Portugaliae Electrochimica Acta 2017, 35(3), 127-136 PORTUGALIAE

ELECTROCHIMICA
DOI: 10.4152/pea.201703127 ACTA
ISSN 1647-1571

Ni Corrosion Product Layer During Immersion in a 3.5%

NaCl Solution: Electrochemical and XPS Characterization

B.I. Onyeachu,a E.E. Oguzie,b,* I.C. Ukaga,b D.I. Njokub and X. Pengc
a
Department of Chemistry, Edo University, Iyamho, Edo State, Nigeria
b
Electrochemistry and Material Science Research Unit, 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 July 29, 2016; accepted February 06, 2017

Abstract
Long term wet corrosion resistance of metals depends on the stability of their corrosion
product layer. With immersion corrosion tests, such stability can be predicted. EIS and
potentiodynamic polarization were complemented with XPS to investigate the
characteristics of Ni corrosion product layer formed after 1 hr. and 72 hr. immersion in
3.5% NaCl solution. Two time constants with decreasing Nyquist semi-circle size and
phase angle maxima, based on EIS characterization during the immersion times,
indicated the formation of an increasingly porous and less adherent corrosion product
layer. The product formation shifted the Ni corrosion potential more negatively and
increased cathodic and anodic current densities, during potentiodynamic polarization.
XPS characterization suggested that a rapid nucleation of NiO could increase H2O
adsorption, subsequently triggering the formation of different forms of Ni(OH)2 in the
corrosion product layer. Consequently, the corrosion resistance of the Ni coating
decreased after 72 hr. immersion in 3.5% NaCl solution.

Keywords: Ni coating, XPS, EIS, NiO, immersion test, corrosion product layer.

Introduction
The corrosion resistance of metallic materials is a function of the corrosion
product layer characteristics formed in the corrosion environment. Surface
modification through nano-crystallization of grain size, which has been achieved
through various sputtering and deposition techniques, has been reported to
greatly improve the corrosion resistance of these metallic materials [1–10].
Nanocrystalline Ni metal and its alloys have gained wide industrial application,
especially because of the good corrosion resistance of Ni. The highly reduced
grain size facilitates a faster nucleation of Ni corrosion products (due to the
higher density of surface atoms), promotes easier linkage of the corrosion

*
Corresponding author. E-mail address: [email protected]
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product nuclei (due to the highly reduced inter–particle spacing), and allows
continuous outward supply of Ni atoms through the abundant grain boundaries to
the reaction front for replenishment and participation in the corrosion process. In
wet environments, these factors ultimately promote the formation of a more
continuous and compact corrosion product layer [6]. Nevertheless, understanding
how prolonged exposure affects the stability of the Ni corrosion product layer, in
such wet environments, is fundamental towards ascertaining its long term
protectiveness. The electrodeposited nanocrystalline Ni coating exhibited higher
corrosion resistance than the microcrystalline counterpart in a 3% NaCl solution,
courtesy of the rapid formation of a fine and compact corrosion product layer
composed of NiO and Ni(OH)2 [6]. The formation of this corrosion product layer
resulted in reduced anodic, cathodic and passivation current densities, as well as
increased passivation potential range. However, the corrosion product layer
characterization focused mainly on a surface probe without due consideration to
a depth profiling approach which could provide more detailed information about
the distribution of the corrosion products, especially at the corrosion product
layer–substrate interface. Recent reports based on electrochemical
characterization, however, have shown that the corrosion resistance of the
electrodeposited Ni coating decreased with prolonged exposure in a more
aggressive 3.5% NaCl containing solution [11]. Therefore, despite establishing
the constituents of the Ni corrosion product layer, characterizing their
transformation mechanism over time, is highly imperative. Such characterization
could provide clearer insight into the usability span of Ni coatings, for wet
application during deployment.
In the present work, we have employed electrochemical techniques to
characterize the corrosion resistance of an electrodeposited Ni coating after 1 hr
and 72 hr immersion in a 3.5% NaCl solution. Subsequently, we have utilized X–
ray photoelectron spectroscopy (XPS) to perform depth profiling of the corrosion
product layer formed by the polarized Ni coating after the immersion times in a
3.5% NaCl solution.

