was greatly unstable and consumed in a more
aggressive 3.5% NaCl solution acidified with 0.05 M H2SO4 solution, thus,
decreasing the Ni-Al corrosion resistance [18]. In order to fully appraise the role
of the Al particle during electrochemical corrosion of a Ni-Al composite in
chloride-containing solutions, an important approach would also be to investigate
this phenomenon in a strongly saline solution with higher chloride ion
concentration.
In the present work, we characterize the corrosion behavior of an
electrodeposited Ni-Al composite, compared with a pure Ni coating, in 2 M NaCl
solution. We focus on the electrochemical characteristics and the surface probe
of the corrosion product layers formed by the coatings.

Experimental
All reagents used in this work were analytical (BDH) grade chemicals used as
source without further purification. All solutions were prepared with deionized
water. The Ni coating and Ni-Al composite were fabricated on 99.9% Ni
substrates with dimensions (12×10×12) mm3, using direct-current
electrodeposition. The preparation of the Ni substrates involved mechanical
abrading to final 800 grit size, using SiC paper, washing with distilled water,
ultrasonic cleaning in acetone and, thereafter, drying with a mechanical dryer.
The procedure for the Ni and Ni-Al electrodeposition has been detailed in our
earlier reports [17, 18]. The average content of the co-deposited Al particle was
found to be 28wt%. The as-deposited coatings were dried in an oven at 105 oC
for 2 h, and kept in an oxygen-free desiccator. The electrochemical corrosion
behavior of the Ni coating and Ni-Al composite was observed in 2 M NaCl
solution at room temperature, using electrochemical impedance spectroscopy

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(EIS) and potentiodynamic polarization techniques, with the aid of a PARSTAT

273A Potentiostat/Galvanostat (Princeton Applied Research) connected to a
signal recovery model 5210 lock-in amplifier for EIS acquisition. The coatings
were embedded in a mixture of paraffin and rosin, so that an area of 100 mm2
was exposed for the corrosion characterization. The prepared coatings were
deployed as working electrodes in a three–electrode system, wherein a platinum
sheet functioned as counter electrode, and a saturated calomel electrode (SCE)
was the reference electrode. The working electrodes were first allowed to attain
open circuit potential (OCP) before the electrochemical characterization. For the
EIS measurement, the coatings were subjected to a signal amplitude perturbation
of 10 mV through a frequency range of 100 kHz to 0.1 Hz. Potentiodynamic
polarization measurement was performed by applying 0.166 mV/s potential scan
between -0.25 V/OCP and +0.40 V/SCE. The surface morphology of the Ni
coating and Ni-Al composite was visualized, before and after polarization, using
the SEM (FEI Inspect/OXFORDINSTRUMENTS-X-Max) hyphenated with an
energy dispersive X–ray (EDAX) spectrophotometer for the acquisition of the
elemental composition.

Results and discussion

EIS characterization
The EIS results obtained for the pure Ni coating and the Ni-Al composite, at
OCP in the 2 M NaCl solution, are expressed in Nyquist, Bode phase angle and
Bode absolute impedance formats, and shown in Fig. 1. In Fig. 1(a), the Nyquist
plots showed curves of incomplete semi-circles: a slight semi-circle at high
frequency and a larger one at low frequency. The size of the Nyquist plot usually
correlates with the corrosion resistance of the material in a corrosion solution
[19-22]. The clearly larger size of the Nyquist plot exhibited by the pure Ni
coating implies higher corrosion resistance compared with the Ni-Al composite.
In the Bode phase angle plots, Fig. 1(b), both coatings displayed two impedance
maxima, Fig. 1(c), which imply that two time constants could be employed to
explain the electrochemical processes occurring at the surfaces of the Ni and Ni-
Al coatings in 2 M NaCl solution. Such two time constants usually represent
impedance processes like charge transfer, mass transfer and film effects
occurring at a corrosion product layer-solution interface and a substrate-solution
interface beneath the corrosion product layer [23]. The high frequency phase
angle maximum in EIS characterization is commonly associated with resistance
to phenomena, such as uptake of water and intrusion of electrolyte salt, whereas
the low frequency maximum concerns resistance to substrate-controlled
processes including localized defects [23]. The pure Ni coating displayed higher
phase angle maxima throughout the frequency scan compared with the Ni-Al
composite, an attestation to the higher corrosion resistance of the former in the 2
M NaCl solution. By fitting the impedance data with the ZSimpWin software,
Fig. 2 shows the most suitable equivalence circuit to model the electrochemical
corrosion mechanism of the Ni coating and Ni-Al composite in 2 M NaCl
solution. The values of the electrical elements in the equivalence circuit are

