Corros Rev 2022; 40(1): 1–37
Review
Imtiaz Ahmed Shozib*, Azlan Ahmad, Ahmad Majdi Abdul-Rani, Mohammadali Beheshti
and Abdul’Azeez Abdu Aliyu
A review on the corrosion resistance of electroless
Ni-P based composite coatings and
electrochemical corrosion testing methods
https://doi.org/10.1515/corrrev-2020-0091
Received October 4, 2020; accepted November 9, 2021;
published online December 9, 2021
Abstract: This paper aims to review the impact of
different factors influencing the corrosion resistance of
electroless Ni-P based coatings. Emphasis has been given
onto the impact of phosphorus content, incorporation of
alloying elements, addition of particles and heat treat-
ment which have been discussed in detail and critically
reviewed. The effect of corrosive media and coating pro-
cess parameters on corrosion resistance are studied
concisely. Furthermore, the role of the incorporation of
various elements and particles’ contents on the corrosion
resistance of electroless Ni-P coating are studied system-
atically. This paper also presents an overview of the latest
electrochemical corrosion measuring techniques. The
following approaches deserve special attention in the
analysis: localized electrochemical impedance spectros-
copy (LEIS), scanning vibrating electrode technique
(SVET), scanning ion-selective electrode technique (SIET),
scanning droplet cell (SDC), scanning electrochemical
microscopy (SECM), scanning Kelvin probe (SKP) and
novel contactless technique (NCT).
Keywords: corrosion measuring techniques; corrosion
resistance; electroless Ni-P coating; heat treatment;
incorporation of SiC particles.
*Corresponding author: Imtiaz Ahmed Shozib, Mechanical
Engineering Department, Universiti Teknologi PETRONAS, Seri
Iskandar, Perak 32610, Malaysia,
E-mail: imtiazshozib87me@gmail.com. https://orcid.org/0000-
0001-8562-9569
Azlan Ahmad, Ahmad Majdi Abdul-Rani and Mohammadali Beheshti,
Mechanical Engineering Department, Universiti Teknologi PETRONAS,
Seri Iskandar, Perak 32610, Malaysia. https://orcid.org/0000-0003-
4884-1127 (M. Beheshti)
Abdul’Azeez Abdu Aliyu, Mechanical Engineering Department, Bayero
University, Kano, Nigeria
1 Introduction
Corrosion is an electrochemical phenomenon with pro-
gressive detrimental impacts on the integrity of materials
as well as huge economic losses for various industries.
Metal corrosion safety is based on through anodic passiv-
ation or by sacrificial anode defence behaviour (Andrade
and Martínez 2010). Moreover, metal coatings may provide
anodic or cathodic protection for the substrate from un-
propitious environment. Basically, metal may corrode
rapidly in different acidic or salty environments by dete-
riorating the surface structure of the metal and thus leaving
metal susceptible to corrosion damage (Bahgat Radwan
et al. 2018). There are basically two ways to damage a
coated metal surface for corrosive species. The primary
reason is associated with the thickness of the coating. If
thin coating is applied on the surface of the substrate it can
get easily damaged. The other reason is if metal is exposed
to a fault or damage to the coating, so that water and cor-
rosive media have complete access to the substrate and
may disperse across the substrate interface (Bubbico et al.
2015). There are numerous types of coating which can be
contemplated as good corrosion prevention measures.
Nowadays, electroless nickel–phosphorous (Ni-P) coatings
have been well known for the best corrosion resistant since
it can blanket the surface of a metal with a thin film (Jian
et al. 2020). Electroless deposition with hypophosphite
bath is the most used electroless Ni plating method having
greater precedence when compared with borane and hy-
drazine reduced bath. Thus, coatings are deposited on the
surface of the substrate by catalytic reduction of Ni ions
using sodium hypophosphite as a reducing agent for its
enormous use. The hypophosphite bath is cost effective
and shows better corrosion protection than other reducing
agents. In addition, borane and hydrazine have also been
used as reducing agents. However, they are found to be
poor in industrial use and can only be applied for special
purposes. Therefore, electroless Ni coating is usually
named as electroless Ni-P coating. The most captivating
2 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
feature of electroless Ni-P coating is that it does not require
any electricity to operate the coating deposition process
upon a metal. Thus, it is considered to be the most cost-
effective coating process. Owing to their excellent corro-
sion and wear resistance, electroless Ni-P coatings have
been broadly used in the energy sectors, electronic,
chemical and mechanical industries. Previous studies
have delineated that the incorporation of different hard
and soft particles in the electroless Ni-P coating dramati-
cally improved the corrosion resistance (Shibli and Dili-
mon 2007; Shozib et al. 2020) and introduced promising
attributes to the performance of coating, which strengthen
their generalizability in various sectors. However, there
were few papers reported the influences of coating pa-
rameters of electroless Ni-P coating on corrosion resistant
properties (Sahoo and Das 2011; Sudagar et al. 2013).
There are several conventional ways to measure the
corrosion rate. One of them is to weight the loss of metal
which has been carried out in the laboratory by gravimetric
determinations. The gravimetric approach provides average
corrosion rate values as it acknowledges the actions over a
certain period. Afterward, electrochemical theory including
kinetics of corrosion with mixed potential was developed
which can eloquently demonstrate corrosion phenomena.
Nevertheless, in electrochemical phenomena, no manual
procedure is required to measure the corrosion rate. In this
case, an electrochemical parameter known as corrosion
current density (icorr) is applied to effortlessly measure the
corrosion rate. Although there are many techniques avail-
able for on-site corrosion identification of various sub-
strates, those of an electrochemical nature are the most
relevant since this is the origin of the corrosion process. The
corrosion potential (Ecorr) and the corrosion current density
(icorr) are the most important parameters for corrosion
evaluation which can be calculated by measuring the po-
larization resistance (Rp). Though these techniques are
very simple and inexpensive, they do not provide sufficient
information to fully explain the corrosion phenomena.
The potentiodynamic technique (PT) and electrochemical
impedance spectroscopy (EIS) methods have been used in
every laboratory for corrosion protection and are commonly
well known for years. However, PT and EIS techniques,
only provide the average data (Niaz and Bakare 2015;
Ningshen et al. 2009) of corrosion behaviour of the metal
surface and therefore, they cannot be extended to analyze
the models of corrosion phenomena for the small surface
areas. The scientists have worked hard to develop new
methods for the investigation of high spatial resolution
corrosion phenomena. Recently, environmental engineers
and corrosion scientists have adopted a large range of
electrochemical techniques to acquire a great deal of
knowledge on reactions between metal substrate and the
electrolytes. The key findings of the exposed techniques
are localized electrochemical impedance spectroscopy
(LEIS), scanning vibrating electrode technique (SVET),
scanning ion-selective electrode technique (SIET), scan-
ning droplet cell (SDC), scanning electrochemical micro-
scopy (SECM), scanning Kelvin probe (SKP) and novel
contactless technique (NCT).
This paper comprises two principal parts. Section 2
discusses the impact of the coating bath compositions,
concentrations, pre-treatment, post heat treatment and
coating process parameters of electroless Ni-P based
coatings on corrosion properties. The objective here is to
review how the coating composition, other pre and post
treatment, and coating process parameters affect the
corrosion properties. The impact of deposited particles and
the incorporation of alloying elements on corrosion resis-
tance, however, are not clear yet. Therefore, the idea of
depositing micro and nanosize particles with different size
and concentrations have become the focus of widespread
research. This discussion has received limited attention in
previous research. Some conflicting results were reported
by different research group. This article aims to investigate
the influences of the parameters on corrosion protection.
The effect of different concentration of deposited particles
in electroless plating bath solution has also been dis-
cussed. In this work, an optimization was carried out to
show the best optimum concentration of SiC nanoparticles
and SiC particle size for corrosion resistance. Section 3
demonstrates an overview of the latest developed electro-
chemical corrosion testing methods. Although conven-
tional electrochemical techniques such as electrochemical
impedance spectroscopy (EIS) have been used for more
than 40 years in corrosion and coating science, evolution
of these techniques into localized methods is a more recent
development.
2 Electroless Ni-P based coating
The electroless coating deposits thin protecting film on the
substrate surface by autocatalytic reaction process. The
most interesting feature of electroless Ni-P coating is that
no power source is required during coating deposition
process. The name behind the electroless Ni-P coating is
considered primarily because the main component in this
deposition is pure nickel and phosphorus. For the most
part, Ni-P alloys are considered synonymous with the term
‘electroless Ni’ since 95% (Narayanan and Seshadri 2009;
Sudagar et al. 2013; Sequeira et al. 2016) of industrial
production uses sodium hypophosphite as reducing agent.
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
After a few dormant years there has been a rapid turnover
of using sodium hypophosphite and it is almost 90% of
all industrial applications. There are some parameters
for coating deposition process which are responsible of
the corrosion properties of electroless Ni-P coating. The
different effects of electroless Ni-P based coatings on
corrosion resistance have been discussed below.
2.1 Effect of phosphorus content
The most common corrosive media using for corrosion
testing is sodium chloride solution. Ni-P deposits in so-
dium chloride solution exhibits a better behaviour
(a strong passivation tendency) than electroless nickel–
boron coatings (Sudagar et al. 2013). Electroless Ni coatings
with high phosphorus contents offer an excellent corrosion
protection whereas moderate and lower amount of phos-
phorus contents are not preferred for unpropitious envi-
ronments (Bigdeli and Allahkaram 2009; Elansezhian et al.
2008; Mallory and Hajdu 1990). Generally, 3–5 wt.%
phosphorus content can be regarded as low phosphorus
content and shows corrosion resistivity in concentrated
caustic soda. 6–10 wt% phosphorus content can be taken
as medium phosphorus content which provides moderate
corrosive protection for some selective fields. Finally, high
phosphorus content is measured as 11–18 wt% and it
effectively works against chlorides, simultaneous me-
chanical stress and most of the applications (Alaneme et al.
2017; Sankara Narayanan et al. 2006). Moreover, electro-
less Ni-P coating can be graded as low (1–4 wt.% P),
average (5–9 wt.% P) and high (10 wt% P or more) based on
their phosphorus content, according to ASTM 733B-04
standard. The phosphorus content in electroless plating
bath solution is considered to have a significant effect on
both chemical (Schorr and Valdez 2016) and electro-
chemical (Court et al. 2000; Kerr et al. 1996, 1997) behav-
iours. The high weight percentage of phosphorus content
can enhance the corrosion potential (Ecorr) and signifi-
cantly reduce corrosion current density (icorr) by con-
ducting the cathodic and anodic reactions during the
3
corrosion process. Generally, the resistance of any alloy to
corrosion depends on the dissolution rate of the passive
film. The electroless Ni-P coating exhibits higher corrosion
resistivity due to its amorphous structure (Fayyad et al.
2018). As a result, it can enhance the phosphorus content
on the surface layer. Amorphous alloys provide greater
resistance from corrosion damage than comparable poly-
crystalline materials because of the absence of grain and
grain boundaries.
The SEM micrographs of electroless Ni-P coating have
been shown in Figure 1. According to the findings of Lu and
Zangari (Lu and Zangari 2002), the variation in surface
morphologies of the electroless Ni-P coatings appear due to
using different concentrations of phosphorus. Electroless
Ni coating with high phosphorus content exhibits a smooth
surface with uniform particle size (Figure 1A) whereas an
electroless Ni coating with low phosphorus is observed
with a fairly rough surface comprising of spherical parti-
cles of asymmetrical sizes (Figure 1B). The existence of
cauliflower-like nodules (Figure 1A) is noticed in the elec-
troless Ni-P coated surface where phosphorus contents
remain high. Due to the increased phosphorous content
of the plates, the nickel lattice disorder can cause a shift
from crystalline to amorphous structure. By contrast, the
average and low contents of phosphorus show microcrys-
talline and crystalline structure. The electroless Ni coated
surface having low phosphorus content delineates Ni (111)
and Ni (200) lattice structure with sharp peaks which is
confirmed by Shibli and Dilimon from the X-ray diffraction
pattern (Shibli and Dilimon 2007) and reveals its crystal-
line nature. On the other hand, in the case of medium
phosphorus content, they found more blurred and diffused
peaks and most remarkably no peaks are identified for the
Ni-P plates with high phosphorus content due to their
amorphous structure in the XRD sequence.
According to Bai et al. (Bai et al. 2003), precise phos-
phorus content of the electroless Ni-P coating has a sig-
nificant impact on decreasing the rate of corrosion and
positively shift the corrosion potential in brine media.
Expanded nickel corrosion provides basic requirements for
phosphorus concentration and thus for the development
Figure 1: SEM micrographs of electroless Ni-
P coated surface: (A) high (13.30 wt%) P
content and (B) low (3.34 wt%) P content
(Sankara Narayanan et al. 2006). (Reprin-
ted with permission, Copyright 2006
Elsevier).
4 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
on the surface of stable intermediate compounds NixPy,
which serve as a passive film barrier. Phosphorus con-
taining in the sodium hypophosphite react with water and
generates phosphorus oxidation by forming a thin film of
hypophosphite anions (H2PO2 ─) on the coated substrate.
The presence of hypophosphite and phosphate anions, as
shown in Equations (1) and (2), were identified by X-ray
photoelectron spectroscopy (XPS) measurement on the
coated surface (Diegle et al. 1988).
P  + 2H2 O/H2 PO−2 + 2H+ + e−
P  + 4H2 O/H2 PO−4 + 6H+ + 5e−
During anodic polarization performed in the corrosive
media (3.5 wt% NaCl solution), the hypophosphite layer is
formed by maintaining at the pH 5.9 (Bonin et al. 2018). The
formation of phosphate anion may also have been antici-
pated because of applying high overpotential (+250 mV)
from the open circuit potential. The electrochemical for-
mation of Ni2+ is achieved through anodic dissolution in
equilibrium aqueous electrochemical system and the exis-
tence of H2PO4 ─ is confirmed by comparing Pourbaix dia-
gram. The Ni hydration is stymied due to the formation of
hypophosphite layer which can block the water molecules
to reach the electrode surface and thus it cannot interact
with Ni. Therefore, the accumulation of phosphorus on the
electrode surface results in increased corrosion resistance
for electroless Ni-P coatings (Balaraju et al. 2006a). It can be
observed that the corrosion resistance increases when the
electroless Ni–high P coating forms the outer layer of the
graded Ni-P coating due to the barrier properties of the un-
derlying Ni–high P layer (Clausmeyer et al. 2016). The ex-
istence of enriched phosphorus is introduced to us by
Kouwe (van der Kouwe 1993) in a different way. He used
glow discharge optical emission spectroscopy to prove the
presence of phosphorus in electroless Ni-P coating. The
enriched phosphorus in the electroless plating bath solution
can be hydrolyzed easily but the hydrolysis of Ni is not
favorable at that condition due to the increment of P content.
Several studies have pointed out the variation in corrosion
resistance with different amount of phosphorus present in
the electroless coating solution (Bai et al. 2003; Lu and
Zangari 2002; Raicheff and Zaprianova 2000). In addition, a
number of researchers also agree to these effects, including
Lu (Lu and Zangari 2002), Lee (Lee and Liang 1991) and Aoki
(Aoki and Takano 1986) by showing lower icorr and better
Ecorr value with electronic effects, structure and homoge-
neity of the coated surface. The phosphorus content range
13–25 wt% in electroless coating acts as an electron acceptor
and can gain 0.4 to 0.8 electrons (Okamoto et al. 1980) from
Ni atom and shows amorphous structure.
The corrosion current density (icorr) for 18 wt% phos-
phorus content exhibited 0.82 × 10−3 mA/cm2 (Shibli and
Dilimon 2007) while it showed 8.7 × 10−3 mA/cm2 for using
10 wt% phosphorus content (Shibli and Dilimon 2007) in
electroless nickel plating bath solution which is nearly 10
times higher. This can be validated by the theoretical fact
that lower icorr value gives higher corrosion resistance. Only
8% difference in phosphorus content can make a huge
difference in corrosion resistance. It is evident from San-
kara Narayanan et al. (2006) that electroless Ni-P coatings
(1)
with higher phosphorus content (13.30 wt%), corrosion
(2) current density value is 0.60 × 10−3 mA/cm2 whereas, with
lower phosphorus (3.34 wt%) content, corrosion current
density value has increased to 4.22 × 10−3 mA/cm2. Figure 2
shows that impact of phosphorus content on the corrosion
current density in both non-aerated and aerated 3.5 wt%
NaCl solution. In non-aerated condition as phosphorus
content increases, the corrosion current density decreases
which results in the higher corrosion resistance. However,
the lowest values of corrosion current densities have been
observed for aerated condition. The corrosion current
density increases slightly in an aerated condition as the
phosphorus content increases.
Balaraju et al. (2006a) showed that for Ni-P coating at
11.36 wt% phosphorus, the value of corrosion current
density is 0.456 × 10−3 mA/cm2. This result exhibited a 33%
deterioration in corrosion protection when he added extra
element (tungsten) in the Ni-P coating solution and made it
ternary alloy composite coating. This deterioration occurs
due to the decrement of almost 6 wt% phosphorus content.
However, for quaternary alloy (Ni-W-Cu-P) composite
coating, though the presence of phosphorus content is only
about 4.92 wt%, the presence of 4.08 wt% copper content
4.5
Corrosion current density, icorr ×10−3
4 In non-aerated 3.5 wt.% NaCl
solution
3.5 In aerated 3.5 wt.% NaCl solution
3
(mA/cm2)
2.5
2
1.5
1
0.5
0
0 5 10 15 20
Phosphorus content (wt. %)
Figure 2: Effect of phosphorus content on current density in non-
aerated (Balaraju et al. 2006a; Cui et al. 2006; Sankara Narayanan
et al. 2006; Shibli and Dilimon 2007) and aerated conditions
(Ashassi-Sorkhabi and Rafizadeh 2004).
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
in the coating solution exhibits a better corrosion resis-
tance than ternary alloy (Ni-W-P) noting the corrosion
current density is 0.481 × 10−3 mA/cm2. As a result, if the
content of tungsten keeps slightly less than 3 wt% and
simultaneously phosphorus content raises to 7–9 wt.%,
then the corrosion resistance must be higher.
Another influence on corrosion resistance of the
weight percentage of phosphorus decrement in electroless
Ni-P plating was found (Ghavidel et al. 2020). The corrosion
current density showed higher corrosion safety when
9.71 wt% phosphorus content was used. However, after
using 2 gm SiC nanoparticle in electroless Ni-P coating, it
lowers the corrosion resistance. This phenomenon hap-
pens due to the incorporation of new nanoparticle which
lowers the phosphorus content in an overall solution. This
can be alleviated by adopting proper concentration of SiC
nanoparticles and sodium hypophosphite in electroless
plating bath solution. There must be a balanced addition of
sodium hypophosphite and SiC nanoparticles in order to
obtain the best protection against corrosion where phos-
phorus content remains at least 9 wt% (Ghavidel et al.
2020). Less than 9 wt% of P content can make grow the
dislocations and crystals boundaries at the interface of
particles and Ni-P matrix. In addition, the compact struc-
ture of the Ni-P coating can be damaged by using an
inappropriate proportion of SiC nanoparticles and thus the
accumulation of particles in the coating can create micro-
holes and porosities in a high proportion. In fact, the
concentration of SiC nanoparticles and its particle size
show some inconsistent value of corrosion current density
which will be discussed later part in this article.
The higher double layer capacitance (Cdl) value shows
better corrosion protection. A total of 28 μF/cm2 double
layer capacitance was measured in 5 wt% NaCl corrosive
media with 10–11 wt % phosphorus content in electroless
Ni-P coating (Zeller 1991). However, in 1.88 wt% NaOH
deaerated condition, Lo et al. (1995) found that the Cdl
values are quite remarkable ranging 100–120 μF/cm2 by
using the phosphorus content 11.8–12.8 wt%. The corrosive
safety could be more improved if NaCl solution was used
instead of NaOH solution as an electrolyte. It can therefore
be concluded from the Cdl values that the electroless
Ni–high P coating is comparatively less porous and shows
better corrosion resistance than electroless Ni–medium
P and Ni–low P coatings.
One of the criteria among the requirements of surgical
instruments is that it should provide low reflection from the
top surface of the tools. The higher brightness of the tools’
surface can irritate visual perception of the surgeon. A
black electroless Ni-P coating can be used as a potential
safeguard to reduce this kind of disruption. Acid etching
5
process in which substrates are submerged into a 9 M nitric
acid solution is needed to prepare the black surface.
However, the incorporation of higher phosphorus content
can hinder the etching procedure. The formation of nickel
oxides (NiO, Ni2O3) and nickel phosphate are responsible
for low reflective black color of Ni-P coating. In the case of
low reflective black surface, phosphorus content should
remain average to get both black surface and corrosion
protected surface. Therefore, optimum phosphorus con-
tent ranging 3–7 wt.% is suitable (Cui et al. 2006) for the
acid etching. Black Ni surface with lower reflectance can be
obtained by incorporating mild phosphorus content in
electroless plating bath solution. The corrosion resistance
of high phosphorus electroless nickel deposits reduces
after black treatment and can be improved by depositing
low phosphorus content. However, in normal condition,
higher phosphorus is suitable for highest corrosion resis-
tance and the Rc value is 5772 Ωcm2 but after black treat-
ment the corrosion resistance is reduced in spite of having
high phosphorus content and shows 3012 Ωcm2 (Cui et al.
2006). It is prudent to keep the phosphorus content slightly
lower than traditional weight percentage to get proper
adhesion and stability of black coating. Higher optical
properties (solar absorbance) are provided by the black-
ened electroless nickel due to its strong adhesion, stability
and uniformity. Therefore, it is commonly used for solar
applications (Farag 2020; Uma Rani et al. 2010) in adverse
space conditions.
2.2 Effect of adding alloying elements
The incorporation of third element in electroless Ni-P based
plating bath solution influences the corrosion behaviour
and coating properties as well. The incorporation of tin or
copper in electroless Ni-P coating raises the thermal sta-
bility of amorphous state and ensures the improvement of
corrosion resistance (Georgieva and Armyanov 2007; Wang
et al. 1999). The addition of 17.2 wt% (Liu and Zhao 2004)
copper in the Ni-P coating solution can exhibit the best
anticorrosion properties. If the copper element is included
in quaternary alloy of electroless Ni-P coating, then above
4 wt% (Balaraju et al. 2006a; Bastidas et al. 2019; Shinato
et al. 2020) Cu content is regarded as the best concentration
for corrosion protection. The inclusion of Cu in electroless
Ni-P-PTFE composite matrix can also enhance the corro-
sion resistance along with coating deposition rate based on
the finding of Zhao (Zhao et al. 2004) where 0.5 gm/L
copper sulfate pentahydrate is used in electroless plating
solution. The addition of Cu element to the Ni-P coating
matrix can speed up the selective dissolution of Ni,
6 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
resulting in enrichment of phosphorus and copper ele-
ments in the coating surface layer, thus increasing the
corrosion resistance of Ni-Cu-P composite coating. This
coating is not only used for the practical condensation of
flue gas but also for potential use in heat exchangers
(Liu et al. 2010). Ternary tungsten alloys (10 wt% W) have
an improvement in corrosion resistance and alloy with up
to 40 wt% tin (Sn) is considered strong resistant to corro-
sive materials (Sudagar et al. 2013).
Balaraju et al. (2006a) found the lower corrosion cur-
rent density (icorr) and higher charge transfer resistance
(Rct) in case of deaerated condition in 3.5 wt% NaCl solu-
tion compared to aerated condition (Figure 3). Electrolyte
containing dissolved oxygen can form OH ─ through
cathodic reaction in aerated condition which is accessible
to the atmosphere. The cathodic depolarization reaction
reduces the charge transfer resistance in aerated condition.
More capacitive corrosion behaviour is noticed in dea-
erated condition which shows the greater homogeneity of
the coated surface. The charge transfer resistance (Rct) is
higher, and corrosion current density is lower for quater-
nary Ni-W-Cu-P composite matrix which provides better
corrosion protection than ternary Ni-W-P composite
coating. This improved corrosion protection can be gained
due to the incorporation of copper in electroless coating
composite matrix which can improve crystallinity and
provide smooth coated surface compared to coarse nodular
ternary Ni-W-P deposit. Copper element has a significant
influence on corrosion resistance in both aerated and
deaerated conditions. There is a difference in wt% of
phosphorus in terms of using ternary and quaternary alloys
to obtain the better protection from corrosion (Table 1).
Though the phosphorus content in Ni-W-Cu-P coating
matrix is much lower than binary (Ni-P) coating, the
corrosion resistance of Ni-W-Cu-P coating and Ni-P coating
is nearly similar to each other due to the inclusion of copper
element in quaternary alloy composite matrix. For ternary
0
Table : Composition (wt. %) of different elements in Ni-P, Ni-W-P
and Ni-W-Cu-P composite coating (Balaraju et al. a).
Coating Ni (wt.%) P (wt.%) W (wt.%) Cu (wt.%)
Ni-P . . – –
Ni-W-P . . . –
Ni-W-Cu-P . . . .
and quaternary alloys 4.5 wt% of tungsten is considered as
the optimum percentage for corrosion protection.
Inclusion of copper in Ni-W-P bath leads to quaternary
Ni-W-Cu-P deposit with improved crystal structure by
decreasing phosphorus content (Balaraju and Rajam
2005). The applicability of electroless Ni-W-P ternary
composite matrix in different sector is really impressive
(Zhou et al. 2019). It can protect the biodiesel storage
container from corrosive damage (Sukkasi et al. 2011).
Moreover, by adopting laser surface treatment on Ni-W-P
composite coating can show amorphous structure with
nanocrystalline Ni and Ni3P phase resulting in improved
anticorrosion performance. The Ni-Mo-P coating also had
an average corrosion-resistant performance and its corro-
sion current density in 3.5 wt% NaCl solution is
14.49 × 10−3 mA/cm2 (Zhao et al. 2020).
2.3 Effect of addition of particles
2.3.1 SiC particles
Bigdeli (Bigdeli and Allahkaram 2009) confirmed that the
inclusion of SiC nanoparticles in Ni-P coatings provided
better protection against corrosion which could be due to a
reduction in the effective metallic area available for
corrosion in Ni-P-SiC composite coating. The different
concentration of SiC nanoparticles using in electroless
Figure 3: Corrosion current density values of
different alloys in deaerated and aerated
conditions (Balaraju et al. 2006a).
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
plating bath solution has an astounding effect on corrosion
resistance. Ghavidel et al. (2020) showed that by addition
of 1 gm/L SiC nanoparticle with 40–60 nm particle size in
electroless Ni-P plating bath solution, corrosion resistance
is higher but when he added 2 gm/L SiC nanoparticles in
electroless bath solution, it deteriorates the corrosion
properties. The surface morphology of Ni-P coating matrix
with 1 gm/L SiC particles has been shown in Figure 4A. No
pores, cavities and cracks can be seen in that SEM image.
It can be clearly observed that the electroless Ni-P-SiC
(1 gm/L SiC) composite coating is uniformly coated on the
substrate. The most striking feature is that the Ni-P-SiC
(1 gm/L SiC) composite coating provides not only barrier
property but also align mechanical interlock between the
substrate and the coating layer. As a consequence, the
coating develops a robust adhesion and exhibits better
corrosion protection. However, the addition of 2 gm/L SiC
nanoparticles in Ni-P coating provides non-uniform sur-
face structure and particles are concentrated in certain
regions as shown in Figure 4B. In addition, the enhanced
concentration of SiC nanoparticles can increase the num-
ber of particles which is responsible for the particles
collision and agglomeration and creates porosity. It results
in somewhat flatter granules and is therefore associated
with coarser flecks. This is widely reported and extensively
explored in the literature by some researchers (Bigdeli and
Allahkaram 2009; Kubisztal et al. 2018) that the maximum
concentration of SiC nanoparticles in the plating bath so-
lution can aggregate the particles due to short interparticle
gap. The use of relatively large concentrations of SiC
nanoparticles in the coating results in dislocations and
crystal boundaries occurring at the particle interface. The
minimum corrosion resistance of Ni-P-SiC (2 gm/L SiC)
composite coating is due to the highest degree of particle
accumulation in its morphology compared to the others.
Zhang et al. (2008) reported that the corrosion resis-
tance of Ni-P-SiC composite coating decreases gradually
with increasing SiC concentration in the coating solution.
Ma et al. (2014) also showed the lower corrosion perfor-
mance when 6 gm/L SiC powder was added into the plating
7
bath solution and provided corrosion current density value
of 306 × 10−3 mA/cm2 which was really high. The coating
process was carried out by sealing the specimens in an
evacuated tempered glass tube and heating them to
different temperatures. The Ni-P-SiC (6 gm/L SiC) com-
posite coating gives worse corrosion resistance compared
to Ni-P-SiC (1 gm/L SiC) coated substrate due to using lower
size (30 nm) of SiC particles in Ni-P-SiC (6 gm/L SiC) com-
posite coating.
Calderón et al. (2014) showed the variation in corrosion
resistance at different concentration of SiC with 25 nm
particle size in electroless Ni-P coating. He reported that
70 gm/L SiC particles gives better corrosion resistance than
20 gm/L and 50 gm/L SiC particles in electroless Ni-P-SiC
composite coating. Ahmadkhaniha et al. (2018) used
20 gm/L SiC particles with average particle size of 50, 100
and 500 nm in electroless Ni-P plating bath solution. He
showed the best corrosion resistance for bigger SiC parti-
cles (500 nm) noting, corrosion current density is only
0.72 × 10−3 mA/cm2. He showed that by using 50 and
100 nm SiC particle size, they have a bit higher corrosion
rate than using 500 nm SiC particles. Calderón used same
concentration of SiC particles (20 gm/L) as Ahmadkhaniha,
but there is a difference in their corrosion current density
(icorr) value only because of using different size of SiC
nanoparticles.
If high concentration of SiC nanoparticles along with
smaller particle size is immersed in the coating composite
matrix, they do not directly contribute to barrier properties
from corrosion damage due to the enriched number of SiC
particle agglomeration. Therefore, it can be concluded that
a correlation exists among the concentration, particle size
and number of SiC particles. The number of SiC particles
goes higher when smaller particle sized SiC are incorpo-
rated in a large concentration in electroless Ni-P plating
bath solution. This phenomenon (Table 2) has occurred
since smaller particle size and higher concentration of SiC
nanoparticles can occupy more space in electroless plating
bath solution. The large number of SiC particles reduces
matrix stability and consistency while their interaction
Figure 4: SEM micrograph of (A) 1 gm/L and
(B) 2 gm/L SiC nanoparticles in electroless
Ni-P plating bath solution (Ghavidel et al.
2020). (Reprinted with permission, Copy-
right 2020 Elsevier).
8 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings

Table : SiC particles phenomena on corrosion resistance.

Addition in coating solution Outcome

SiC concentration (gm/L) SiC particle size (nm) Number of SiC particles Agglomeration and collision Corrosion resistance

High Low Increased Increased Decreased

Low High Decreased Decreased Increased

with the matrix can inhibit the formation of a passive layer (CCD) to study the combined effects of two independent
resulting in SiC particles collision and agglomeration being variables i.e. concentration of SiC nanoparticles and size of
initiated and eventually causes porosity. However, small SiC nanoparticles. Statistical analysis was conducted to
number of SiC particles prevents the particles collision and optimize the corrosion resistance of electroless Ni-P-SiC
agglomeration. Bigger size of SiC particles (like 500 nm) composite coating. 11 set of experimental variables has
results in bigger passive range with small number of SiC been listed in Table 4.
particles which can be related to the more coverage of Ni-P ANOVA analysis for quadratic model of electroless Ni-
matrix. Higher concentration of SiC particle is not suitable P-SiC composite coating has been shown in Table 5.
for better corrosion resistance. In fact, several researchers Analysis of variance (ANOVA) was employed to determine
depicted different opinion about SiC particle size and its the significant parameters that affect the corrosion current
concentration on corrosion resistance (Table 3). density. It uses the concept of lower p-value and higher
Therefore, it is highly difficult to prognosticate which F-value to find the significant factors. The p-value is a
concentration and particle size would be the best for the parameter by which the null hypothesis can be rejected. If
lowest corrosion current density. Hence, an optimization the p-value is less than 0.05, then the parameter is
can fix this issue with proper modeling. The optimization considered as significant. The F-value is the ratio of the
was carried out using a design expert software adopting summation of square of the factors to the variance of the
response surface methodology which can provide a better errors. Hence, a higher value of F will suggest a relatively
result and exhibit the optimum value of SiC particle size better factor with respect to others. Here, the p-value of the
and its concentration for enhanced corrosion protection. model was 0.0115 which is regarded as significant model
The experiment was based on central composite design terms. Model F-value of 4573.65 implied that the model is
significant. In this case B, B2 and B3 are significant model
terms. Values greater than 0.1000 indicate the model terms
Table : List of corrosion current density values by using different are not significant. The higher F-value (7558.02) of SiC
concentrations and particle sizes of SiC in electroless Ni-P plating particle size indicates that particle size has greater influ-
bath solution. ence on corrosion resistance than the concentration of SiC
particle. Using the Design Expert software, the results were
SiC SiC particle Corrosion References
completely analyzed via ANOVA. Equations (3) and (4)
concentration size (nm) current density,
(gm/L) icorr (mA/cm)
Table : Eleven sets of experimental variables were selected from
.  . × – Ghavidel et al.
Table  for the central composite design.
  . × – ()
  . × –
Run Concentration of Size of SiC Corrosion current
  . × –
SiC particle (gm/L) particle (nm) density, icorr (mA/cm)
   × – Calderón et al.
   × – ()  .  . × –
   × –    . × –
  . × – Ahmadkhaniha    . × –
  . × – et al. ()  .  . × –
  . × – Wang et al.    . × –
  . × – ()    . × –
  . × –    . × –
  . × –    . × –
.  . × – Bigdeli and     × –
Allahkaram    . × –
()    . × –
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings 9

Table : ANOVA analysis for quadratic model of electroless Ni-P-SiC concentration of SiC nanoparticles is higher and the least
composite coating. particle size of SiC nanoparticles is used in the plating bath
solution. As seen in (Figure 6), this phenomenon can be
Source Sum of df Mean F-value p-Value
clearly observed from the red zone of the 3D surface plot
squares square
and contour plot.
Model .  . . .
In 3.5 wt% NaCl electrolyte (salty media), Ni-SiC-PTFE
A-SiC .  . . .
(Polytetrafluoroethylene) composite coating shows higher
concentration
B-SiC particle .  . . . corrosion resistance than Ni-PTFE composite coating and
size this is confirmed by the corrosion resistance (Rc) value. The
AB .  . . . concentration of SiC particles were used as 8 to 10 gm/L
A .  . . . with larger particle size (Huang et al. 2004). The enhance-
B .  . . .
ment of corrosion resistance of Ni-SiC-PTFE composite
AB .  . . .
AB .  . . . coating is mainly due to presence of small number of par-
A .  . . . ticles thus prevention of agglomeration of SiC and PTFE
B .  . . . nanoparticles. The SiC and PTFE nanoparticles together can
Residual .  . improve the surface autocatalytic properties triggered by
Cor total . 
thin Ni layer. The Ni-SiC-PTFE and Ni-PTFE composite
coated surface are pore free, homogenous, and uniform in
represent the final equations in terms of coded factors and terms of their surface structure.
actual factors, respectively.
Final equation in terms of coded factors:
2.3.2 TiO2 particles
Corrosion current density 
= (365.14 − 36.57×A  + 442.64×B  − 24.73×AB  TiO2 nanoparticles and TiO2 sol play a very significant role
(3) for higher corrosion resistance. There are two mechanisms
− 22.13×A2 − 327.68 ×B2 − 10.94×A2 B 
responsible behind the improvement of corrosion protec-
+ 46.16×AB2 − 20.23×A3 − 460.27×B3 ) tion by incorporating TiO2 nanoparticles. Firstly, these TiO2
nanoparticles serve as inert physical barriers to the initia-
Final equation in terms of actual factors:
tion and creation of corrosion defects, changing the nickel
Corrosion current density  layer’s microstructure and thus enhancing the coating’s
= (39.9151 + 0.1209×A  − 1.6785×B  corrosion resistance. Secondly, the TiO2 nanoparticles
− 0.0448×AB  + 0.5655×A2 + 0.0203 ×B2 (4) dispersion in the nickel layer inhibits the creation of
several corrosion micro-cells. Therefore, localized corro-
− 0.000485×A B  + 0.000084×AB
2 2
sion is inhibited in the presence of TiO2 due to uniform and
− 0.0218×A3 − 0.000034×B3 )