Experimental
Materials preparation
The reagents used for all solutions preparation were of analytical (BDH) grade
and were used without further purification. All solutions were prepared using
distilled water. The Ni coating was fabricated using direct current
electrodeposition, on pure (99.9%) Ni substrate, with the dimensions (12 X 10 X
12) mm3. The substrates were prepared by mechanically abrading to final 800
grit size using SiC paper, followed by washing with distilled water, cleaning in
acetone (with ultrasonic vibration) and drying with a mechanical dryer. The
procedure for the Ni coating electrodeposition has been detailed in our earlier
reports [11, 12]. The as-deposited Ni coating samples were, thereafter, dried in
an oven at 105 ºC for 2 hr and kept in an oxygen-free desiccator.

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Electrochemical characterization
The electrochemical characteristics of the Ni corrosion product layer were
investigated after immersing the Ni coating samples for 1 hr and 72 hr in a 3.5%
NaCl solution. The Ni coating was utilized as working electrode in a three
electrode system, where a platinum sheet functioned as the counter electrode, and
a saturated calomel electrode (SCE), connected through a Luggin capillary, was
used as reference electrode. The working electrode was prepared by embedding
in a mixture of paraffin and rosin, so that a working area of 100 mm2 was
exposed for the corrosion characterization. The employed electrochemical
techniques include electrochemical impedance spectroscopy (EIS) and
potentiodynamic polarization. The coating samples were first allowed to attain
stable open circuit potentials for 30 min before each experiment. The
electrochemical measurements were performed by using a PARSTAT 273A
Potentiostat/Galvanostat (Princeton Applied Research) connected to a signal
recovery model 5210 lock–in amplifier for EIS acquisition. The EIS
measurement was performed by applying a signal amplitude perturbation of 10
mV in a frequency range of 100 kHz to 0.1 Hz. Potentiodynamic polarization
measurement was performed during a 0.166 mV/s potential scan from -0.25
V/OCP to +0.25 V/SCE.

Corrosion product characterization

The chemistry of formation and transformation of the Ni corrosion products after
1 hr and 72 hr exposure with subsequent polarization in a 3.5% NaCl solution,
was characterized using the XPS–ESCALAB 250 Thermo VG X–ray
spectrometer with monochromatic AlKα (1486.6 eV) radiation source at a pass
energy of 1 keV and on a sample area of 2 mm X 2 mm. Sputtering was
performed at a rate of 0.04 nm/s for 0, 10 and 40 sec. Subsequent spectra peak
deconvolution of the Ni 2p3/2, and O 1s peaks was performed with the aid of
XPSPEAK4.1 processing software (Chemistry Ltd., CUHK) in the Shirley
background after calibrating with the C 1s peak at 284.6 eV.

Results and discussion

Electrochemical impedance spectroscopy (EIS)
During the immersion times, the EIS characterization at OCP can provide
information concerning the mechanism and rate of charge transfer both at the
surface of the Ni coating and through a corrosion product layer formed in the
3.5% NaCl solution. The EIS results have been represented in the Nyquist, Bode
phase angle and Bode modulus formats, as shown in Fig. 1. In the plot of real
impedance against imaginary impedance, the Nyquist plot, after each immersion
time, Fig. 1(a), revealed a small semi–circle at high frequency and a large
incomplete semi–circle spanning through the intermediate to the low frequency
region, with a slight diffusion phenomenon. Such diffusion can be attributed to
the movement of reaction species like hydroxide and chloride ions, as well as
oxygen, through a very thin layer, such as a corrosion product, formed on the
coating surface [6, 13–16]. The shape of the impedance plot is synonymous with

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the formation of a corrosion product layer experiencing partially localized

breakdown [17]. The size of the Nyquist semi–circle correlates with the
corrosion resistance of the electrode. From the decrease in the size of the Nyquist
plots after 72 hr immersion, it is obvious that the corrosion resistance of the Ni
coating in the 3.5% NaCl solution decreased as immersion time increased. The
corresponding Bode phase angle plots for the coating are shown in Figure 1(b).
After both immersion times, the phase angle plots revealed two impedance loops,
which decreased in maxima after 72 hr immersion, at high and low frequency.
The phase angle plots indicate that the mechanism of the Ni coating corrosion in
the 3.5% NaCl solution can be explained using two time constants which
correspond to the charge transfer processes occurring at a corrosion product
layer–NaCl interface and at the substrate–NaCl interface (beneath the corrosion
product layer). The reduction in the maximum phase angle, and the noticeable
shift of the high frequency loop towards lower frequency after 72 hr immersion,
can be attributed to certain localized thinning of the Ni corrosion product layer
[18]. In a previous work [11], SEM surface characterization also revealed that the
corrosion products, which formed sparsely in the crevices between the large
surface grains of a similar Ni coating, were highly prone to attack by chloride
ions, leading to localized pitting corrosion after prolonged immersion up to 72 hr
in a 3.5% NaCl solution.