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detailed in Table 1. Rs is the solution resistance between the reference and

working electrodes; Qpo and Rpo, respectively, stand for the capacitance of a
corrosion product layer and its resistance to transfer of ions; and Qdl and Rct,
respectively, represent the capacitance of the double layer and resistance to
charge transfer in the regions beneath the corrosion product layer. The Qdl for the
Ni-Al composite was approximately three times as high as that of the Ni coating,
which implies greater solution percolation within the composite.

120000 100
(a)
Ni-Al Ni-Al (b)
90
Ni Ni
100000
80
Imaginary Impedance (Ω cm )
2

Phase of Impedance (deg.)

70
80000
60
10500

60000 9000 50
Imaginary Impedance (Ω cm )
2

7500
40
6000

40000
4500
30
3000

1500 20
20000
0
0 1500 3000 4500 6000 7500
2
9000 10500
10
Real Impedance ( Ωcm )

0 0
0 20000 40000 60000 80000 100000 120000 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10
2
Real Impedance (Ωcm ) Frequency (Hz)

5
1.6x10
Ni-Al (c)
1.4x10
5 Ni
Absolute Impedance (Ωcm )

5
2

1.2x10

5
1.0x10

4
8.0x10

4
6.0x10

4
4.0x10

4
2.0x10

0.0
-2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10

Frequency (Hz)

Figure 1. Nyquist (a), phase angle (b) and absolute impedance (c) plots for Ni coating
and Ni-Al composite in 2 M NaCl solution.

Figure 2. Equivalence circuit model for Ni coating and Ni-Al composite in 2 M NaCl
solution.

More so, the Rct, which is a measure of the corrosion resistance of the coatings,
was far lower for the composite than for the Ni coating. Thus, the Al particle
increased the porosity of the Ni coating, which promoted the 2 M NaCl solution
penetration through the numerous micro pores on the composite surface. Based
on the surface hydration characteristic well known for the Al2O3, as reported
elsewhere [21], the solution accumulation in the composite interior should,
therefore, favor its transformation into Al(OH)3 which, in turn, is rapidly
consumed in the presence of high chloride concentration in the 2 M NaCl
solution. The Al2O3 to Al(OH)3 transformation, in the presence of water and
subsequent dissolution by chloride ions, was also reported [24, 25]. This explains

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the lower corrosion resistance of the Ni-Al composite at open circuit potential,
compared with the pure Ni coating, in 2 M NaCl solution.

Table 1. Equivalence circuit parameters for Ni coating and Ni-Al composite in 2 M

NaCl solution.
Sample Rs (Ω cm2) Qpo (F/cm2) n1 Rf (Ω cm2) Qdl (F/cm2) n2 Rct (Ω cm2)
Ni 4.712 8.368 X 10–5 0.6 1.14 X 10 4
5.855 X 10–5 0.8 4.297 X 105
Ni–Al 7.049 8.672 X 10–5 0.8 0.76 X 104 15.210 X 10-5 0.7 0.01 X 105

Potentiodynamic polarization characterization

Potentiodynamic polarization curves derived for the Ni coating and Ni-Al
composite in 2 M NaCl solution are presented in Fig. 3. The values of the
polarization parameters, such as corrosion potential (Ecorr) and corrosion current
density (icorr), which were derived from the intersection of the cathodic and
anodic Tafel slopes drawn ±5 mV around the transition potential, are given in
Table 2. The polarization result shows that the Ni-Al composite displayed a
strongly more negative Ecorr (-527 mV), compared with the pure Ni coating (-229
mV). This reveals greater propensity for the Ni-Al composite to become
dissoluble in the 2 M NaCl solution. Furthermore, the icorr value of 5.057 µA/cm2
for the composite was far greater than the icorr value of 0.1958 µA/cm2 for the
pure Ni coating.

0.5

0.4 Ni-Al
Ni
0.3

0.2
Potential (V/SCE)

0.1

0.0

-0.1

-0.2

-0.3

-0.4

-0.5
-0.6
-9 -8 -7 -6 -5 -4 -3 -2 -1 0
10 10 10 10 10 10 10 10 10 10
2
Current Density (A/cm )

Figure 3. Potentiodynamic polarization plots for Ni coating and Ni-Al composite in 2

M NaCl solution.