Here, A and B represent the concentration of SiC par-

ticle and size of SiC particle, respectively. The equation can
be used in terms of actual factors to make predictions about
the response of each factor for given levels.
The predicted ramp response (Figure 5) implies that
the best corrosion current density can be prognosticated by
using 3.32 gm/L SiC concentration with 500 nm SiC particle
size. The higher corrosion resistance can be achieved with
larger SiC particles addition whereas the SiC nanoparticle
concentration should keep low in range in electroless Ni-P
plating bath solution. The blue dot (Figure 5C) indicates the
lowest value of 1.14 × 10−3 mA/cm2 corrosion current den-
sity. It can be clearly delineated from (Figure 6) that the
blue zone is the safest zone for getting the best corrosion
resistance by employing the corrosion current density
value. The corrosion protection gets hampered when the Figure 5: The predicted parameters (A, B) and outcome (C).
10 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Figure 6: (A) Second-order 3D response surface plot and (B) contour plot to show the variation of corrosion current density with concentration
of SiC particle and size of SiC particle with indicating predicted optimum value.
homogeneous surface structure (Abdel Aal 2008). Baghery
et al. (2010) used different concentration of titanium di-
oxide nanoparticles (Degussa P-25 anatase) with a particle
size of 25 nm. It can be observed from his research that
higher concentration of TiO2 nanoparticles in electroless
nickel plating gives the better corrosion resistance in
1.35 wt% NaCl solution. Highest corrosion resistance has
therefore been recorded for 8.3 wt% TiO2 and considered as
the best corrosion current density value. The most notice-
able part is that here the author did not use sodium
hypophosphite as reducing agent. If he used sodium
hypophosphite, then the defense against corrosion would
be more phenomenal due to the impact of the phosphorus
content. A barrier against corrosion is formed by TiO2
nanoparticles through filling up the small holes in the
metal matrix and making the upper surface more compact
(Novakovic et al. 2006; Sekhavat Pour et al. 2018).
Wu et al. (2015) showed that Ni-P-TiO2 sol’s corrosion
current density is 1.02 × 10−3 mA/cm2 but Promphet et al.
(2017) showed the corrosion current density value is
5.6 × 10−3 mA/cm2 for the same particle TiO2 sol incorpo-
ration. This difference occurs because of the variation of
phosphorus and TiO2 sol content in electroless plating bath
solution. Xiaoyan used 30 gm/L sodium hypophosphite
(7.88 wt% P) and 20 ml TiO2 sol. On the other hand,
Promphet used 20 gm/L sodium hypophosphite where the
phosphorus content was less than 7 wt% and 1 ml TiO2 sol.
It can be easily inferred from the results that higher phos-
phorus and higher TiO2 content gives the best anticorrosion
behaviour. The transparent TiO2 sol is obtained by the
mixture of 27 mL Ti(OBu)4, 5 mL diethanolamine (DEA) and
44.7 mL ethanol with a constant 2 h magnetic stirrer.
Moreover, there is a difference in corrosion current density
value of adding TiO2 nanoparticles and TiO2 sol in elec-
troless solution. In essence, the addition of TiO2 sol shows
greater resistance to corrosion than TiO2 nanoparticles. The
corrosion potential (Ecorr) of the electroless Ni-P-TiO2 sol-
RGO coated surface changes dramatically towards positive
potential and displays the highest Ecorr value with lower
corrosion current density (icorr) (Khorasani and Sanjabi
2016; Promphet et al. 2017) relative to other surfaces, sug-
gesting that the full coverage of the reduced graphene
oxide (RGO) layers on the coated surface functions as a
passive layer. It can decrease oxygen permeability and
protect electron and ion transport between the contacted
surface and electrolyte solution. Uysal (2019) used 10 gm/L
TiO2 nanoparticles in his experiment but the corrosion
resistance diminishes drastically and the icorr value showed
for Ni-P-TiO2-GO composite coating is really high noting
52.7 × 10−3 mA/cm2. Though he used higher contents of TiO2
nanoparticles, his experimental evaluation did not show
remarkable results due to inclusion of graphene oxide (GO)
in electroless Ni-P-TiO2 composite matrix.
It can be referred to the reduction of the coating
uniformity and the formation of surface cavities during
the blackening process, which increase the corrosion rate
of the black electroless Ni-P coating (Cui et al. 2006;
Zanella et al. 2011). After applying two steps zincating
bath and deposition of TiO2 antireflection layer (ARL) on
the substrate, icorr showed the value of 4 × 10−3 mA/cm2.
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
The zincating bath comprises of ZnO, NaOH, NaNO3, and
KNaC4H4O6.4H2O chemicals with 4, 120, 1 and 50 gm/L
concentrations respectively (Khollari et al. 2019). The
reduction in corrosion current density means that the
TiO2 layer slows down the corrosion kinetics of black
electroless Ni-P coating. The anodic reaction may reduce
due to the uniform distribution of TiO2 layer which acts as
a ceramic barrier (Ćurković et al. 2013). Electroless black
Ni-P-TiO2 composite coatings are commonly used in op-
tical instruments, biosensors, material absorbents and
photothermal converters (Kathavate et al. 2019; Xing
et al. 2013).
Various concentrations of sodium dodecyl sulphate
(SDS) and dodecyl trimethyl ammonium bromide (DTAB)
can be used as the surfactants in electroless Ni-P-TiO2
plating solution. However, not all level of concentrations
has the positive effect on corrosion protection. It should be
noted that different critical micelle concentration (CMC) of
surfactant (SDS and DTAB) used in electroless Ni-P-TiO2
solution show different values of corrosion current density.
Thus, the optimal level should be chosen to get better
corrosion resistance. Only with the use of cationic surfac-
tant DTAB (1 × CMC) and anionic surfactant SDS (1.5 × CMC)
concentration, they showed better results compared to
using other concentrations. The molecules of the surfac-
tants can prevent the conglomeration of TiO2 nanoparticles
in electroless plating bath solution thereby rendering the
coated surface more uniform and creating a barrier against
corrosive ions. The current densities were measured as
5.38 × 10−3 mA/cm2 and 6.99 × 10−3 mA/cm2 (Tamilarasan
et al. 2015) for DTAB and SDS surfactant, respectively. The
most interesting aspect that has been found is that TiO2
nanoparticles and phosphorus content also have a crucial
effect along with the surfactants on corrosion resistance
because of their varying results. The better corrosion pro-
tection of (1 × CMC) DTAB surfactant has been acquired due
to the presence of higher contents of TiO2 nanoparticles
(6.95 wt%) (Tamilarasan et al. 2015) whereas for other
concentrations of SDS and DTAB, the contents of phos-
phorus and TiO2 nanoparticles were both lower. The
corrosion behaviour by using (SDS or DTAB) surfactants in
electroless Ni-P-TiO2 composite coating shows a better
protection but this could be attributed up to the mark if
higher concentration (5–6 gm/L) of TiO2 nanoparticles
were used in electroless plating bath solution. It is clear
from the above discussions that the addition of different
surfactants with their respective TiO2 nanoparticles and
phosphorus content in plating bath significantly affects the
corrosion behaviour. The explanation behind the incre-
ment of TiO2 particles’ contents in the Ni-P composite
matrix under the influence of the surfactants (CMC
11
concentration) is due to the reduction of surface tension
during the plating process.
2.3.3 Other particles
Electroless Ni-P-CeO2 and Ni-P-Si3N4 composite coatings
exhibit a significant improvement in corrosion resistance
in 3.5 wt% sodium chloride solution compared to electro-
less Ni-P coating (Balaraju et al. 2001; Jin et al. 2008).
Owing to the lower accountability of CeO2 containing
composite coating for local-cell corrosion, corrosion
resistance is higher in the CeO2 containing coating. More-
over, Fe3O4 containing Ni-P composite coating also has a
positive effect on corrosion protection on cyclic oxidation
test at 800 °C (Zuleta et al. 2009) but at 900 °C the corrosion
protection deteriorates due to the deviation from parabolic
kinetics. The inclusion of 20 nm sized SiO2 nanoparticles in
the Ni-P matrix can enhance the corrosion properties in
salty environment (Rabizadeh and Allahkaram 2011). The
deposition of Zn in electroless Ni-P composite coating
provides good corrosion resistance in the salty corrosive
media (Assaf et al. 2018; Ranganatha et al. 2010). In a
recent study it is found that the inclusion of carbon
nanotubes (CNTs) in the porous Ni-P composite matrix can
be saturated into very small pores, making the passive film
more stable and compact. The excellent electrochemical
characteristics of Ni-P-CNT coating have extensive appli-
cations in electronic industries due to its anticorrosive
nature. The first step is to activate the CNTs through single
step activation method with palladium–tin catalytic nuclei
(Ang et al. 1999; Liu et al. 2020) to make compatible with
the electroless Ni-P coating. These activated nanotubes are
used as precursors for electroless Ni-P coating to obtain
nickel and palladium decorated nanotubes. The incorpo-
ration of alumina (Al2O3) particles in electroless plating
bath solution can enhance the corrosion resistance but the
particle size of Al2O3 can play a vital role in this regard. The
larger particles (approximately 1000 nm, Balaraju et al.
2006b) using in the bath give remarkable protection from
corrosive damages while by using smaller alumina parti-
cles shows lower corrosion resistance than as-plate Ni-P
coating.
The incorporation of different sols in electroless
plating solution can enhance the corrosion properties
remarkably without modifying the other properties. Hybrid
silica, titania, alumina and zirconia sols are some of the
examples (Chiba et al. 2018; Hughes et al. 2015; Klomjit and
Buchheit 2020; Song et al. 2006; Trueba and Trasatti 2015;
Zheng and Yi 2017).
Another important constraint on all the work dis-
cussed in the field of corrosion is the inclusion of B4C
12 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
(Araghi and Paydar 2010), Si3N4 (Das et al. 2007), PTFE (Wu
et al. 2005)and Ti3C2Tx@TiO2/MoS2 (Du et al. 2020) parti-
cles in the electroless Ni-P composite coating matrix re-
duces the corrosion resistance due to the generation of
microcracks and porosity which leads to easy access to the
corrosive media and defects the coating matrix surface. The
increment of anodic polarization is another reason behind
the corrosive attack (Abdel Aal 2008; Baghery et al. 2010;
Huang and Xiong 2008). The formation of microcells
throughout the MoS2 nanoparticles and the active chloride
ion (Cl−) damage the anticorrosion ability of the Ni–P–
MoS2 coated surface (Hu et al. 2009a). The electroless Ni-
P-Ti3C2Tx@TiO2/MoS2 composite coating also produces
micro holes and pits due to the least corrosion current
density on the coated surface, resulting in an increased
corrosion rate (Hu et al. 2009b; Morales et al. 2011).
2.4 Effect of double layer and pretreatment
A double black layer of electroless Ni-P coating has some
definite applications. In the case of sunlight absorptions, a
double black Ni-P composite coating can be used with a
coarse sandblast. Normally, 1–2 h is enough for single layer
Ni-P coating deposition. Extended time (3 h) is normally
required for double black layer coating deposition. It can
be seen from the measurement of the corrosion rate in
1.35 wt% NaCl electrolyte that single layer Ni-P coating had
a corrosion rate of 0.5 mm per year (mpy), while for the
double layer Ni-P coating it was 0.4 mm per year (mpy)
(Sosa Domínguez et al. 2017). The upper discussion dem-
onstrates that the black Ni-P double layer coating provides
higher corrosion resistance against unpropitious atmo-
sphere. The free paths of the first layer become partially
blocked between the electrolyte and the substrate due to
the appearance of low frequency time-constant related to
corrosion which is attributed by the second layer. However,
another research opposes this hypothesis. There has been
shown that as-plated single Ni-P coating exhibited higher
corrosion resistance than duplex Ni-P coatings. The per-
centage of corroded surface after 336 h for single Ni-P
coating is only 1.50%, while for duplex Ni-P coatings, the
corroded surface was recorded as 8.68% after 336 h (Bonin
et al. 2018). For deposition of duplex nickel–phosphorus/
nickel–boron (Ni-P/Ni-B) coatings, samples are first
immersed in Ni-P plating and after that samples are directly
immersed into the nickel–boron (Ni-B) plating bath. The
plating bath used for deposition is based on sodium hy-
droxide, nickel (II) chloride hexahydrate and sodium
borohydride as reducing agent and mixed oxide tungsten
as stabilizer. Thus, Ni-P/Ni-B duplex coating is formed and
shows the value of 3.53 × 10−3 mA/cm2 corrosion current
density (Vitry et al. 2012b). The top layer has a greater
influence on corrosion resistance in case of duplex
coating (Hu et al. 2019). In other words, the top layer of
electroless nickel coating is used for its barrier properties
because the upper coating is free from moving porosities
and other significant defects that might threaten its
durability. Vitry et al. (2012b) and Narayanan et al. (2003)
used same duplex Ni-P/Ni-B coating for their experiment.
However, the corrosion current density value of their
experiment was different due to the variation in coating
thickness. The coating thickness of Vitry’s sample was
25 µm and showed higher corrosion resistance than San-
kar’s sample where coating thickness was reported to be
20 µm. From the above findings it can be concluded that
the higher coating thickness gives greater protection
against corrosion.
The double nickel immersion pretreatment carries
excellent corrosion properties with a value of 2.216 × 10−3
mA/cm2 corrosion current density. In double Ni immersion
pretreatment method, nickel immersion solution was
conducted with 68 wt% concentrated nitric acid for 5 s (Yin
and Chen 2013) to remove the nickel film obtained in the
first nickel immersion process. The sample was then
cleaned with distilled water, and activation was repeated
and thus it is called double immersion pretreatment
method.
The pretreatment of a substrate by Zn before immer-
sion in electroless Ni-P bath can improve the corrosion
resistance. The thin layer of Zn is coated on the substrate by
using electroplating method as pretreatment. The tradi-
tional and sonochemical warm water processing including
as-synthesized Zn crystals for the transformation into the
ZnO phases provides good corrosion resistance. It has been
noted that corrosion resistance for Zn pretreated Ni-P
coating was increased to 66% from normal Ni-P coating.
The ZnO nanosheets are formed under the Ni-P coating
matrix and acts as a barrier by raising the stability of ZnO
nanoparticles which can keep the surface away from cor-
rosive damages (Sharifalhoseini et al. 2018). From surface
and grain boundaries, the additional scattering centers of
ZnO is found which can create chemical effect on the
improved corrosion resistance (Dhoke et al. 2009).
Organic and inorganic nanosized particles are being
used comprehensively in a different engineering fields
including photochemistry, electrochemistry, ultracapacitors
and supercapacitors (Marzocchi et al. 2007; Sharifalhoseini
and Entezari 2015; Xu et al. 2017). In addition, the substantial
improvement in the strength and corrosion resistance of
different materials changed by nanoparticles has made
nanotechnology suitable for a wide range of engineering
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
applications. ZnO is also used in biomedical applications
due to its nontoxic and biocompatible feature (Wang et al.
2013; Xu et al. 2013). In addition, this ceramic oxide can be
used as building blocks for electronic and optoelectronic
devices (e.g. solar cells, lasers and ultraviolet light emit-
ters) known for its high electron communication ability and
near ultraviolet emission (Ameen et al. 2012; Li et al. 2015).
2.5 Effect of heat treatment
A number of studies have examined that heat treatment
reduces the corrosion resistance of electroless Ni-P coating
consistently. The increased corrosion phenomena are
found due to the transition in microstructure of the heat-
treated coatings. In as-deposited condition, electroless
coatings usually show an amorphous structure that di-
vulges greater corrosion resistance. However, due to the
application of heat treatment, crystalline structures are
found, and grain boundaries are formed as active sites for
corrosion attack. There are different temperature ranges for
heat treatment which reveal the variations in corrosion
characteristics. It has been experimentally demonstrated
that phosphorus content might be reduced from the coated
substrate when more than 300 °C (Srinivasan et al. 2010)
heat treatment is applied. This can be evident from previ-
ous discussion that low phosphorus content decreases the
corrosion resistance. The decrement of phosphorus con-
tent of the coating reduces the corrosion resistance by
forming nickel phosphide (Ni3P) phase around 320 °C.
Increased heat-treatment temperature can enhance the
phosphorus segregation and form Ni3P phase. Therefore, it
is deduced that heat treated substrates are not generally
amorphous. Heat treated coatings display lower corrosion
resistance due to the grain boundary of its definite struc-
ture. The additional borders are normally seen between
nodules in nanocomposite coatings that have the effect of
subduing deformation and enable the formation of
microcell corrosion. These microcell attacks on the surface
of the object may increase with the lapse of time and can
cause a severe damage to the object. The heat treatment
affects the corrosion potentials and does not change the
morphology (Figure 7) of the coating structures remarkably
to form a passive region. Therefore, heat treatment vastly
escalates the value of corrosion current density resulting in
an enhancement in corrosion rate.
The electroless Ni–high phosphorus content com-
mences to lose its amorphous structure at the temperature
above 260 °C. With medium and high phosphorus content,
intermediary metastable phases such as NiP2 and Ni12P5
can evolve before stable Ni3P phase is formed. Nickel–
13
phosphorus (Ni3P) stable phase is established when the
temperature of the heat treatment exceeds 380 °C (Guo
et al. 2003; Keong et al. 2003; Sahayaraj et al. 2014). The
electroless Ni-P coating becomes crystalline upon heat
treatment at 400 °C for 1 h and form face centered cubic
(f.c.c) Ni and body-centered tetragonal (b.c.t) Ni3P phases.
After heat treatment, the electroless Ni-P coating possesses
a strong orientation of Ni along (111) and (200) peak. During
the heat treatment process, Ni-P coating matrix increases
the proliferation of the Ni atom along (111) crystal among
other significant phases which is responsible for improved
corrosion current density. Unfortunately, in case of heat-
treated electroless Ni-P coating, a mixture of crystalline Ni
(111) and Ni3P (231) phase is constructed with a greater
number of grain boundaries that can drastically lower the
corrosion resistance (Sankara Narayanan et al. 2006). The
stage transition takes place within the surface, leading to
the precipitation of the Ni3P process at 400 °C. Moreover, it
has been experimentally demonstrated from XRD analysis
(Hari Krishnan et al. 2006; Sahoo and Das 2011) that as-
plated Ni-P coating shows short range order broad peak.
However, after heat treatment Ni phase peak shows
sharper apex than Ni3P phase peak (Vitry 2012a). The heat-
treated Ni-P coated substrates do not make the transition of
its surface to a passive form and the corrosion current
density increases as the potential increases. As a result, the
corrosion resistance reduces due to the drastic change of
corrosion current density. The expose of corroded surface
after 168 h for as plated Ni-P coating is only 0.27% and for
heat treated Ni-P coating, it exhibited 10.87% (Bonin et al.
2018). Therefore, it can be inferred that heat-treated elec-
troless Ni-P coatings are less defensive than as-plated
coatings. Corrosion parameters of different electroless Ni-P
based coatings in before and after heat-treated conditions
have been shown in Table 6.
Figure 7: Surface morphology of heat-treated Ni-P coating (Wu et al.
2015). (Reprinted with permission, Copyright 2015 Elsevier).
14 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Heat treatment (HT) of the Ni-P coating upon twinning-
induced plasticity (TWIP) steel was applied at 350 and
700 °C for 1 h in argon atmosphere (Hamada et al. 2015; Liu
et al. 2016). The post heat treatments drastically increase
the corrosion current density which is the sign of decreased
corrosion resistance. As-plated Ni-P coating on TWIP steel
shows a single large diffraction ridge which signifies the
characteristics of fully amorphous structure. The large
diffraction ridge is obtainable due to high phosphorus
content with saturated amorphous domain (Hu et al. 2006).
The most striking observation in this finding is 700 °C heat
treatment provides higher corrosion resistance than the
heat treatment carried at 350 °C. Thus, it can be deduced
that there is no consistent relationship exists between the
corrosion current density and the temperature of heat
treatment for TWIP steel substrate. The corrosion rate of
electroless Ni-P coating at 350 °C is much higher in 0.5 wt%
H2SO4 solution due to the diffusion of iron and manganese
from the TWIP steel surface. It is well known that manga-
nese in the aqueous solutions appears to form manganese
oxides (MnO) and give rise to Mn2+ ions with hydrogen
evolution resulting in high corrosion rate.
The ternary Ni-P-SiC alloy composite coating shows
some surprising corrosion properties in heat treated con-
dition at different temperatures according to the finding of
some researchers (Bigdeli and Allahkaram 2009; Ghavidel
et al. 2020; Wang et al. 2013). The coating structure of as-
deposited Ni-P-SiC composite matrix shows the amorphous
nature and uniform distribution of SiC nanoparticles which
indicates better corrosion protection. After applying higher
temperature heat treatment, Ni reacts with SiC and nickel
silicide is formed with free carbons. The electroless nano-
composite coating crystallizes into nickel crystal, nickel
phosphide (NixPy), and nickel silicide when the heat-
treated temperature rises to 400 °C. No phase transition
takes place before 200 °C heat treatment and this phe-
nomenon is confirmed by a single wide peak profile. The
diffraction peak starts to disappear gradually at 600 °C
(Chen et al. 2002) heat-treated condition. There have been
studies of the analysis of nano-sized SiC particulates in the
Ni-P coating matrix, the SiC nanoparticles have the sig-
nificant influence on corrosion resistance (Allahkaram
et al. 2011; Bigdeli and Allahkaram 2009; Jiang et al. 2020).
Ghavidel et al. (2020) reported on his experiment that Ni-P
coating and the incorporation of 40 nm sized SiC nano-
particles in Ni-P composite matrix showed poor corrosion
resistance at 400 °C heat treated condition. However, both
Ni-P coating and Ni-P-SiC composite matrix at 300 °C heat
treated condition sharply reduces the corrosion current
density, resulting in higher corrosion resistance. Heat
treatment has adverse effect on corrosion resistance but at
a certain limit of heat-treated temperature corrosion
resistance can be increased. Heat treatment at ≤300 °C is
favorable for corrosion protection and it has been already
proved by previous research (Ghavidel et al. 2020; Vitry
et al. 2012b; Wang et al. 2013). Wang et al. (2013) showed
some different results by adopting two different heat-
treated temperatures. He used 500 nm particle sized SiC
nanoparticles and selected 275 and 400 °C as heat treated
temperatures. He showed the highest corrosion resistance
(0.07 × 10−3 mA/cm2 current density) holds good for 400 °C
heat treated temperature that is literally under debate
while a number of studies suggesting that more than
300 °C temperature is not suitable for better corrosion
protection (Bigdeli and Allahkaram 2009; Hamada et al.
2015; Narayanan et al. 2003; Novakovic and Vassiliou 2009;
Wu et al. 2015).
Ma et al. (2014) showed in his research article that at
400 and 600 °C heat treated Ni-P-SiC coated samples
reveal higher corrosion resistance than as-plated Ni-P-SiC
coated sample. However, this result obtained by (Ma et al.
2014) highly contradicts with the findings of other
researchers. Bigdeli and Allahkaram (2009) reported that
the coating structure and improved density at 400 °C heat
treatment, increased corrosion resistance of Ni-P and
Ni-P-SiC composite coatings. In this experiment, nano-
sized (average size 40 nm) β-silicon carbide particles were
used for SiC codeposition. This result also contradicts
with previous researchers’ outcomes. Most of the
researchers showed that heat treatment (400 °C for 1 h)
has adverse effect on corrosion resistance (Bigdeli and
Allahkaram 2009; Hamada et al. 2015; Narayanan et al.
2003; Novakovic and Vassiliou 2009; Wu et al. 2015).
Bigdeli et al. added hexadecyltrimethyl ammonium bro-
mide (HTAB) for particles dispersion and surface charge
adjustment in the Ni-P-SiC plating solution. That is quite
uncommon addition in his experiment and has not been
adopted by the other researchers. So, this may vary the
results and exhibit quite opposite value. Moreover, Huang
et al. (2004) showed also some different result on heat
treatment effect. He showed that proper heat-treatment
at 400 °C for 1 h significantly improves the corrosion
resistance. But it contradicts from previous results and
researchers’ inspections. Nevertheless, he selected an
ethoxylate type additive (2,4,7,9-tetramethyl-5-decyne-
4,7-diol ethoxylate) as surfactant for particle dispersion
which is quite different addition from other researchers
experiment. This additive may increase corrosion resis-
tance despite of applying heat-treatment (400 °C and 1 h).
In his experiment, he added 8–10 gm/L SiC powder
in electroless Ni-P-PTFE coating bath solution which
exhibited the highest corrosion resistance after applying
Table : Corrosion parameters of different electroless Ni-P based coatings under heat treatment conditions.