Figure 1. Nyquist (a), Phase angle (b), and Absolute impedance (c) plots for nickel
coating after 1 hr and 72 hr immersion in a 3.5% NaCl solution.

Our impedance observation differs markedly from the report of [6] for
nanocrystaline Ni coating in a 3% NaCl solution without an immersion time
experiment. According to them, the Nyquist diffusion phenomenon was observed
at low frequency, and corresponded with a single time constant in the phase
angle plot. It, therefore, indicates that concentration and time can seriously

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modify the electrochemical characteristics of the Ni corrosion product layer in

aqueous NaCl solutions.

Scheme 1. Equivalent circuit model fittings for nickel coating impedance behaviour
after 1 hr and 72 hr immersion in a 3.5% NaCl solution.

In order to correlate the impedance result with electrical elements, the ZSimpWin
software was deployed to derive an appropriate electric model for the impedance
phenomenon. According to the two time constants exhibited in the Phase angle
plots, three different models were tested, as shown in Scheme 1(a), 1(b) and 1(c).
Consequently, the equivalent circuit model in Scheme 1(c) with the best overlap
between experimental and fitting curves (especially at the low frequency regions)
and least chi–square value was adapted to model the impedance behavior of the
Ni coating in a 3.5% NaCl solution. The values of the resultant electrical
elements derived by using the ZSimpWin software are presented in Table 1. In
the model, Rs is the solution resistance, the elements Qpo and Rpo are,
respectively, the corrosion product layer capacitance and pore resistance, while
Qdl and Rct represent, respectively, the capacitance of charge and resistance to
charge transfer at the electric double layer formed beneath the corrosion product
layer.

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The R values are measures of the compactness and corrosion resistance of the
corrosion product layer, while the Q values depict its dielectric properties. The
decrease in R values and increase in Q values, after 72 hr immersion, confirm
that the Ni corrosion product layer became more porous and increased the
diffusion of stored charges across its interface (even as the value of n2=0.5
further confirms). This is the reason for the decrease in corrosion resistance of
the Ni coating with immersion time in a 3.5% NaCl solution.

Table 1. Impedance parameters for Ni coating after 1 hr and 72 hr immersion in a 3.5%

NaCl solution.
Immersion time Rs (Ω cm2) Qpo (F/cm2) n1 Rf (Ω cm2) Qdl (F/cm2) n2 Rct (Ω cm2)
1 hr 6.14 2.72 X 10–6 0.9 6389 1.84 X 10–5 0.5 4.56 X 105
72 hr 6.37 1.01 X 10–5 0.8 6334 5.46 X 10-5 0.5 5.79 X 104

0.3
1 hr
0.2 72 hr

0.1

0.0
Potential (V/SCE)

-0.1

-0.2

-0.3

-0.4

-0.5

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

Figure 2. Potentiodynamic polarization plots for nickel coating after 1 hr and 72 hr

immersion in a 3.5% NaCl solution.

Potentiodynamic polarization
It is well known that, during a potential scan, the simultaneous anodic and
cathodic half–reactions occurring at the metal surface usually lead to the
formation of a corrosion product layer, and its characteristics influence the
properties of the polarization curve and its derivable parameters. The
potentiodynamic polarization plots for the Ni coating after 1 hr and 72 hr
immersion in the 3.5% NaCl solution are presented in Fig. 2. The derivable
polarization parameters, namely, the corrosion potential (Ecorr) and corrosion
current density (jcorr) were extrapolated from the intersection of the anodic and
cathodic Tafel slopes drawn ±10 mV around the OCP. The values are presented
in Table 2. Based on Table 2, the Ecorr value became more negative, changing
from –288 mV after 1 hr to –315 mV after 72 hr immersion in the 3.5% NaCl
solution. This indicates the increased tendency for dissolution in the solution.
The jcorr value, on the other hand, is a measure of the corrosion rate of the
coating. Accordingly, there was a higher jcorr value of 0.522 µA/cm2 after 72 hr
immersion, compared with 0.139 µA/cm2 after 1 hr, showing that the corrosion
product layer, with time, could not impede the rate of electron transfer through its
interface.