The icorr value is a measure of the corrosion rate of the coatings. Thus, there is a
higher rate of cathodic and anodic half-reaction occurring on the surface of the
Ni-Al composite, compared with the Ni coating in 2 M NaCl solution. This
strongly correlates with the mechanism of solution accumulation in the
composite pores at open circuit (equilibrium) potential, as reported during EIS
measurement. Away from the equilibrium potential during anodic polarization,
both Ni coating and Ni–Al composite exhibited similar phenomena, namely: (i)
an active region during early scan; (ii) a region where the applied potential
caused only minimal increase in current density, and could be regarded as a
passive region caused by a corrosion product layer formation; (iii) a region where
the current density sharply increases with the applied potential, attributed to the
initiation of serious localized phenomena, such as pitting corrosion; and (iv) a
region whereby the coatings attempt a gradual transition to trans-passivation.

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Although the Ni-Al composite displayed higher current density than the Ni
coating, in the passive region (which implies greater transport of charges through
the Ni-Al corrosion product layer), surprisingly, the composite sustained its
passive nature over a longer potential range. This strongly indicates that, during
the polarization, an increased outward migration of Al3+ ions occurs from the
composite interior through the corrosion product layer grain’s boundaries to the
reaction front for the sustenance of passivation (which prolongs the passive
potential). However, the Al corrosion products are simultaneously consumed as
they form (which results in higher current than that of the Ni coating in that
region). This phenomenon provides more support for the strong surface hydration
of the formed Al2O3 and its transformation into Al(OH)3, which is readily
consumed by chloride ions in the 2 M NaCl solution.

Table 2. Polarization parameters for Ni coating Ni-Al composite in 2 M NaCl solution.

Sample Ecorr (mV) jcorr (µA/cm2) βa (mV/dec) βc (mV/dec)
Ni -229 0.196 240 -137
Ni – Al -527 5.057 276 -176

SEM characterization
After polarization in 2 M NaCl solution, the electrodeposited Ni coating, Fig.
4(a), transformed such that the Ni corrosion products scattered on the surfaces of
the Ni grains; however, with no clear linkage into a continuous layer. At some
points, obvious consumption of the Ni grains could be noticed. The surface of the
as-deposited Ni-Al composite (where the Al particle preferentially incorporated
within the Ni grain boundaries), Fig. 4(c), was transformed into a corrosion
product layer, somewhat, smoother when compared with the Ni coating, Fig.
4(d). The layer was, nevertheless, characterized by serious cracks, which led to
obvious collapse of some portions. It is important to notice that, apart from the
regions where the layer collapsed, numerous holes could be seen at the triple
junction of the cracks along the Ni-Al corrosion product layer, which is strongly
attributed to the points of serious consumption by chloride ions in the 2 M NaCl
solution. Since Al2O3 formation should predominantly occur at the Ni grain
boundaries and assist in the linkage of the Ni corrosion product layer, given that
the Al particle is mainly incorporated therein, it must be the Al products
consumption by the chloride ion that vigorously destroys the grain boundary
adhesion and locally causes the collapse of the layer portions. This Al product
consumption by chloride ions can be verified from the EDAX acquisition of Cl
and Na with high composition of Al and O (than Ni), at a crack along the
corrosion product layer, Figure 4(e). This is, therefore, the reason for the lower
corrosion resistance of the Ni-Al composite, than that of the pure Ni coating, in 2
M NaCl solution.

Conclusion
The electrodeposited Ni-Al composite exhibited lower corrosion resistance in 2
M NaCl solution, compared with the pure Ni coating, because the Al particle
increases the porosity of the Ni coating and encourages the solution penetration

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during corrosion. This leads to an increased rate of dissolution of the composite

surface. The Al corrosion products are readily consumed in the highly
concentrated chloride solution, leading to serious cracking and localized collapse
of the composite corrosion product layer.

Figure 4. SEM surface feature of Ni coating (a) as-deposited, (b) as-polarized; Ni-Al
composite (c) as-deposited, (d) as-polarized; and (e) EDAX analysis of Ni-Al corrosion
layer.

Acknowledgements
Onyeachu B. Ikenna is grateful to The World Academy of Sciences (TWAS) and
the Chinese Academy of Sciences (CAS) for the award of a Postgraduate
Fellowship.

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