Coating Substrate with (condition) Before heat treatment Heat treated condition After heat treatment References

icorr (mA/cm) Ecorr (mV vs. SHE) icorr (mA/cm) Ecorr (mV vs. SHE)

Ni-P coating AZ Mg alloy . × – −  °C,  h . × – − Ghavidel et al. ()
TWIP steel  × – −  °C,  h  × – − Hamada et al. ()
AZ Mg alloy . × – −  °C,  h  × – − Ghavidel et al. ()
Steel (HTAB additive used) . × – −  °C,  h . × – − Bigdeli and
Allahkaram ()
TWIP steel  × – −  °C,  h  × – − Hamada et al. ()
Carbon steel . × – −.  °C,  mint. (vacuum . × – −. Novakovic and
heat treatment) Vassiliou ()
Ni-P-SiC coating AZD Mg alloy (SiC particle size  nm used) . × – −  °C,  h . × – − Wang et al. ()
AZ Mg alloy (SiC particle size – nm used) . × – −  °C,  h . × – − Ghavidel et al. ()
AZ Mg alloy (SiC particle size – nm used) . × – −  °C,  h  × – − Ghavidel et al. ()
AZD Mg alloy (SiC particle size  nm used) . × – −  °C,  h . × – − Wang et al. ()
Steel (SiC particle size  nm and HTAB additive . × – −  °C,  h . × – − Bigdeli and
used) Allahkaram ()
Ni-P-TiO Z Al alloy ( mL TiO sol used) . × – −  °C,  h with argon . × – − Wu et al. ()
coating flow
Carbon steel (. gm TiO particles used) . × – −.  °C,  mint. (vacuum . × – −. Novakovic and
heat treatment) Vassiliou ()
Duplex Ni-P/Ni- Aluminium . × – −.  °C,  h . × – −. Vitry et al. (b)
B coating Mild steel . × – −  °C,  h . × – − Narayanan et al. ()
I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
15
16 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
heat treatment at 400 °C. The additional surfactant may
activate the SiC and PTFE particles and retards autocat-
alytic chemical reactions between substrate and the
electrolyte.
Conceptually similar outcome of heat-treated coating
has also been carried out by Wu et al. (2015) at 400 °C heat
treatment in which heat-treated Ni-P and Ni-P-TiO2 sol
composite coating possessed higher corrosion rate than as-
plated composite coatings. Samples with as-plated Ni-P
coatings, the corrosion current density is 1.33 × 10−3 mA/
cm2 but for heat-treated Ni-P coatings, corrosion current
density is 1.48 × 10−3 mA/cm2 which indicates that heat
treatment adversely affects the corrosion resistance of as-
plated coatings. Though heat treated Ni-P-TiO2 sol com-
posite coating showed lower corrosion resistance, its
corrosion current density value is quite small noting only
2.03 × 10−3 mA/cm2 (Wu et al. 2015). The lower current
density value has been possible to obtain because of using
TiO2 sol in electroless plating bath solution and 6 °C/min
(Wu et al. 2015) heat is applied isothermally in argon flow
which is 99.99% pure. These conditional parameters can
prevent oxidation and avoid consequent microcracks on
the coated surface. Due to showing the lower current
density for the Ni-P-TiO2 sol composite coating, some re-
searchers have selected 400 °C as ideal heat treatment
temperature (Liu et al. 2007; Vojtěch et al. 2009). However,
the optimum temperature for heat treatment should not
exceed 300 °C to get better corrosion protection as it has
been discussed earlier.
Vacuum heat treatment at 800 °C for 10 min duration of
electroless Ni-P coating exhibits lower corrosion resistance
than as-plated Ni-P coating. The addition of 0.5 gm/L TiO2
in electroless Ni-P coating and applying vacuum heat
treatment at similar conditions can slightly increase the
corrosion resistance but still the corrosion resistance re-
mains lower compared to as plated Ni-P coating. During
heat treatment, the deposition of TiO2 nanoparticles in the
electroless plating solution may inhibit the growth of
nodular shaped spherical grains. The vacuum heat treat-
ment is carried out generally by a 300 ls−1 diffusion
pumping which can create a close high vacuum environ-
ment and then samples are thermally treated for 10 min
using molybdenum (Mo) foil resistor (Novakovic and Vas-
siliou 2009). The thickness of Mo foil resistor is 0.15 mm
and through this thin resistor alternate current (AC) can
flow. A mixture of crystalline nickel and nickel–phos-
phides phase is generated after vacuum heat treatment so
that areas with different active/passive corrosion cells are
formed. On the surface of electroless Ni vacuum heat
treated composite coating micro-voids are observed and
these small pores can significantly reduce the corrosion
resistance.
Heat treatment of the system at 180 °C with a duration
of 4 h (Vitry et al. 2012b) causes a notable enhancement in
the corrosion potential of the Ni-P/Ni-B duplex system and
increases corrosion resistance (icorr 1.10 × 10−3 mA/cm2) but
for as-plated duplex Ni-P/Ni-B system, the icorr value is
3.53 × 10−3 mA/cm2 (Vitry et al. 2012b). The lower temper-
ature (180 °C) heat treatment causes a slight densification
of the duplex coating resulting in high corrosion resis-
tance. The top layer (Ni–B) of the duplex Ni-P/Ni-B com-
posite coating is not greatly modified by the low
temperature heat treatment. Similar heat treatment tem-
perature has also been selected by Delaunois and Lienard
(2002) and Vitry et al. (2008) in which heat treatment is
carried out under Ar (with 5% H2) to prevent oxidation at
180 °C.
Among TiB2, ZrB2 and TiC particles on the stability of
high phosphorus electroless nickel plating bath, TiC offers
better corrosion resistance. Heat treatment at 400 °C for 1 h
affects the corrosion protection (Huang et al. 2019).
There is an interesting scenario of heat treatment
which has been observed from the upper discussions. Heat
treated Ni-P coatings at 300 °C exhibited better corrosion
resistance compared to other heat treatment temperatures
and thus it can be selected as the standard heat-treated
temperature. It is therefore clear from the upper discussion
that heat treatment up to 300 °C is considerable for higher
corrosion resistance, but more than 300 °C is not desirable
at all.
Different corrosion parameters of electroless Ni-P
based coatings immersed in 3.5 wt% NaCl solution have
been shown in Table 7
2.6 Effect of corrosive media
Sodium chloride solution is the most common electrolyte
used during the corrosion test for laboratory purposes. In
3.5 wt% NaCl solution, electroless Ni-P and Ni-P-SiC-PTFE
composite coatings revealed higher corrosion resistance
than in 2.67 wt% H2SO4 solution (Huang et al. 2004). The
incorporation of either SiC or TiO2 particles marginally in-
crease the corrosion resistance of the coating in 3.5 wt%
NaCl solution but adversely affects their corrosion resis-
tance in 2.67 wt% H2SO4 solution. The previous study
suggested that the lower corrosion resistance was resulted
from the non-uniformity and lower density caused by
co-deposition of PTFE particles in electroless Ni-P com-
posite matrix (Wu et al. 2005). However, electroless
Table : Corrosion parameters of electroless Ni-P based coatings immersed in . wt% NaCl solution.

Sample with condition icorr (mA/cm) Ecorr (mV vs. SHE) Rct (Ω cm) Cdl (µF) Corrosion rate (mpy) References

Ni-P (.% P) . × – − , . – Sankara Narayanan et al. ()
Ni-P (.% P) – –  – – Cui et al. ()
Ni-P (.% P) . × – − – – – Balaraju et al. (b)
Ni-P (.% P) . × – − , . – Sankara Narayanan et al. ()
Ni-P (.% P) . × – −   – Sankara Narayanan et al. ()
Ni-P (.% P) in aerated condition . × – − – – . Ashassi-Sorkhabi and Rafizadeh ()
Ni-P (.% P) in aerated condition . × – − – – . Ashassi-Sorkhabi and Rafizadeh ()
Ni-P (.% P) in aerated condition . × – − – – . Ashassi-Sorkhabi and Rafizadeh ()
Ni-P (.% P) in deaerated condition . × – − , – . Balaraju et al. (a)
Ni-W-P in deaerated condition . × – − , – . Balaraju et al. (a)
Ni-W-Cu-P in deaerated condition . × – − , – . Balaraju et al. (a)
Ni-Cu-P . × – −  – – Cissé et al. ()
Ni-P with  gm SiC (particle size – nm) . × – − – – – Ghavidel et al. ()
Ni-P with  gm SiC (heat-treated at  °C) . × – − – – – Ghavidel et al. ()
Ni-P with  gm/L SiC (particle size  nm)  × – − – – . Calderón et al. ()
Ni-P with  gm/L SiC (particle size  nm)  × – − – – . Calderón et al. ()
Ni-P with  gm/L SiC (particle size  nm) . × – − – – – Ahmadkhaniha et al. ()
Ni-P with  gm/L SiC (particle size  nm and . × – − – – – Bigdeli and Allahkaram ()
HTAB additives used)
Ni-P with  gm/L SiC  × – − – – – Ma et al. ()
Ni-P with  gm/L SiC (heat-treated at  °C) . × –  – – – Ma et al. ()
Ni-P-SiC (HTAB additives used and heat treated at  °C) . × – − , – – Bigdeli and Allahkaram ()
Ni-SiC-PTFE (as-plated) – – , – – Huang et al. ()
Ni-SiC-PTFE (heat-treated at  °C) – – , – – Huang et al. ()
Ni-PTFE (as-plated) – –  – – Huang et al. ()
Ni-PTFE (heat-treated at  °C) – – , – Huang et al. ()
Ni-TiO (. wt% TiO) . × – − , – . Baghery et al. ()
Ni-TiO (. wt% TiO) . × – − , – . Baghery et al. ()
Ni-TiO (. wt% TiO) . × – − , – . Baghery et al. ()
Black Ni-P-TiO coating  × – − – – – Khollari et al. ()
Ni-P-TiO ( gm TiO) . × – −  . . Tamilarasan et al. ()
Ni-P- . gm TiO with (. × CMC) SDS surfactant . × – −  . . Tamilarasan et al. ()
Ni-P- . gmTiO with ( × CMC) DTAB surfactant . × – −  . . Tamilarasan et al. ()
Ni-P- mL TiO sol and .% P content . × – − – – – Wu et al. ()
Ni-P-TiO sol (heat-treated at  °C with argon flow) . × – − – – – Wu et al. ()
Ni-P-TiO-GO . × –   – – Uysal ()
Promphet et al. ()
I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings

Ni-P- mL TiO sol and <% P content . × – − – – –

Ni-P-TiO sol-RGO . × –  – – – Promphet et al. ()
Ni-P-TiO (vacuum heat treated at  °C) . × – −. – – – Novakovic and Vassiliou ()
Ni-P-AlO ( nm) . × – − – – – Balaraju et al. (b)
17
 18 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings

Ni-P-PTFE coating surprisingly showed higher corrosion

resistance in 2.67 wt% H2SO4 solution rather than 3.5 wt%
NaCl solution, which exhibited completely opposite char-

Sosa Domínguez et al. ()

acteristics of other researchers’ findings. Hamada et al.

Sharifalhoseini et al. ()

(2015) used 0.5 wt% H2SO4 solution as corrosive media for
Balaraju et al. (b)

his experiment. The Ni-P coating on a twinning-induced

Khollari et al. ()

Yin and Chen ()
Vitry et al. (b)
Vitry et al. (b)
plasticity (TWIP) steel containing 25 wt% Mn and 3 wt% Al
Cui et al. ()
Du et al. ()

shows average corrosion resistivity in 0.5 wt% H2SO4 so-

References

lution indicating 20 × 10−3 mA/cm2 (Hamada et al. 2015)

corrosion current density due to the absence of grain
boundaries and surface defects. If 3.5 wt% NaCl electrolyte
was used instead of 0.5 wt% H2SO4, the corrosion current
–
–
–

–
–
–
–
–
Corrosion rate (mpy)

.

density value might be less than 20 × 10−3 mA/cm2 and the

improved corrosion resistance could be reported. There-
fore, it can be concluded that corrosion resistance in salty
atmosphere provides better results than in acidic media.
Shibli and Dilimon (2007) used 32 wt% NaOH solution
as an electrolyte and they showed corrosion current den-
sity value is 0.82 × 10−3 mA/cm2. This superior corrosion
–
–
–
–
–
–
–
–
–
Cdl (µF)

resistance behaviour is possible due to the enrichment of

phosphorus (18 wt%) content. If they used NaCl electrolyte
Rct (Ω cm)

–
.


,
–
–
–
–

instead of NaOH, then the corrosion current density could

be lower than 0.82 × 10−3 mA/cm2 and highest corrosion
resistance could be achieved. The differences in the
corrosion rates in various solutions are very large. Elsener
Ecorr (mV vs. SHE)

−
−
–
−
−
−.
−
−
−

et al. (2008) showed that the worst one is in the 5 wt% HCl,
and the best is in the 10 wt% NaCl. The corrosion resistance
in the four solutions for the Ni-Cu-P and Ni-Sn-Cu-P de-
posits increases according to the following sequence: 5 wt
% HCl, 2.67 wt% H2SO4, 50 wt% NaOH and 10 wt% NaCl.
The data showed that Sn does not usually improve the
icorr (mA/cm)

–
. × –
 × –

. × –
. × –
. × –
. × –
. × –
 × –

corrosion resistance of the Ni-P based alloy deposits in HCl,

H2SO4, NaCl and NaOH solutions. However, phosphorus
and copper content usually improve the corrosion resis-
tance in the four solutions.
Charge transfer resistance (Rct) for electroless Ni-Cu-P
coated substrate in 5.35 wt% H2SO4 solution was 108 Ωcm2
while it was 9210 Ωcm2 in 3.5 wt% NaCl solution (Cissé et al.
2010). The result showed a marginal improvement of
Ni-P (double pretreatment with Ni immersion)

corrosion resistance in 3.5 wt% NaCl solution which is

almost 90 times higher compared to acidic medium. The
Duplex Ni-P/Ni-B heat-treated at  °C

findings also showed a slight trend towards passivation in

sulfuric acid and hydrochloric acid by the presence of a
current plateau in anodic polarization in acidic media.
Duplex Ni-P/Ni-B as-plated
Ni-P-TiCTx@TiO/MoS

Ni-P (pre-coated with Zn)

There was no passivity pattern in the measurement range

Ni-P with zincating bath
Sample with condition

Ni-P-AlO ( nm)

which is consistent with the work of Mimani and Mayanna

Black Ni-P (.% P)
Table : (continued)

Ni-P (double layer)

(1996). However, in the anodic range, a substantial

decrease in corrosion current densities is observed in the
presence of alloy for (3.5 wt% NaCl) salty environment.
Corrosion rate of electroless Ni-P coating in different en-
vironments has been shown in Table 8.
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings 19

2.7 Effect of coating process parameters

2.7.1 Time

The corrosion current density of as-deposit samples

inconsistently increases with increase of coating deposi-
tion time (i.e. decrease of phosphorus content). Thus, it
increases the corrosion rate. From Figure 8, it must be wise
to keep the coating deposition time in electroless Ni-P so-
lution between 1 and 1.5 h.