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Table 2. Polarization parameters for Ni coating after 1 hr and 72 hr immersion in a

3.5% NaCl solution.
Immersion time Ecorr (mV) jcorr (µA/cm2) βa (mV/dec) βc
(mV/dec)

1 hr. -288 0.139 129 -175

72 hr. -315 0.522 167 -154

Furthermore, Fig. 2 shows that immersion time caused an increase in both the
cathodic and anodic current densities. A highly favorable cathodic reaction,
which can proceed in such a neutral solution as the 3.5% NaCl solution, is the
reduction of oxygen and water molecules into hydroxide ions (Equation 1).
Such phenomenon would favor the formation of Ni(OH)2, rather than the more
protective NiO. The higher anodic current density reveals an increase in the
oxidation rate of Ni atoms after the longer immersion time, and may also be
facilitated by the localized adsorption and penetration of chloride ions during the
prolonged immersion, which deteriorate both the microstructure and adherence
of the corrosion product layer. Nevertheless, a slight reduction in anodic current
density occurred between 150 and 250 mV after the prolonged immersion, and
can be related to increased thickness of the corrosion product layer.

2H2O + O2 + 4e– → 4OH– (1)

(a )
H y d r a te d N i(O H ) 2
H 2 O ( a d s .)
N i(O H )2
OH-

N i 2 p 3/2 O 1s

8 60 859 85 8 8 57 856 85 5 85 4 536 535 53 4 5 33 532 531 5 30

B in d in g E n ergy (eV ) B in d in g E n erg y (eV )

(b )

Ni
2-
O
N iO

N i 2 p 3/2 O 1s
858 857 856 855 854 853 852 851 850 534 533 532 531 530 529 528 527 526

B in d i n g E n e r g y ( e V ) B in d in g E n e r g y (e V )

(c )

Ni
O 2-
N iO

N i 2 p 3 /2 O 1s

858 857 856 85 5 8 54 853 852 851 8 50 536 534 532 530 528 526 524

B in d in g E n erg y (eV ) B in d i n g E n e r g y ( e V )

Figure 3. XPS characterization of (a) outer, (b) middle and (c) inner layer of a corrosion
product formed by polarized nickel coating after 1 hr immersion in a 3.5% NaCl
solution.

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X–ray photoelectron spectroscopy (XPS)

XPS depth profiling was employed to characterize the corrosion product layer
formed by the polarized Ni coating after each immersion time. By sputtering at
0.04 nm/s for 0, 10 and 40 s, a depth profiling occurred for 0, 0.4 and 1.6 nm, and
is henceforth regarded as outer, middle and inner layer, respectively. The C 1s
peak remained at 284.6 eV throughout the detections. The Ni 2p3/2 peaks were
detected at 852.6, 853.7, 856, 857.7 and 858.7 eV binding energies. The O 1s
peaks were detected between 529 eV and 533.7 eV. After 1 hr immersion with
subsequent polarization in a 3.5% NaCl solution, Fig. 3(a) reveals that the
surface of the Ni coating contained Ni species deconvoluted at 856.7 eV (most
enriched), 857.7 eV and 858.6 eV (least enriched), with corresponding O 1s
peaks at 532.4 eV and 533.5 eV. The binding energy at 856.7 eV is consistent
with the formation of Ni(OH)2 [11, 12, 19–21].

(a) H y d r a te d N i(O H )2

H 2 O ( a d s .)
N i ( O H ) 2 ( s a t .)

OH-

N i 2 p 3 /2 O 1s
870 868 866 864 862 860 858 856 854 852 850 536 535 534 533 532 531 530

B in d in g E n e r g y (e V ) B in d in g E n e r g y (e V )

(b)

N i( O H )2 N iO
Ni OH-

O2-

N i 2 p 3/2 O 1s

860 858 856 854 852 850 536 535 534 533 532 531 530 529 528

B in d in g E n e r g y (e V ) B in d in g E n e r g y ( e V )

(c)

OH-
Ni
N i(O H )2 N iO
2-
O

N i 2 p 3/2 O 1s
860 858 856 854 852 850 536 535 534 533 532 531 530 529 528

B in d in g E n e r g y (e V ) B in d in g E n e r g y ( e V )

Figure 4. XPS characterization of (a) outer, (b) middle and (c) inner layer of the
corrosion product formed by polarized nickel coating after 72 hr immersion in a 3.5%
NaCl solution.