2.7.2 Temperature

Temperature is an important parameter which affects the Figure 8: Effect of electroless Ni-P coating deposition time on
rate of deposition of electroless Ni-P coating. The reactions corrosion rate (Ashassi-Sorkhabi and Rafizadeh 2004).
occur during the deposition process are endothermic. As a
consequence, the deposition rate increases by increasing
salty baths are maintained at 80–90 °C while the alkaline
the temperature. The impact of bath temperatures (Taheri
baths can be run at lower temperature (40 °C).
2002) on the deposition rate of the coating has been shown
in Figure 9. Corrosion resistance increases with enhanced
bath temperature at certain limit. The bulk of the acidic and 2.7.3 pH

Table : Corrosion rate of electroless Ni-P (– wt% P) coatings

Many of the reactions involved in the deposition process of
in different environments at  °C except where the temperature is electroless Ni-P coating are susceptible to changes in so-
specified (Sudagar et al. ). lution pH. By increasing the pH of the coating bath solu-
tion, the phosphorus release from the hypophosphite is
Corrosive media Corrosion rate × − (mm/year) retarded whereas nickel-reduction reaction is accelerated.
Acetic acid . Equation (7) is the simplified form of Equations (5) and (6),
Acetone . corresponds to nickel reduction while Equation (8) corre-
Aluminium sulphate (%)  sponds to phosphorus reduction. From Equation (7), it can
Ammonia (%) 
be concluded that the higher the concentration of H+ in the
Ammonium nitrate (%) 
Ammonium sulphate (saturated) 
electroless bath is, the less the deposition of the Ni will be.
Brine (.% salt) at  °C 
Calcium chloride (%) .
Citric acid (saturated) 
Cupric chloride (%) 
Ethylene glycol .
Ferric chloride (%) 
Formic acid (%) 
Hydrochloric acid (%) 
Hydrochloric acid (%) 
Lactic acid (%) 
Lead acetate (%) .
Nitric acid (%) 
Oxalic acid (%) 
Phenol (%) .
Phosphoric acid (%) 
Sodium carbonate (saturated) 
Sodium hydroxide (%) at  °C .
Sodium sulphate (%) .
Sulfuric acid (%) 
Water, acid mine (pH .) 
Figure 9: Effect of bath temperature of the coating solution on the
Reproduced with permission, Copyright  Elsevier. coating deposition rate (Taheri 2002).
20 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Figure 10: Effect of coating solution pH on phosphorus content
(Fayyad et al. 2019).
At lower pH, the percentage of Ni content in the coating is
low and the phosphorus content remains high. As the pH
increases, Equation (7) is shifted to the right direction,
causing a decrease in the concentration of H+, i.e., an in-
crease in the Ni content in the coating. On the contrary, as
the pH of the electroless bath decreases, the concentration
of the OH− ions decrease and, consequently, the percentage
of the P in the coating increases, which has been shown in
Figure 10. Therefore, decreasing the pH of the solution
increases the phosphorus content of the coating resulting
in higher corrosion resistance.
3NaH2 PO2 + 3H2 O  + NiSO4 / 3NaH2 PO3 + H2 SO4 + 2H2 +  Ni
2H2 PO−2 + Ni++ + 2H2 O  / 2H2 PO−3  +H2 + 2H+ +  Ni
Ni2+ + H2 PO−2 + H2 O  / Ni0 + H2 PO−3 + 2H+
3H2 PO−2 / H2 PO−3 + H2 O  + 2OH− + 2P
2.7.4 Coating thickness
The coating thickness is one of the parameters which is
responsible for the porosity of the coating surface. As the
Table : Electroless Ni-P deposits at various thicknesses.
Coating thickness (µm) Corrosion current
density, icorr (mA/cm)
  × –
  × –
. . × –
. . × –
. . × –
thickness of the coating increases, the pores and tiny holes
on coating surface diminishes, leading to enhanced
corrosion resistance. Thicker coatings passivate at the
lower corrosion current density and thus possess greater
resistance to corrosion. The coating thickness of electroless
Ni-P coated substrate was reported to be influenced by
phosphorus content (Shibli and Dilimon 2007). This refers
to the reduction of the coating’s porosity due to increased
coating thickness. There is a close relation between the
thickness of the coating and its corrosion resistance, as
shown in Table 9.
Summary of the coating parameters of electroless Ni-P
coated substrates in NaCl solution have been shown in
Table 10. As mentioned in the previous sections, there are
various coating process parameters of electroless Ni-P
based coatings which can highly influence the properties of
corrosion resistance. Figure 11 demonstrates the range of
these parameters that can effectively improve corrosion
resistance of electroless Ni-P coating.
3 Latest developed
electrochemical techniques
3.1 Localized electrochemical impedance
spectroscopy
The most recent development of electrochemical imped-
ance spectroscopy (LEIS) is instigated by Lillard et al.
(5)
(1992) which is further termed as localized electrochemical
(6) impedance spectroscopy (LEIS). The coated samples which
have poor electrochemical activity can be measured by
(7) the LEIS system. An external voltage like previously
mentioned in EIS method is applied to the LEIS system. A
(8)
movable LEIS probe can measure the local potential dif-
ference. The schematic diagram for LEIS measurement has
been shown in Figure 12. The electronic devices used in the
LEIS setup are a gamry potentiostat which is integrated
with a frequency response analyzer (FRA), two differential
amplifiers, a LEIS probe and a computer monitor to
Corrosion potential, Phosphorus References
Ecorr (mV vs. SHE) content (wt. %)
− – Taheri ()
− – Taheri ()
−  Shibli and Dilimon ()
−  Shibli and Dilimon ()
−  Shibli and Dilimon ()
Table : Summary of the coating parameters of electroless Ni-P coated substrates in NaCl solution.

Substrate Coating solution Elemental Coating operational parameters Results References

composition

NiSO (gm/L) NaHPO (gm/L) Ni (wt.%) P (wt.%) Time (min) Temperature (°C) pH icorr (mA/cm) Ecorr (mV vs. SHE)

Mild steel   . .   . . × – − Ashassi-Sorkhabi and Rafizadeh ()
  . .   . . × – − Ashassi-Sorkhabi and Rafizadeh ()
  . .   . . × – − Ashassi-Sorkhabi and Rafizadeh ()
  . .   . . × – − Ashassi-Sorkhabi and Rafizadeh ()
  . .   . . × – − Ashassi-Sorkhabi and Rafizadeh ()
  . .   . . × – − Ashassi-Sorkhabi and Rafizadeh ()
      . . × – − Narayanan et al. ()
  . .   . . × – − Shibli and Chinchu ()
  . .   . . × – − Balaraju et al. (b)
.  . .   . . × – − Sankara Narayanan et al. ()
.  . .   . . × – − Sankara Narayanan et al. ()
  . .    . × – − Sankara Narayanan et al. ()
 . . .    . × – − Balaraju et al. (a)
Copper . . . .   . . × – − Shashikala and Sridhar ()
       . × –  Gawad et al. ()
Steel .  . .   . . × – − Promphet et al. ()
  . .    . × – − Sharifalhoseini et al. ()
Aluminium   . .    . × – − Yin and Chen ()
 Al alloy   . .    . × – − Lee ()
 Al alloy   . .   . . × – − Khollari et al. ()
Z Al alloy   . .    . × – − Wu et al. ()
AZ Mg alloy   . .    . × – − Ghavidel et al. ()
Carbon steel   . .   . . × – − Tamilarasan et al. ()
  . .    . × – − Luo et al. ()
  . .   . . × – − Luo et al. ()
      . . × – − Balaraju et al. ()
  . .    . × – − Fayyad et al. ()
  . .   . . × – − Momenzadeh and Sanjabi ()
  . .   . . × – − Novakovic and Vassiliou ()
Brass   . .    . × – − Gholizadeh-Gheshlaghi et al. ()
Polyester fabric .  . .    . × – − Jiang and Guo ()
Polymer carbon    .   . . × – − Su et al. ()
I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
21
22 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Figure 11: Factors influencing the corrosion resistance for
electroless Ni-P based coatings.
visualize the data. Global and local impedances are
recorded concurrently with a four-channel frequency
response analyzer. Furthermore, transfer functions are
generally analyzed by frequency response analyzer. A dual
microprobe system has been introduced in this setup
which is encompassed in the movable LEIS probe. The
space between the two microprobes (micro reference
electrodes) is denoted by ‘d’. The most modern LEIS in-
struments have a tolerance of around 1 nanovolt (nV).
Differential amplifiers are used to monitor the data of local
potential and current density by applying high input
impedance. The two microprobes can sense the local po-
tential difference from where current density can be
calculated. The LEIS probe can travel in a three-
dimensional motion and it is controlled by imposing digi-
tal signal. With providing information of position, velocity
and direction, an encoder can regulate the positioning
system of the LEIS probe (Cui et al. 2015; Huang et al. 2011).
To enhance the ratio of signal and noise, the amplitude of
sinusoidal voltage should be set as large as possible by
performing the regulation of potentiostat. Some LEIS ex-
periments have been conducted by using 50 acquisition
cycles, seven points frequency per decade and 100 mV
peak signal (Huang et al. 2007).
The dual microprobe (microelectrodes) consists of
metallic wires. Each microprobe has its own metallic wires
and they are connected with the individual differential
amplifier. The diameter of those metallic wires can be
measured in micrometers which are very tiny in nature.
Molten glasses are used to seal the wires having very thin
internal diameter, and the sealing process is carried out by
a nichrome wire with a current controllable resistance
heater (Jaffe and Nuccitelli 1974). However, in the case of
Ag/AgCl microelectrodes, epoxy resin is used instead
of molten glass for sealing the silver wires. A thin layer of
silver chloride is formed according to the following elec-
trochemical reaction by anodizing the silver microelec-
trode in KCl solution:
Ag  + Cl− ⇄  AgCl  + e− (9)
It is necessary to first clean the silver microelectrode in
2 M KCl solution at the condition of 241.20 VSHE at the rate of
100 mV/s. After passing 5–10 min, potentiodynamic
oxidation occurs in that electrolyte with possessing 241.40
VSHE (Huang et al. 2011). The electrochemical tests are
usually conducted at room temperature using a standard
three-electrode cell. The dimension variation of Ag wires
can make difference the potential value. The potential
difference can be obtained by a platinum grid (counter
electrode) with respect to a reference electrode as shown in
the schematic diagram (Figure 12). There is a major impact
of the microprobe size and its position on of LEIS mea-
surement. A small microprobe is always desirable for the
experiment. The resistance of electrolyte must be reduced
in order to decrease the contribution of high frequencies, in
accordance with experimental results for different probe
positions above the working electrode (substrate).
The local current density can be measured by the
closest microprobe through controlling ohmic drop. The
LEIS measurement can therefore be improved using local
interfacial impedance to avoid high frequency. A recent
study has indicated that the consequences of the probe size
(Abreu et al. 2017). Some authors have also suggested using
the micro capillary electrochemical setup to solve the
probe dimension difficulty (Pilaski et al. 2002).
3.2 Scanning vibrating electrochemical
technique
Scanning vibrating electrochemical technique (SVET)
setup employs a conductive vibrating probe that de-
termines the potential difference between the probe and
the substrate in an electrolyte. The vibrating probe is
mounted on a piezoelectric actuator (Figure 13). A mea-
surement probe can be positioned closely above the sur-
face of the sample. The scanning probe instrument consists
of a very thin platinum tip. This tip of SVET probe measures
potential difference (ΔV). The SVET probe is typically
positioned 150 µm apart from the current source point
which normally supplies 60 nA current to the system. The
probe is wrapped with an insulated thin platinum–iridium
(Pt-Ir) wire. The tip is spherical in shape with 10 µm
diameter and coated with black platinum. The probe is
positioned 100 µm above from the surface and the fre-
quency of vibration probe normally remains at 398 Hz
(Gnedenkov et al. 2016). The piezoelectric motor can move
in all three dimensions. The piezo ceramic device controls
the movement of the probe allowing vibration amplitudes
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings 23

Gamry potentiostat

Reference electrode

Frequency Response
Differential Analyzer (FRA)
Amplifier
Counter electrode

Differential
Amplifier

Positioning system (x, y, z)

Working electrode Figure 12: A schematic diagram of LEIS setup.

(d) from 1 to 60 µm in the direction perpendicular (Z axis) to
the sample surface. An amount of 100 µA current (Bastos
et al. 2017) flows between the graphite electrodes (B to C).
This current is naturally generated from electrochemical
corrosion or biological process and is externally controlled
by a galvanostat. Potential difference is calculated from the
circuit at selected points (A to D). The reference micro-
electrodes which contain low impedance are used to
measure the ohmic drop in solution. Two reference mi-
croelectrodes are kept in a fixed position and they are
moved together. Due to the developed compact electric
field in the electrolyte solution, the potential difference
exists. The current density (I) can be easily determined by
measuring the potential difference ( ΔV), the amplitude of
vibration (d) and the solution resistivity (ρ) with the help of
Equation (13). To get the value of current density, the
method is repeated in a settled framework and acquires the
data from the plot of current density over a selected sample
surface (Dolgikh et al. 2016). From this current (I), corro-
sion rate can be measured.
I  = −(1/ρ) (ΔV/2d) (10)
The SVET probe position is regulated by an auto-
generated computer command. The close loop linear en-
coders can identify the exact position of the probe. The
vibrating nature of the probe in the perpendicular direction
to the substrate surface can generate a zone where AC signal
is developed. A lock-in amplifier (LIA) device is used to
extract the AC signal with its carrier wave from an extremely
noisy environment and converts it to a DC signal by using
input phase angle. The LIA is able to capture and demodu-
late not just small AC signals but also large signals. The LIA

LIA
Piezo-electric x, y, z
actuator axis

A SVET D
+ probe −
B
C

d
Figure 13: Schematic presentation of SVET.
24 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
acts as a rectifier in this SVET setup. The input phase angle is
usually determined by manually changing the phase input
of lock-in amplifier until no response is detected. The opti-
mum phase angle can be gained by adding 90°. Some
commercial equipment can be able to acquire the reference
phase angle directly. The converted DC signal which is ob-
tained from LIA device can then be plotted to represent the
distribution of local activity. The SVET signal chain config-
uration has been shown in Figure 14.
The use of SVET in corrosion studies is subject to
certain experimental drawbacks. The processing of data
acquisition takes longer time in the matrix. Another diffi-
culty can develop if the sample is not completely flat or is
not placed properly accordance with the scanning probe
(Jadhav and Gelling 2019). Larger amplitude vibrations
may damage the substrate (McMurray et al. 2003) and in-
hibits the electrochemical corrosion reaction by rippling of
the electrolytes resulting in an inaccurate value of current
density. SVET methods can be applied to determine
galvanic corrosion rate (Battocchi et al. 2005; Ogle et al.
2000; Simões et al. 2007), pitting corrosion (Dorman et al.
2017; Vuillemin et al. 2003; Williams et al. 2010), crevice
corrosion (Isaacs 1996), stress corrosion cracking (Isaacs
1988), corrosion due to microorganisms (Abdul-Rani et al.
2019; Chen et al. 2015; Franklin et al. 1991; Iken et al. 2008),
inorganic coatings (Manhabosco et al. 2015), coated ma-
terials (Ahmad et al. 2016; Bastos et al. 2010b), corrosion
inhibitors (Bastos et al. 2010a; Kallip et al. 2012; Kumar
et al. 2017; Toloei et al. 2013), corrosion of weldments
(Bertoncello et al. 2015; Lollini et al. 2019) and corrosion of
polymers (He et al. 2004).
Figure 14: SVET signal chain configuration.
3.3 Scanning ion-selective electrode
technique
The scanning ion-selective electrode technique (SIET)
works noninvasively and gives accurate measurements of
the pH and the presence of specific ionic species just
above surface of electrolyte (Fix et al. 2011). The sche-
matic diagram of SIET setup has been shown in
Figure 15A. The SIET probe contains a microelectrode
(Figure 15B) consisting of a glass or plastic micropipette
which is used for ion detection at the tip of the electrode
along with pH variance detection (Cabrini et al. 2017).
Ammann et al. (1985) had highlighted some technical
studies on ion-selective microelectrodes. A selective
ionophore-based membrane like oil is packed within a
glass-capillary microelectrode. Between the ion-selective
membrane and the metallic tip, an ion-to-electron trans-
ducer is mounted which is constructed from a conductive
polymer poly (3-octylthiophene-2,5-diyl). The electrode’s
ion-sensitive tip is approximately 10 μm long (Lamaka
et al. 2010) and for various applications, this can range
from 10 to 100 μm. A needle like Pt-Ir wire with an open
tip is the base of the microelectrode. A competitive lateral
resolution results from different diameter of the orifice of
ion-selective glass-capillary microelectrode which ranges
from 0.1 to 5 µm (Ammann et al. 1985).
Scanning ion-selective electrode technique functions
as a micro-potentiometric instrument which works on an
active solution surface to measure specific ions at a quasi-
constant micro-distance. Potentiometric experiments are
done under zero current circumstances in a two-electrode
galvanic cell. A potentiometric cell is made up of a refer-
ence electrode and a microelectrode specific for ions. A
Figure 15: (A) Typical set up for SIET method (B) glass-capillary ion-
selective microelectrode with liquid membrane.
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
SIET system includes the mentioned key elements: an ion-
selective microelectrode positioned on a 3D computer-
controlled stepper-motor system, which is used to place
and transfer the microelectrode above the specimen. A
video camera is located above the surface of the sample,
fitted with a long-distance lens which provides magnifi-
cation up to 400 times. It enhances and digitizes the po-
tential difference evaluated inside this potentiometric cell.
Ag/AgCl wires are used as a reference electrode. The
micropipette including the reference electrode is placed on
the computer-controlled 3D stepper motor. The sample is
dissolved in the electrolyte and both electrodes are carried
into the sample’s vicinity. Video-assisted camera optics
captures the image data, help place the probe and hold the
distance between sample and probe. Pre-assessment and
post-assessment of SIET is extensively required for the
microelectrode calibration. The travelling with motion and
speed of the micropipette across the surface of the sample
can be controlled by a computer-generated command. A 3D
data represents the spread of pH or ionic concentration of
sample. SIET tests are carried out in the context of
potentiometry. Throughout this control mode the potential
differences leading to variation in ionic concentration
are evaluated. On the basis of its ability to allow the specific
ions through the membrane, ionophore membranes are
used in ion selective electrode. The chemical potential
changes due to the diffusion of the ions through the
membrane and thus potential variations are observed by
means of the internal and external reference electrodes.
Usually, a silver chlorinated wire which is immersed
into the electrolytes is used as a reference electrode. For
SIET experiments, selective microelectrodes are generally
placed 50 μm above from the tracked surface. According to
the Nernst equation, calibration of H+-selective micro-
electrode is performed using the buffer solution. An ASET-2
(Science Wares) programming software can scan the
respective area. The potential can be calculated by using
1 PΩ rated input impedance preamplifier (Gnedenkov et al.
2016). The ion selective electrodes have some drawbacks
due to its physical structure. The micropipettes of glass are
delicate and therefore fragile. During the analysis and in
the calibration procedure, the transparent nature of glass
makes it difficult to obtain the correct distance between the
probe and the sample.
3.4 Scanning droplet cell technique
A scanning droplet cell (SDC) is a traditional three elec-
trode experiment with a localized electrochemical cell
25
scanned across the surface of the sample. A positive
displacement pump is used in the SDC technique which
can force the electrolyte from a gas-purged reservoir
through a small diameter tube. The narrow tube generates
a convection profile which can be controlled through pump
rate. The electrolyte is then sprinkled into the single
droplet on the surface of the substrate which acts as a
working electrode. The cohesive forces between liquid
molecules grasp this droplet on the surface and later can be
dragged across the sample by dint of capillary action. As
electrochemical reaction takes place between electrolyte
and electrode, contact portion of the sample with droplet is
measured. SDC experiments can be configured in one of the
two ways. Firstly, by applying a constant bias such as po-
tential or current and increment the position of the droplet
creating a data map. Secondly, by applying a static or dy-
namic electrochemical signal to perform experiments such
as Tafel or EIS as the droplet is held in a fixed position.
Because the droplet is a self-contained, three electrode
chemical cell. The force sensor which is mounted on a fixed
position of the scanning flow cell (SFC) can measure the
force of the droplet when pressed against the working
electrode. The SFC consists of inlet and outlet channels
which are intersected in a polycarbonate block and it also
has an elliptical opening at the bottom of the cell body
(Figure 16). The reference and the counter electrode are
positioned directly into the channels of the SFC cell and the
working electrode is located directly under the elliptical
opening into an automatic three-dimensional stage. Ag/
AgCl is used as reference electrode while platinum wire is
used as counter electrode. To avoid the leakage of the
electrolyte, a 150 µm (Schuppert et al. 2012) thick silicon
gasket is attached at the opening of the electrode. The
working electrode is 500 µm (Kulyk et al. 2015) far from the
bottom of the cell. The droplet contact area and the capil-
lary size should be as small as possible (Kollender et al.
2015; Snowden et al. 2010). Since the sample measurement
area is very small, the induced current range is as little as in
picoamperes. The high resolution potentiostat can mea-
sure this small amount of current. A constant polarization
is applied during the time of scanning the SDC head and
the droplet across the surface in one direction and then the
responses (current, voltage and open circuit potential) are
measured. Although the droplet motion on the surface is a
dynamic process, the ohmic drop should be considered as
well. Moreover, as it is a flow-type cell, it makes fast com-
bination with downstream analysis or even with spec-
trometry. The SDC technique is suitable for both DC and AC
measurements with the same configuration one after the
other (Cherevko et al. 2014; Efaw et al. 2019).
26 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Figure 16: 3D diagram of scanning droplet cell.
3.5 Scanning electrochemical microscopy
Scanning electrochemical microscopy (SECM) methods
can analyse the electric potential of working electrode
(substrate) with higher accuracy. Using this technique, it
can easily access to scan the surface reactions in macro-
scopic scale. The experimental setup (Figure 17) of SECM
consolidates a piezo-electric actuator, a biopotentiostat
and an ultra-microelectrode (UME) which is used as a
SECM probe. The SECM probes are made of a noble metal
and they are normally rigid. Ultra-microelectrod tip is
vertically positioned above the surface of the substrate and
can capture the topographic view of the surface of the
substrate. Substrate and UME tip is regarded as working
electrodes whereas platinum electrode can be used as a
reference electrode. DC voltage is generally applied to the
SECM probe to measure the current response. The bipo-
tentiostat polarizes the UME tip as well as the substrate
individually and it can measure the currents. Potentiostat
is used to amplify the probe signal which is later converted
to a digital signal. One electrode is responsible for con-
ducting electrochemical reactions between the electrolytes
and the substrate whereas the other one can measure the
response. By changing the polarization level, tip collection
and tip generation data can be monitored. A stepper motor
gets response through the signal of position controller by a
computer-generated program. The positioning system can
scan the location of the measuring tip and through
generating a data map; it can calculate the electrochemical
parameters. The electric signal is then transmitted to the
mechanical energy and piezo-electric actuator can drive
the UME probe. The two-dimensional (X and Y) movements
of the probe are controlled by a position controller but the
vertical movement of the SECM probe is conducted
manually with respect to the substrate surface. Current is
recorded according to SECM probe position and is scanned
Figure 17: Schematic diagram of SECM experimental setup.
in either X or Y direction. The sensitivity of the SECM is
100 µV (Beheshti et al. 2016, 2020).
3.6 Scanning Kelvin probe
Scanning Kelvin probe (SKP) is a nondestructive method
which does not require any conducting path between the
kelvin probe and the substrate. Kelvin probe can measure
work function difference in different media like vacuum,
humid air, open air or using a drop of electrolyte on the
surface by a non-destructive capacitance method (Wicinski
et al. 2016). The metallic probe is generally made from
tungsten which is enclosed by brass container. The vibra-
tion frequency and the maximum extent of vibration of the
probe can be regulated in terms of their required speed and
predefined height. The probe vibration produces current
that is quashed by external potential. The specific config-
uration of the SKP setup can measure the capacitive height
at the time of collecting data which in turn allows the
Kelvin probe to falter the specific profile. Two parallel ca-
pacitors plate are used to measure the capacitive height.
Between two parallel plates, one plate is regarded as the
Kelvin probe surface and another plate is considered as the
surface of the substrate. When the needle of the Kelvin
probe is near the substrate then the energy variances of the
electrons are observed. The energy that is required to
remove an electron from the surface of the conductor forms
the concept of work function and this work function dif-
ference varies the potential of conductive materials. The
flow of electron can shift from the higher work function to
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
the lower work function depending on the conductors’
properties. The relative work function can be associated
with the value of corrosion potential (Ecorr). When two
conductive surfaces come into electrical contact, the po-
tential difference is induced. Thus, positive and negative
charges are developed by the two different metals.
The respective potentials are denoted by EF1 and EF2
while Φ1 and Φ2 represent the work function of the
respective plates. When two parallel conductors are not
electrically connected then there will not generate any
potential difference (VC). There also shows a variation in
charge and energy level between two plates (Figure 18A).
On the other hand, charge and energy level appear in an
equilibrium position when the plates are connected elec-
trically. Figure 18B delineates the scenario of the connec-
tions between two plates. In this case, potential difference
(VC) is developed by the resultant flow of charge due to the
electrical connection between the two conductors. The
differences of work function can be equated by the multi-
plication of potential difference (VC) and electron charge
(e) and is represent by Equation (11).
−eVC = f1 − f2 (11)
An equal and opposite backing potential (VB) is
applied in the plates to neutralize the potential difference
(VC) during the vibration of the probe. To obtain the value
of work function difference, the neutralize condition is
essential during the measurements. This Volta potential
can be termed as corrosion potential and determined by
using following Equation (12).
Corrosion Potential  =  K + (f1 − f2 )/e (12)
where ( f1 − f2 ) is the work function difference between
the substrate and Kelvin probe. K is constant whose value
can vary for different probe material.
The height regulating scanning Kelvin probe (HR-SKP)
system was introduced to obtain the potential difference
27
for the rough, curved, and irregular surfaces. The experi-
mental setup of HR-SKP has been shown in Figure 19. This
type of Kelvin probe consists of different electromechanical
parts including a stepper motor, piezo electric actuator,
speaker, isolator and a needle. The Kelvin probe is nor-
mally instructed by an acoustic signal ranging 1–2 kHz
frequency (Wapner et al. 2005). The sample chamber can
be positioned by a computer-generated command to fix the
position between the needle and the substrate surface. A
thin wire made by nickel/chromium is used as needle. The
appropriate positioning of the needle is controlled by three
stepper motors which can provide three dimensional di-
rections. For height regulation, fast and accurate move-
ments piezo-electric actuator is used which can move in Z
direction and set the position vertically from the substrate
surface. A function generator generates sinusoidal current
at a frequency of 10 Hz keeping 300 mV voltage for the
distance control circuit. Two computer screens are used to
visualize the performance of the two control circuits which
are internally connected to each other. At the very begin-
ning of the experiment, X and Y directed stepper motors are
driven by computer command to locate the corresponding
point of the substrate surface. The piezoelectric actuator is
moved by a height regulating circuit. If precise height is
needed and the height is not adjusted with the actuator,
then additional Z-stepper motor can be used combinedly
with piezoelectric actuator to adjust the height. Only the
needle distance is set manually while other all commands
are performed automatically with computer-generated
program. A LIA is applied for the potential measurement.
After positioning the probe in a correct point upon the
substrate surface, the Volta potential is measured by the
potential control circuit. The LIA then commands the probe
and the needle is moved to a next position.
This work function can be correlated to the corrosion or
open circuit potential of bare or coated metals. One
example of the application of the SKP is the study of the
Figure 18: Energy and charge levels of the
plates when they are (A) not electrically
connected, (B) electrically connected.
28 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings

Figure 19: Experimental setup of the HR-SKP.

surface of a material beneath a coating to detect active
corrosion sites or identify the potential for future corrosion
site development. This technique has been additionally
applied to the field of forensic, solar cell research and the
development of organic light emitting diodes. Based on the
principle of a capacitor, SKP allows the user to set and
maintain the probe-to-sample distance enabling the
researcher to negate topographical contribution across real
world surface. In addition to being a non-destructive
technique (NDT), SKP also allows for electrochemical
analysis in the absence of electrolytes preserving the
sample for future analysis. The SKP non-contacting optical
surface profile (OSP) is an option which generates relative
height information that can be used as the basis for con-
stant distance mode operation. The OSP technique can also
be used to map topographic changes on a sample surface to
characterize corrosion pit size, number and depth.
separation. The effect can be accomplished either by
putting the substrate in a magnetic field, or by using direct
current (DC) or alternating current (AC). The approach is
based on the observation that the electrode can be polar-
ized by positioning it under the action of an external
electrical field produced by the application of a current
between two externals (A and C) graphite electrodes. By
applying an external voltage or current to the substrate (M),
the applied current can flow in parallel field lines across the
electrolyte and electrostatically polarizes the substrate and
thus measuring the response. The reference electrodes
(REFA and REFC) can record the differences in potential.
Figure 20 demonstrates the schematic representation of

3.7 Novel contactless technique

A modern measurement technique has recently been

established that does not require direct physical contact
between potentiostat and the substrate to calculate the
polarization resistance (Rp). The system here developed is
called the contactless technique for corrosion system.
Normally, it is essential to establish a direct contact among
all the electrodes to measure the polarization resistance
and potential difference using suitable wires in order to
polarize the substrate which acts as a working electrode.
When a current flow between the electrolyte and the sub- Figure 20: Schematic representation of electrode arrangements for
strate, then it gets polarized and generates electrostatic novel contactless technique.
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
four-electrode system experimental setup, where all four
electrodes are connected with a galvanostat. The system
comprises substrate ‘M’ as the working electrode and tank
is filled with the electrolyte. The most notable feature in
this novel technique is that the substrate (M) is not con-
nected electrically with the galvanostat and it is positioned
vertically which is parallel to the reference and counter
electrodes. Current is applied with a galvanostat/poten-
tiostat by two graphite electrodes (A and C) to measure the
response. Two saturated calomel reference electrodes
(REFA and REFC) located adjacent to the bar are used to
measure the voltage variation at both sides of the substrate
(M) before and after the applied current. During corrosion
process, the concentration of electrolyte may decrease due
to the formation of soluble corrosive products.
The measurement procedure of corrosion rate for this
novel contactless method is performed by employing
several steps. The equation Re = VRe/Iap is used to calculate
the electrolyte resistance. An external current (Iap)
(Andrade et al. 2008) is applied to the immersed substrate
(M) in the electrolyte without touching it. This applied
current polarizes the substrate by changing the potential
through generating external electric field in the sur-
rounding electrolyte. VRe is measured at the absence of the
substrate (M) in the electrolyte with the four-electrode
arrangement. After that the substrate (M) is immersed into
the electrolyte and Ve+M is measured utilizing the same
arrangement. The voltage differences between the refer-
ence electrodes (REFA and REFC) is regarded as the value of
Ve+M where Ve+M = V2 − V0. Before testing, the voltage drop
(V0) is measured between the reference electrodes and
another voltage drop (V2) between the reference electrodes
is counted after applying Iap current for a certain time
usually taking less than 1 min to obtain the stable value of
V2. The substrate resistance (RM) can be considered anal-
ogous to traditional polarization resistance (Rp). After
several hours and days, Ve+M is then measured periodically
to acquire RM values and to analyze whether it is equivalent
to Rp or not. Figure 21 shows the electrical circuit for the
contactless method where current flows parallelly through
the substrate bar and the electrolyte. Two different paths
are assumed for the current where one polarizes the sub-
strate bar (M) and the other travels through the electrolyte.
The following expression can determine the corrosion
resistance of the substrate bar:
1 1 1
= + (13)
Re+M Re RM
where, Re+M specifies the resistance when the substrate is
present in the electrolyte, Re is the electrolyte resistance in
the absence of the substrate and RM is the resistance of the
29
Figure 21: Electrical model used to represent the configuration of
non-contact method.
substrate. Using the Stern–Geary relationship, the corro-
sion current (icorr) can be determined from RM (Stern and
Geary 1957). The theoretical framework can be connected to
the fact that the currents produced in the substrate are
significantly proportional to the induced voltage due to the
separation of charges, fulfilling the principle of the linear
polarization method (Feliu et al. 1989). The ratio of the
current and electric potential (induced voltage) is consid-
ered as the polarization resistance if the currents are
directly proportional to the electric potential, which de-
pends on the substrate condition. The feasibility of calcu-
lating the rate of corrosion without physical contact of the
working electrode may unlock new horizon for smart ap-
plications and can be termed as non-destructive testing
(NDT).
Summary of the latest electrochemical corrosion
measuring techniques has been shown in Table 11.
4 Conclusions
This review article outlines the overall aspects on corrosion
resistance for electroless Ni-P based composite coatings. It
can be prognosticated that progressive modifications by
varying different coating bath compositions and process
parameters may provide new benefits and properties for Ni-
P based composite coatings. The different concentration of
soluble salt, complexing agent and buffer solution does not
create any noticeable impact on corrosion properties of
electroless Ni-P based composite coatings whereas reducing
agent (sodium hypophosphite) has a significant influence
on corrosion resistance. In Ni-P electroless coatings, phos-
phorus content between 9 and 18 wt% shows the best result
in terms of corrosion resistance. However, heat treatment up
to 300 °C for electroless Ni-P composite coated substrate
has a detrimental effect on corrosion properties. The striking
Table : Summary of the latest electrochemical techniques.
30

Method Advantages Disadvantages Properties Specifications Applications

measured

LEIS Provides local impedance which cannot be
obtained by any other method, good for
insulated substrates, self-healing mechanism
SVET Real time mechanistic information, D-D
data presentation with image, simple experi-
mental setup
SIET Can be combined with SVET, easy way to
measure ion concentration
SDC Minimum electrolyte contact with surface, can
do all the electro-chemistry technique with
simple set up
SECM Several modes of operation, can be combined
with other techniques
SKP No need of an electrolyte, short experiments,
with the help of capacitive height measure-
ment roughned surface can be measured,
contactless method
NCT It can provide visual inspection, empirical
Unintended inductance in circuit, slow Local capacitance, Sensitivity:  nV; polarization Inorganic/organic coating research, in-
measuring technique resistance voltage: ± V; probe: Dual hibitor studies, coating defects, inter-
probe system facial impedance properties of coated
metals
Not suitable for irregular sample shape, Potential difference, Sensitivity:  nV to  V; piezo Bare metals corrosion, pits or crevices,
and high amplitude of vibration, elec- current density vibration range: up to  µm; biological systems
trolyte may disappear, long duration probe material: Pt/Ir
measurement
Fouling and damage to the ion selective Local pH, ion Piezo vibration range: up to Defects in coating or pits, kinetics of
electrode, Microcapillary tip is prone to concentration  µm; probe material: Pt/Ir electrochemical process
breakage
Droplet drag, surface energy issues Potential, current Reference & counter elec- Small area with large sample
trode: Ag/AgCl & Pt wire; po-
larization voltage: ± V
Sometimes needs a redox active medi- Current, potential Sensitivity:  µV; piezo vi- Biological sensors, reaction kinetics,
ator, needs a bipotentiostat difference bration range: (–) µm; porous membrane study
polarization voltage: ± V
Low resolution of SKP, need of probe Work function, po- Sensitivity:  nV to  V; piezo Measure corrosion under thin layers,
calibration tential difference, vibration range: up to  µm; rough or irregular surface, forensic
current probe material: Tungsten research
Concentration of electrolyte may Current, metal Four electrodes are used Reinforce steel
I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings

analysis, physical and electrochemical testing decrease resistance (RM)