Although higher binding energies are commonly correlated with higher oxidation
state species, the phenomenon for a Ni oxidation to Ni+3 was not observed during
the polarization experiments. The Ni 2p3/2 peaks at 857.7 eV and 858.6 eV could,
therefore, be attributed to the formation of different polymorphs of Ni(OH)2 with
a greater degree of intercalated species like water molecules [22, 23]. The O 1s
peaks were therefore attributed to the OH– (532.4 eV) and H2O(ads.) (533.5 eV). In
the middle and inner layers, only NiO and unreacted Ni at 853.5 eV and 852.6
eV [11, 12], respectively, were detected. These peaks corresponded with O 1s

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peak at 530 eV, which confirms the formation of O2– compounds. The peak area,
hence, concentration of the NiO also increased with the increasing depth of the
corrosion product layer. This result confirms that the corrosion resistance of the
Ni coating in a 3.5% NaCl solution is courtesy of the formation of a thin layer of
NiO just beneath a hydroxide–enriched outer layer. Based on this configuration
of an O2––enriched layer directly beneath a OH––enriched layer, it can also be
proposed that the formation of the Ni(OH)2 species could be initiated by
precursors like NiO–H2O(ads.), whereby the NiO particles act as nucleation sites to
trigger the adsorption of H2O molecules (see Equation 2).

Ni + [O] → NiO + H2O → NiO–H2O(ads) → Ni(OH)2 (2)

After 72 hr immersion in a 3.5% NaCl solution with subsequent polarization,

only the Ni 2p3/2 peak at 857.7 eV, with an associated satellite peak at 864 eV,
was detected on the outer layer of the corrosion product (see Fig. 4).
The corresponding O 1s peak was observed at 533.5 eV. Compared with the
characterization after 1 hr immersion, the persistence of the peak at 857.7 eV
definitely means that the adsorption of water molecules is a characteristic of the
Ni corrosion product layer. The peak must, therefore, be attributed to the
formation of a more hydrated form of Ni(OH)2, such as the α–Ni(OH)2 [22, 23].
The middle and inner layers contained Ni compounds detected at 853.6 eV and
856 eV which, respectively, signifies NiO and Ni(OH)2. This peak at 856 eV
must, hence, be a less hydrated Ni(OH)2 (such as β–Ni(OH)2) than the more
hydrated α–Ni(OH)2 at 857.7 eV. While the NiO concentration increased with a
greater layer thickness, the reverse occurred for the Ni(OH)2 constituent. This
result implies that the corrosion product layer also becomes more dehydrated
with a greater layer thickness. Nevertheless, the non–dominance of the NiO at
the corrosion product layer–substrate interface after 72 hr, compared with after 1
hr, is the reason for the decrease in the coating corrosion resistance during
immersion in a 3.5% NaCl solution. Thus, the formed NiO must be more
amorphous than crystalline, which causes it to readily be converted in the less
protective Ni(OH)2 species, via adsorption of water molecules. The increased
adsorption also implies higher incorporation and diffusion of chloride ions within
the matrix of the corrosion product layer. This, subsequently, will locally
deteriorate the corrosion product layer–substrate interface. SEM characterization
of the pitting corrosion of such electrodeposited Ni coating, arising due to
increased localized deterioration of the Ni corrosion product layer in a 3.5%
NaCl solution, has been undertaken in an earlier report [11]. This is the reason
for the increase in the corrosion rate of the Ni coating with prolonged immersion
in a 3.5% NaCl solution.

Conclusion
The protection characteristic of the corrosion product layer formed by an
electrodeposited Ni coating has been investigated in a 3.5% NaCl solution, using
immersion time experiments. The corrosion resistance of the Ni coating

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decreases after 72 hr immersion, due to the enrichment of the corrosion product

layer with less protective Ni(OH)2 species which are readily hydrated on the
surface, but dehydrated with a greater corrosion product layer thickness. The
corrosion product layer also exhibited increasing porosity and weaker adhesion
with the substrate, after the prolonged immersion time.

Acknowledgements
Onyeachu B. Ikenna acknowledges The World Academy of Science (TWAS) and
the Chinese Academy of Science (CAS) for the award of a TWAS-CAS
Postgraduate Fellowship.

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