 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
feature of the incorporation of nanoparticles (such as TiO2,
SiC) to the electroless Ni-P plating bath solution is that it
provides remarkable protection against corrosion. The ef-
fect of coating deposition time, bath solution temperature,
pH of the coating solution of electroless Ni-P coatings has a
slight impact on corrosion resistance. It is expected that the
review presented of the effect of different factors on the
aqueous corrosion behaviour of electroless Ni-P composite
coatings will be helpful to the researchers working on the
corrosive materials and their consistent development.
Moreover, a succinct overview of recent developed
electrochemical techniques is provided in this paper.
Although these techniques provide useful information by
showing a new horizon in the corrosion measurement
process, the required training, the interpretation of the
measurement complexity, the time required for calibra-
tion, and the sample setting may be challenging for a
researcher. With further developments in both instru-
mentation and software, the great advancements in elec-
trochemical techniques over the last few years will
certainly continue.
Acknowledgments: Imtiaz Ahmed Shozib would like to
express his deep and sincere gratitude to his research su-
pervisor, Dr. Azlan Ahmad, Lecturer, Universiti Teknologi
PETRONAS, for providing him the valuable guidance
throughout the writing of this review paper: Dr. Ahmad’s
dynamism, vision, sincerity and motivation have deeply
inspired him. Special thanks go to co-supervisor, Dr. Ahmad
Majdi Abdul-Rani, Assoc. Prof., Universiti Teknologi PET-
RONAS for his valuable suggestions and evaluations, and to
Dr. Mohammadali Beheshti and Dr. Abdul’Azeez Abdu Aliyu
for their constant encouragement and genuine support
throughout this work.
Author contributions: All the authors have accepted
responsibility for the entire content of this submitted
manuscript and approved submission.
Research funding: This research did not receive any
specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
Conflict of interest statement: The authors declare no
conflicts of interest regarding this article.
References
Abdel Aal, A. (2008). Hard and corrosion resistant nanocomposite
coating for Al alloy. Mater. Sci. Eng. A 474: 181–187.
Abdul-Rani, A.M., Rao, T., Axinte, E., Hastuty, S., Parameswari, R.P.,
Subramaniam, J.R., and Thyagarajan, S.P. (2019).
Characterization, adhesion strength and in-vitro cytotoxicity
31
investigation of hydroxyapatite coating synthesized on Zr-based
BMG by electro discharge process. Surf. Coating. Technol. 370:
213–226.
de Abreu, C.P., de Assis, C.M., Suegama, P.H., Costa, I., Keddam, M.,
de Melo, H.G., and Vivier, V. (2017). Influence of probe size for
local electrochemical impedance measurements. Electrochim.
Acta 233: 256–261.
Ahmad, A., Lajis, M.A., Yusuf, N.K., and Wagiman, A. (2016). Hot press
forging as the direct recycling technique of aluminium—a review.
ARPN J. Eng. Appl. Sci 11: 2258–2265.
Ahmadkhaniha, D., Eriksson, F., Leisner, P., and Zanella, C. (2018).
Effect of SiC particle size and heat-treatment on microhardness
and corrosion resistance of NiP electrodeposited coatings.
J. Alloys Compd. 769: 1080–1087.
Alaneme, K.K., Okotete, E.A., and Bodunrin, M.O. (2017).
Microstructural analysis and corrosion behavior of Fe, B, and Fe-
B-modified Cu-Zn-Al shape memory alloys. Corrosion Rev. 35:
3–11.
Allahkaram, S.R., Nazari, M.H., Mamaghani, S., and Zarebidaki, A.
(2011). Characterization and corrosion behavior of electroless
Ni–P/nano-SiC coating inside the CO2 containing media in the
presence of acetic acid. Mater. Des. 32: 750–755.
Ameen, S., Shaheer Akhtar, M., and Shin, H.S. (2012). Growth and
characterization of nanospikes decorated ZnO sheets and their
solar cell application. Chem. Eng. J. 195–196: 307–313.
Ammann, D., Pretsch, E., Simon, W., Lindner, E., Bezegh, A., and
Pungor, E. (1985). Lipophilic salts as membrane additives and
their influence on the properties of macro- and micro-electrodes
based on neutral carriers. Anal. Chim. Acta 171: 119–129.
Andrade, C. and Martínez, I. (2010). Techniques for measuring the
corrosion rate (polarization resistance) and the corrosion
potential of reinforced concrete structures. In: Non-destructive
evaluation of reinforced concrete structures: non-destructive
testing methods, pp. 284–316.
Andrade, C., Martínez, I., and Castellote, M. (2008). Feasibility of
determining corrosion rates by means of stray current-induced
polarisation. J. Appl. Electrochem. 38: 1467–1476.
Ang, L.M., Hor, T.S.A., Xu, G.Q., Tung, C., Zhao, S., and Wang, J.L.S.
(1999). Fabrication of nanostructures by hydroxylamine seeding
of gold nanoparticle templates. Chem. Mater. 11: 2115–2118.
Aoki, K. and Takano, O. (1986). Corrosion characteristics of crystalline
and amorphous electroless nickel-tungsten-phosphorus
deposits. Plat. Surf. Finish. 73: 136–141.
Araghi, A. and Paydar, M.H. (2010). Electroless deposition of Ni–P–
B4C composite coating on AZ91D magnesium alloy and
investigation on its wear and corrosion resistance. Mater. Des.
31: 3095–3099.
Ashassi-Sorkhabi, H. and Rafizadeh, S.H. (2004). Effect of coating
time and heat treatment on structures and corrosion
characteristics of electroless Ni–P alloy deposits. Surf. Coating.
Technol. 176: 318–326.
Assaf, F.H., Abou-Krisha, M.M., Daoush, W.M., and Eissa, A.A. (2018).
Fabrication of Zn-Ni-Mn alloy by electrodeposition and its
characterization. Corrosion Rev. 36: 547–558.
Baghery, P., Farzam, M., Mousavi, A.B., and Hosseini, M. (2010).
Ni–TiO2 nanocomposite coating with high resistance to
corrosion and wear. Surf. Coating. Technol. 204: 3804–3810.
Bahgat Radwan, A., Abdullah, A.M., and Alnuaimi, N.A. (2018). Recent
advances in corrosion resistant superhydrophobic coatings.
Corrosion Rev. 36: 127–153.
32 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Bai, A., Chuang, P.-Y., and Hu, C.-C. (2003). The corrosion behavior of
Ni–P deposits with high phosphorous contents in brine media.
Mater. Chem. Phys. 82: 93–100.
Balaraju, J.N., Selvi, V.E., Grips, V.K.W., and Rajam, K.S. (2006a).
Electrochemical studies on electroless ternary and quaternary
Ni–P based alloys. Electrochim. Acta 52: 1064–1074.
Balaraju, J.N., Kalavati, and Rajam, K.S. (2006b). Influence of particle
size on the microstructure, hardness and corrosion resistance of
electroless Ni–P–Al2O3 composite coatings. Surf. Coating.
Technol. 200: 3933–3941.
Balaraju, J.N. and Rajam, K.S. (2005). Electroless deposition of Ni–Cu–
P, Ni–W–P and Ni–W–Cu–P alloys. Surf. Coating. Technol. 195:
154–161.
Balaraju, J., Sankara Narayanan, T., and Seshadri, S. (2001).
Evaluation of the corrosion resistance of electroless Ni-P and Ni-P
composite coatings by electrochemical impedance
spectroscopy. J. Solid State Electrochem. 5: 334–338.
Bastidas, D.M., Valdez, B., Schorr, M., and Bastidas, J.M. (2019).
Corrosion of copper intrauterine devices: review and recent
developments. Corrosion Rev. 37: 307–320.
Bastos, A.C., Karavai, O.V., Zheludkevich, M.L., Yasakau, K.A., and
Ferreira, M.G.S. (2010a). Localised measurements of pH and
dissolved oxygen as complements to SVET in the investigation of
corrosion at defects in coated aluminum alloy. Electroanalysis
22: 2009–2016.
Bastos, A.C., Zheludkevich, M.L., Klüppel, I., Grundmeier, G., and
Ferreira, M.G.S. (2010b). Modification of zinc powder to improve
the corrosion resistance of weldable primers. Prog. Org. Coating
69: 184–192.
Bastos, A.C., Quevedo, M.C., Karavai, O.V., and Ferreira, M.G.S.
(2017). Review—on the application of the scanning vibrating
electrode technique (SVET) to corrosion research. J. Electrochem.
Soc. 164: C973–C990.
Battocchi, D., He, J., Bierwagen, G.P., and Tallman, D.E. (2005).
Emulation and study of the corrosion behavior of Al alloy 2024-T3
using a wire beam electrode (WBE) in conjunction with scanning
vibrating electrode technique (SVET). Corrosion Sci. 47:
1165–1176.
Beheshti, M., Kakooei, S., Ismail, M.C., and Shahrestani, S. (2016).
Design and implementation of scanning electrochemical
microscopy (SECM) for scanning open circuit potential system
on damaged coated surfaces. J. Eng. Appl. Sci. 11:
14299–14302.
Beheshti, M., Ismail, M.C., Kakooei, S., and Shahrestani, S. (2020).
Influence of temperature and potential range on Zn-Ni deposition
properties formed by cyclic voltammetry electrodeposition in
chloride bath solution. Corrosion Rev. 38: 127–136.
Bertoncello, J.C.B., Manhabosco, S.M., and Dick, L.F.P. (2015).
Corrosion study of the friction stir lap joint of AA7050-T76511 on
AA2024-T3 using the scanning vibrating electrode technique.
Corrosion Sci. 94: 359–367.
Bigdeli, F. and Allahkaram, S.R. (2009). An investigation on corrosion
resistance of as-applied and heat treated Ni–P/nanoSiC
coatings. Mater. Des. 30: 4450–4453.
Bonin, L., Vitry, V., and Delaunois, F. (2018). Corrosion behaviour of
electroless high boron-mid phosphorous nickel duplex coatings
in the as-plated and heat-treated states in NaCl, H2SO4, NaOH
and Na2SO4 media. Mater. Chem. Phys. 208: 77–84.
Bubbico, R., Celata, G.P., D’Annibale, F., Mazzarotta, B., and
Menale, C. (2015). Experimental analysis of corrosion and
erosion phenomena on metal surfaces by nanofluids. Chem. Eng.
Res. Des. 104: 605–614.
Cabrini, M., Lorenzi, S., Pastore, T., and Bolzoni, F.M. (2017).
Environmentally assisted cracking of pipeline steels in CO2
containing environment at near-neutral pH. Corrosion Rev. 35:
309–323.
Calderón, J.A., Henao, J.E., and Gómez, M.A. (2014). Erosion–
corrosion resistance of Ni composite coatings with embedded
SiC nanoparticles. Electrochim. Acta 124: 190–198.
Chen, C.K., Feng, H.M., Lin, H.C., and Hon, M.H. (2002). The effect of
heat treatment on the microstructure of electroless Ni–P coatings
containing SiC particles. Thin Solid Films 416: 31–37.
Chen, K., Dai, J., and Zhang, X. (2015). Improvement of corrosion
resistance of magnesium alloys for biomedical applications.
Corrosion Rev. 33: 101–117.
Cherevko, S., Zeradjanin, A.R., Topalov, A.A., Kulyk, N.,
Katsounaros, I., and Mayrhofer, K.J.J. (2014). Dissolution of noble
metals during oxygen evolution in acidic media. ChemCatChem
6: 2219–2223.
Chiba, M., Yamada, C., Okuyama, H., Sugiura, M., Pletincx, S.,
Verbruggen, H., Hyono, A., Graeve, I., Terryn, H., and
Takahashi, H. (2018). Development of novel surface treatments
for corrosion protection of aluminum: self-repairing coatings.
Corrosion Rev. 36: 55–64.
Cissé, M., Abouchane, M., Anik, T., Himm, K., Belakhmima, R.A.,
Ebn Touhami, M., Touir, R., and Amiar, A. (2010). Corrosion
resistance of electroless Ni-Cu-P ternary alloy coatings in acidic
and neutral corrosive mediums. Int. J. Corros. 2010: 1–6.
Clausmeyer, J., Masa, J., Ventosa, E., Öhl, D., and Schuhmann, W.
(2016). Nanoelectrodes reveal the electrochemistry of single
nickelhydroxide nanoparticles. Chem. Commun. 52: 2408–2411.
Court, S.W., Barker, B.D., and Walsh, F.C. (2000). Electrochemical
measurements of electroless nickel coatings on zincated
aluminium substrates. Trans. IMF 78: 157–162.
Cui, G., Li, N., Li, D., Zheng, J., and Wu, Q. (2006). The physical and
electrochemical properties of electroless deposited nickel–
phosphorus black coatings. Surf. Coating. Technol. 200:
6808–6814.
Cui, G., Li, Z., Yang, C., and Wei, X. (2015). Study on the interference
corrosion of cathodic protection system. Corrosion Rev. 33:
233–247.
Ćurković, L., Ćurković, H.O., Salopek, S., Renjo, M.M., and Šegota, S.
(2013). Enhancement of corrosion protection of AISI 304
stainless steel by nanostructured sol–gel TiO2 films. Corrosion
Sci. 77: 176–184.
Das, C.M., Limaye, P.K., Grover, A.K., and Suri, A.K. (2007). Preparation
and characterization of silicon nitride codeposited electroless
nickel composite coatings. J. Alloys Compd. 436: 328–334.
Delaunois, F. and Lienard, P. (2002). Heat treatments for electroless
nickel–boron plating on aluminium alloys. Surf. Coating.
Technol. 160: 239–248.
Dhoke, S.K., Khanna, A.S., and Sinha, T.J.M. (2009). Effect of nano-
ZnO particles on the corrosion behavior of alkyd-based
waterborne coatings. Prog. Org. Coating 64: 371–382.
Diegle, R.B., Sorensen, N.R., Clayton, C.R., Helfand, M.A., and Yu, Y.C.
(1988). An XPS investigation into the passivity of an amorphous
Ni-20P alloy. J. Electrochem. Soc. 135: 1085–1092.
Dolgikh, O., Demeter, A., Lamaka, S.V., Taryba, M., Bastos, A.C.,
Quevedo, M.C., and Deconinck, J. (2016). Simulation of the role of
vibration on Scanning Vibrating Electrode Technique
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
measurements close to a disc in plane. Electrochim. Acta 203:
379–387.
Dorman, S.E.G., Rausch, J.W., Arunachalam, S., and Fawaz, S.A.
(2017). Examination and prediction of corrosion fatigue damage
and inhibition. Corrosion Rev. 35: 355–363.
Du, Y., Zhang, X., Wei, L., Yu, B., Wang, Y., Wang, Y., and Ye, S. (2020).
Electrodeposition of a Ni-P composite coating reinforced with
Ti3C2Tx@TiO2/MoS2 particles. Mater. Chem. Phys. 241: 1–8.
Efaw, C.M., da Silva, T., Davis, P.H., Li, L., Graugnard, E., and
Hurley, M.F. (2019). Toward improving ambient volta potential
measurements with SKPFM for corrosion studies. J. Electrochem.
Soc. 166: 3018–3027.
Elansezhian, R., Ramamoorthy, B., and Nair, P.K. (2008). Effect of
surfactants on the mechanical properties of electroless (Ni–P)
coating. Surf. Coating. Technol. 203: 709–712.
Elsener, B., Crobu, M., Scorciapino, M.A., and Rossi, A. (2008).
Electroless deposited Ni–P alloys: corrosion resistance
mechanism. J. Appl. Electrochem. 38: 1053–1060.
Farag, A.A. (2020). Applications of nanomaterials in corrosion
protection coatings and inhibitors. Corrosion Rev. 38: 67–86.
Fayyad, E.M., Abdullah, A.M., Hassan, M.K., Mohamed, A.M.,
Jarjoura, G., and Farhat, Z. (2018). Recent advances in
electroless-plated Ni-P and its composites for erosion and
corrosion applications: a review. Emerg. Mater. 1: 3–24.
Fayyad, E.M., Abdullah, A.M., Mohamed, A.M.A., Jarjoura, G.,
Farhat, Z., and Hassan, M.K. (2019). Effect of electroless bath
composition on the mechanical, chemical, and electrochemical
properties of new NiP–C3N4 nanocomposite coatings. Surf.
Coating. Technol. 362: 239–251.
Feliu, S., González, J.A., Andrade, C., and Feliu, V. (1989). Polarization
resistance measurements in large concrete specimens:
mathematical solution for a unidirectional current distribution.
Mater. Struct. 22: 199–205.
Fix, D., Skorb, E.V., Shchukin, D.G., and Möhwald, H. (2011).
Quantitative analysis of scanning electric current density and
pH-value observations in corrosion studies. Meas. Sci. Technol.
22: 1–8.
Franklin, M.J., White, D.C., and Isaacs, H.S. (1991). Pitting corrosion by
bacteria on carbon steel, determined by the scanning vibrating
electrode technique. Corrosion Sci. 32: 945–952.
Gawad, S.A., Baraka, A.M., Morsi, M.S., and Eltoum, M.S.A. (2013).
Development of electroless Ni-P-Al2O3 and Ni-P-TiO2 composite
coatings from alkaline hypophosphite gluconate baths and their
properties. Int. J. Electrochem. Sci. 8: 1722–1734.
Georgieva, J. and Armyanov, S. (2007). Electroless deposition and
some properties of Ni–Cu–P and Ni–Sn–P coatings. J. Solid State
Electrochem. 11: 869–876.
Ghavidel, N., Allahkaram, S.R., Naderi, R., Barzegar, M., and
Bakhshandeh, H. (2020). Corrosion and wear behavior of an
electroless Ni-P/nano-SiC coating on AZ31 Mg alloy obtained
through environmentally-friendly conversion coating. Surf.
Coating. Technol. 382: 1–17.
Gholizadeh-Gheshlaghi, M., Seifzadeh, D., Shoghi, P., and
Habibi-Yangjeh, A. (2018). Electroless Ni-P/nano-WO3 coating
and its mechanical and corrosion protection properties. J. Alloys
Compd. 769: 149–160.
Gnedenkov, A.S., Sinebryukhov, S.L., Mashtalyar, D.V., and
Gnedenkov, S.V. (2016). Localized corrosion of the Mg alloys with
inhibitor-containing coatings: SVET and SIET studies. Corrosion
Sci. 102: 269–278.
33
Guo, Z., Keong, K.G., and Sha, W. (2003). Crystallisation and phase
transformation behaviour of electroless nickel phosphorus
platings during continuous heating. J. Alloys Compd. 358:
112–119.
Hamada, A.S., Sahu, P., and Porter, D.A. (2015). Indentation property
and corrosion resistance of electroless nickel–phosphorus
coatings deposited on austenitic high-Mn TWIP steel. Appl. Surf.
Sci. 356: 1–8.
Hari Krishnan, K., Praveen, J., Ganesan, M., Kavimani, P.M., John, S.,
and Srinivasan, K.N. (2006). Electroless Ni-P-based composite
coatings. Mater. Perform. 45: 36–39.
He, J., Tallman, D.E., and Bierwagen, G.P. (2004). Conjugated
polymers for corrosion control: scanning vibrating electrode
studies of polypyrrole-aluminum alloy interactions.
J. Electrochem. Soc. 151: 644–651.
Hu, C., Xu, M., Zhang, J., Hu, B., and Yu, G. (2019). High corrosion
resistance of electroless Ni/Ni-B coating from fluoride-free baths
on AZ31 magnesium alloy. J. Alloys Compd. 770: 48–57.
Hu, X., Jiang, P., Wan, J., Xu, Y., and Sun, X. (2009a). Study of corrosion
and friction reduction of electroless Ni–P coating with
molybdenum disulfide nanoparticles. J. Coating Technol. Res. 6:
275–281.
Hu, X.G., Cai, W.J., Xu, Y.F., Wan, J.C., and Sun, X.J. (2009b).
Electroless Ni–P–(nano-MoS2) composite coatings and their
corrosion properties. Surf. Eng. 25: 361–366.
Hu, Y., Wang, T., Meng, J., and Rao, Q. (2006). Structure and phase
transformation behaviour of electroless Ni–W–P on aluminium
alloy. Surf. Coating. Technol. 201: 988–992.
Huang, V.M.-W., Vivier, V., Frateur, I., Orazem, M.E., and Tribollet, B.
(2007). The global and local impedance response of a blocking
disk electrode with local constant-phase-element behavior.
J. Electrochem. Soc. 154: 89–98.
Huang, V.M., Wu, S.-L., Orazem, M.E., Pébère, N., Tribollet, B., and
Vivier, V. (2011). Local electrochemical impedance spectroscopy:
a review and some recent developments. Electrochim. Acta 56:
8048–8057.
Huang, Y.S., Zeng, X.T., Hu, X.F., and Liu, F.M. (2004). Corrosion
resistance properties of electroless nickel composite coatings.
Electrochim. Acta 49: 4313–4319.
Huang, Z.H., Zhou, Y.J., and Nguyen, T.T. (2019). Study of nickel matrix
composite coatings deposited from electroless plating bath
loaded with TiB2, ZrB2 and TiC particles for improved wear and
corrosion resistance. Surf. Coating. Technol. 364: 323–329.
Huang, Z. and Xiong, D. (2008). MoS2 coated with Al2O3 for Ni–MoS2/
Al2O3 composite coatings by pulse electrodeposition. Surf.
Coating. Technol. 202: 3208–3214.
Hughes, A.E., Parvizi, R., and Forsyth, M. (2015). Microstructure and
corrosion of AA2024. Corrosion Rev. 33: 1–30.
Iken, H., Etcheverry, L., Bergel, A., and Basseguy, R. (2008). Local
analysis of oxygen reduction catalysis by scanning vibrating
electrode technique: a new approach to the study of
biocorrosion. Electrochim. Acta 54: 60–65.
Isaacs, H.S. (1988). Initiation of stress corrosion cracking of
sensitized type 304 stainless steel in dilute thiosulfate solution.
J. Electrochem. Soc. 135: 2180–2183.
Isaacs, H.S. (1996). Location of corrosion on iron and carbon steel
surfaces with crevices. J. Electrochem. Soc. 143: 178–183.
Jadhav, N. and Gelling, V.J. (2019). Review—the use of localized
electrochemical techniques for corrosion studies. J. Electrochem.
Soc. 166: 3461–3476.
34 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Jaffe, L.F. and Nuccitelli, R. (1974). An ultrasensitive vibrating probe for
measuring steady extracellular currents. J. Cell Biol. 63:
614–628.
Jian, S.-Y., Chang, J.-K., Lin, K.-F., Chen, T.-Y., Yuan, J.-H., and
Ger, M.-D. (2020). Characteristic V-Mn conversion coating in
reinforcing corrosion resistance of electroless Ni-P coated LZ91
Mg alloy. Surf. Coating. Technol. 394: 1–13.
Jiang, S.X. and Guo, R.H. (2011). Electromagnetic shielding and
corrosion resistance of electroless Ni–P/Cu–Ni multilayer
plated polyester fabric. Surf. Coating. Technol. 205:
4274–4279.
Jiang, W., Niu, Q., Cheng, L., Zhou, T., and Xie, H. (2020).
Characterization of silicon acrylic resin containing silica
nanoparticles as candidate materials for antifouling and
anticorrosion properties in seawater. Corrosion Rev.,
https://doi.org/10.1515/corrrev-2019-0091 (Epub ahead of print).
Jin, H.M., Jiang, S.H., and Zhang, L.N. (2008). Microstructure and
corrosion behavior of electroless deposited Ni–P/CeO2 coating.
Chin. Chem. Lett. 19: 1367–1370.
Kallip, S., Bastos, A.C., Yasakau, K.A., Zheludkevich, M.L., and
Ferreira, M.G.S. (2012). Synergistic corrosion inhibition on
galvanically coupled metallic materials. Electrochem. Commun.
20: 101–104.
Kathavate, V.S., Bagal, N.S., and Deshpande, P.P. (2019). Corrosion
protection performance of nano-TiO2-containing phosphate
coatings obtained by anodic electrochemical treatment.
Corrosion Rev. 37: 565–578.
Keong, K.G., Sha, W., and Malinov, S. (2003). Computer modelling of
the non-isothermal crystallization kinetics of electroless nickel–
phosphorus deposits. J. Non-Cryst. Solids 324: 230–241.
Kerr, C., Barker, D., and Walsh, F. (1997). Porosity and corrosion rate
measurements for electroless nickel deposits on steel using
electrochemical techniques. Trans. IMF 75: 81–87.
Kerr, C., Barker, D., and Walsh, F.C. (1996). Studies of porosity in
electroless nickel deposits on ferrous substrates. Trans. IMF 74:
214–220.
Khollari, M.A.R., Ghorbani, M., and Afshar, A. (2019). Fabrication and
characterization of TiO2 deposited black electroless Ni-P solar
absorber. Appl. Surf. Sci. 496: 1–9.
Khorasani, S.A.H. and Sanjabi, S. (2016). High corrosion resistance Ni-
reduced graphene oxide nanocomposite coating. Corrosion Rev.
34: 305–312.
Klomjit, P. and Buchheit, R.G. (2020). Cooperative and synergistic
corrosion inhibition of AA 7075-T6 by praseodymium and CaSO4.
Corrosion Rev. 38: 365–380.
Kollender, J.P., Voith, M., Schneiderbauer, S., Mardare, A.I., and
Hassel, A.W. (2015). Highly customisable scanning droplet cell
microscopes using 3D-printing. J. Electroanal. Chem. 740:
53–60.
van der Kouwe, E.T. (1993). EIS as a means of evaluating electroless
nickel deposits. Electrochim. Acta 38: 2093–2097.
Kubisztal, J., Kubisztal, M., Stach, S., and Haneczok, G. (2018).
Corrosion resistance of anodic coatings studied by scanning
microscopy and electrochemical methods. Surf. Coating.
Technol. 350: 419–427.
Kulyk, N., Cherevko, S., Auinger, M., Laska, C., and Mayrhofer, K.J.J.
(2015). Numerical simulation of an electrochemical flow cell with
V-shape channel geometry. J. Electrochem. Soc. 162: 860–866.
Kumar, R., Chahal, S., Dahiya, S., Dahiya, N., Kumar, S., and Lata, S.
(2017). Experimental and theoretical approach to exploit the
corrosion inhibition activity of 3-formyl chromone derivatives on
mild steel in 1 m H2SO4. Corrosion Rev. 35: 95–110.
Lamaka, S., Souto, R.M., and Ferreira, M.G.S. (2010). In-situ
visualization of local corrosion by scanning ion-selective
electrode technique (SIET). In: Méndez-Vilas, A. and Díaz, J.,
Microscopy: Science, technology, applications and education,
Vol. 3, Formatex Research Center, Badajoz, Spain,
pp. 2162–2173.
Lee, C.-K. (2012). Comparative corrosion resistance of electroless Ni-
P/nano-TiO2 and Ni-P/nano-CNT composite coatings on 5083
aluminum alloy. Int. J. Electrochem. Sci. 7: 12941–12954.
Lee, S.-L. and Liang, H.-H. (1991). Structures and corrosion
characteristics of electroless Ni-Mo-P alloy deposits. Plat. Surf.
Finish. 78: 82–86.
Li, X., Wang, Z., Qiu, Y., Pan, Q., and Hu, P. (2015). 3D graphene/ZnO
nanorods composite networks as supercapacitor electrodes.
J. Alloys Compd. 620: 31–37.
Lillard, R.S., Moran, P.J., and Isaacs, H.S. (1992). A novel method for
generating quantitative local electrochemical impedance
spectroscopy. J. Electrochem. Soc. 139: 1007–1012.
Liu, G., Yang, L., Wang, L., Wang, S., Chongyang, L., and Wang, J.
(2010). Corrosion behavior of electroless deposited Ni–Cu–P
coating in flue gas condensate. Surf. Coating. Technol. 204:
3382–3386.
Liu, Q., Zhou, Q., Venezuela, J., Zhang, M., Wang, J., and Atrens, A.
(2016). A review of the influence of hydrogen on the mechanical
properties of DP, TRIP, and TWIP advanced high-strength steels
for auto construction. Corrosion Rev. 34: 127–152.
Liu, X., Tan, Y., Zhang, X., Liao, Q., and Wang, Z. (2020). Fabrication
and performance evaluation of nickel-rich conductive coating for
carbon steel grounding grids in saline-alkali soil solution.
Corrosion Rev. 38: 263–271.
Liu, Y.Y., Yu, J., Huang, H., Xu, B.H., Liu, X.L., Gao, Y., and Dong, X.L.
(2007). Synthesis and tribological behavior of electroless Ni–P–
WC nanocomposite coatings. Surf. Coating. Technol. 201:
7246–7251.
Liu, Y. and Zhao, Q. (2004). Study of electroless Ni–Cu–P coatings and
their anti-corrosion properties. Appl. Surf. Sci. 228: 57–62.
Lo, P., Tsai, W., Lee, J., and Hung, M. (1995). The electrochemical
behavior of electroless plated Ni‐P alloys in concentrated NaOH
solution. J. Electrochem. Soc. 142: 91–96.
Lollini, F., Carsana, M., Gastaldi, M., and Redaelli, E. (2019). Corrosion
behaviour of stainless steel reinforcement in concrete. Corrosion
Rev. 37: 3–19.
Lu, G. and Zangari, G. (2002). Corrosion resistance of ternary Ni-P
based alloys in sulfuric acid solutions. Electrochim. Acta 47:
2969–2979.
Luo, H., Leitch, M., Behnamian, Y., Ma, Y., Zeng, H., and Luo, J.-L.
(2015). Development of electroless Ni–P/nano-WC composite
coatings and investigation on its properties. Surf. Coating.
Technol. 277: 99–106.
Luo, H., Leitch, M., Zeng, H., and Luo, J.-L. (2018). Characterization of
microstructure and properties of electroless duplex Ni-WP/Ni-P
nano-ZrO2 composite coating. Mater. Today Phys. 4: 36–42.
Ma, C., Wu, F., Ning, Y., Xia, F., and Liu, Y. (2014). Effect of heat
treatment on structures and corrosion characteristics of
electroless Ni–P–SiC nanocomposite coatings. Ceram. Int. 40:
9279–9284.
Mallory, G.O. and Hajdu, J.B. (1990). Electroless plating: fundamentals
and applications. Cambridge University Press.
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Manhabosco, S.M., Batista, R.J.C., da Silva, S.N., and Dick, L.F.P.
(2015). Determination of current maps by SVET of hot-dip
galvanized steel under simultaneous straining. Electrochim. Acta
168: 89–96.
Marzocchi, V., Iglesias-Rubianes, L., Thompson, G.E., and Bellucci, F.
(2007). The influence of tartaric acid additions on the anodizing
behaviour of AA2024-T3 alloy in sulphuric acid. Corrosion Rev.
25: 461–474.
McMurray, H.N., Williams, D., and Worsley, D.A. (2003). Artifacts
induced by large-amplitude probe vibrations in localized
corrosion measured by SVET. J. Electrochem. Soc. 150: 567–578.
Mimani, T. and Mayanna, S.M. (1996). The effect of microstructure on
the corrosion behaviour of electroless Ni-P alloys in acidic media.
Surf. Coating. Technol. 79: 246–251.
Momenzadeh, M. and Sanjabi, S. (2012). The effect of TiO2
nanoparticle codeposition on microstructure and corrosion
resistance of electroless Ni-P coating. Mater. Corros. 63:
614–619.
Morales, A.G.R., Guzmán, M.O.C., and Arteaga, C.C. (2011). A brief
review on fabrication and applications of auto-organized TiO2
nanotube arrays. Corrosion Rev. 29: 105–121.
Narayanan, T.S.N.S., Krishnaveni, K., and Seshadri, S.K. (2003).
Electroless Ni–P/Ni–B duplex coatings: preparation and
evaluation of microhardness, wear and corrosion resistance.
Mater. Chem. Phys. 82: 771–779.
Narayanan, T.S.N.S. and Seshadri, S.K. (2009). Recent advances in
surface treatment and electrodeposition. Corrosion Rev. 27:
533–600.
Niaz, A. and Bakare, M.S. (2015). Electrochemical corrosion testing
and characterization of potential assisted passive layer on HVOF
Inconel 625 coating. Corrosion Rev. 33: 63–76.
Ningshen, S., Mudali, U.K., and Raj, B. (2009). Electrochemical
impedance spectroscopy and its applications in corrosion
research. Corrosion Rev. 27: 493–531.
Novakovic, J., Vassiliou, P., Samara, K., and Argyropoulos, T. (2006).
Electroless NiP–TiO2 composite coatings: their production and
properties. Surf. Coating. Technol. 201: 895–901.
Novakovic, J. and Vassiliou, P. (2009). Vacuum thermal treated
electroless NiP–TiO2 composite coatings. Electrochim. Acta 54:
2499–2503.
Ogle, K., Baudu, V., Garrigues, L., and Philippe, X. (2000). Localized
electrochemical methods applied to cut edge corrosion.
J. Electrochem. Soc. 147: 3654–3660.
Okamoto, Y., Nitta, Y., Imanaka, T., and Teranishi, S. (1980). Surface
state and catalytic activity and selectivity of nickel catalysts in
hydrogenation reactions: III. Electronic and catalytic properties
of nickel catalysts. J. Catal. 64: 397–404.
Pilaski, M., Hamelmann, T., Moehring, A., and Lohrengel, M.M. (2002).
Impedance spectroscopy in micro systems. Electrochim. Acta 47:
2127–2134.
Promphet, N., Rattanawaleedirojn, P., and Rodthongkum, N. (2017).
Electroless NiP-TiO2 sol-RGO: a smart coating for enhanced
corrosion resistance and conductivity of steel. Surf. Coating.
Technol. 325: 604–610.
Rabizadeh, T. and Allahkaram, S.R. (2011). Corrosion resistance
enhancement of Ni–P electroless coatings by incorporation of
nano-SiO2 particles. Mater. Des. 32: 133–138.
Raicheff, R. and Zaprianova, V. (2000). Effect of crystallization on the
electrochemical corrosion behavior of some nickel-based
amorphous alloys. J. Mater. Sci. Lett. 19: 3–5.
35
Ranganatha, S., Venkatesha, T.V., and Vathsala, K. (2010).
Development of electroless Ni–Zn–P/nano-TiO2 composite
coatings and their properties. Appl. Surf. Sci. 256:
7377–7383.
Sahayaraj, M.E., Jappes, J.T.W., Siva, I., and Saravanan, M.S.S. (2014).
A comparative corrosion study of electroless Ni-P coatings
treated by microwave and conventional furnace annealing.
Corrosion Rev. 32: 43–49.
Sahoo, P. and Das, S.K. (2011). Tribology of electroless nickel
coatings – a review. Mater. Des. 32: 1760–1775.
Sankara Narayanan, T.S.N., Baskaran, I., Krishnaveni, K., and
Parthiban, S. (2006). Deposition of electroless Ni–P graded
coatings and evaluation of their corrosion resistance. Surf.
Coating. Technol. 200: 3438–3445.
Schorr, M. and Valdez, B. (2016). The phosphoric acid industry:
equipment, materials, and corrosion. Corrosion Rev. 34: 85–102.
Schuppert, A.K., Topalov, A.A., Katsounaros, I., Klemm, S.O., and
Mayrhofer, K.J.J. (2012). A scanning flow cell system for fully
automated screening of electrocatalyst materials.
J. Electrochem. Soc. 159: 670–675.
Sekhavat Pour, Z., Ghaemy, M., Bordbar, S., and Karimi-Maleh, H.
(2018). Effects of surface treatment of TiO2 nanoparticles on the
adhesion and anticorrosion properties of the epoxy coating on
mild steel using electrochemical technique. Prog. Org. Coating
119: 99–108.
Sequeira, C.A.C., Cardoso, D.S.P., Amaral, L., Šljukić, B., and
Santos, D.M.F. (2016). On the performance of commercially
available corrosion-resistant nickel alloys: a review. Corrosion
Rev. 34: 187–200.
Sharifalhoseini, Z. and Entezari, M.H. (2015). The new aspects of the
anticorrosive ZnO@SiO2 core–shell NPs in stabilizing of the
electrolytic Ni bath and the Ni coating structure; electrochemical
behavior of the resulting nano-composite coatings. J. Colloid
Interface Sci. 455: 110–116.
Sharifalhoseini, Z., Entezari, M.H., and Shahidi, M. (2018). Direct
growth of ZnO nanostructures on the Zn electroplated mild steel
to create the surface roughness and improve the corrosion
protection of the electroless Ni-P coating. Mater. Sci. Eng., B 231:
18–27.
Shashikala, A.R. and Sridhar, B.S. (2020). Codeposition of electroless
Ni-P/ZnO nano composites and evaluation of corrosion
resistance of the coatings. Mater. Today: Proceedings,
https://doi.org/10.1016/j.matpr.2020.05.447 (Epub ahead
of print).
Shibli, S.M.A. and Chinchu, K.S. (2016). Development and
electrochemical characterization of Ni‐P coated tungsten
incorporated electroless nickel coatings. Mater. Chem. Phys.
178: 21–30.
Shibli, S.M.A. and Dilimon, V.S. (2007). Effect of phosphorous
content and TiO2-reinforcement on Ni–P electroless plates for
hydrogen evolution reaction. Int. J. Hydrogen Energy 32:
1694–1700.
Shinato, K.W., Zewde, A.A., and Jin, Y. (2020). Corrosion protection of
copper and copper alloys in different corrosive medium using
environmentally friendly corrosion inhibitors. Corrosion Rev. 38:
101–109.
Shozib, I.A., Ahmad, A., Majdi, A., and Tasnim, N. (2020). Electroless
Ni-P-TiO2 (ENPT) composite coating: a review on microstructural
characteristics and multifarious properties for surgical
instruments. Solid State Technol. 63: 3989–3996.
36 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Simões, A.M., Bastos, A.C., Ferreira, M.G., González-García, Y.,
González, S., and Souto, R.M. (2007). Use of SVET and SECM to
study the galvanic corrosion of an iron–zinc cell. Corrosion Sci.
49: 726–739.
Snowden, M.E., King, P.H., Covington, J.A., Macpherson, J.V., and
Unwin, P.R. (2010). Fabrication of versatile channel flow cells for
quantitative electroanalysis using prototyping. Anal. Chem. 82:
3124–3131.
Song, L.Z., Song, S.Z., and Zhao, J. (2006). Preparation and corrosion
resistance of NiP/TiO2 composite film on carbon steel in sulfuric
acid solution. Acta Metall. Sin. 19: 117–123.
Sosa Domínguez, A., Pérez Bueno, J.J., Zamudio Torres, I., and
Mendoza López, M.L. (2017). Characterization and corrosion
resistance of electroless black Ni-P coatings of double black
layer on carbon steel. Surf. Coating. Technol. 326: 192–199.
Srinivasan, K.N., Meenakshi, R., Santhi, A., Thangavelu, P.R., and
John, S. (2010). Studies on development of electroless Ni–B bath
for corrosion resistance and wear resistance applications. Surf.
Eng. 26: 153–158.
Stern, M. and Geary, A.L. (1957). Electrochemical polarization: I. A
theoretical analysis of the shape of polarization curves.
J. Electrochem. Soc. 104: 56–63.
Su, Y., Zhou, B., Liu, L., Lian, J., and Li, G. (2015). Electromagnetic
shielding and corrosion resistance of electroless Ni‐P and Ni‐P‐
Cu coatings on polymer/carbon fiber composites. Polym.
Compos. 36: 923–930.
Sudagar, J., Lian, J., and Sha, W. (2013). Electroless nickel, alloy,
composite and nano coatings – a critical review. J. Alloys Compd.
571: 183–204.
Sukkasi, S., Sahapatsombut, U., Sukjamsri, C., Saenapitak, S., and
Boonyongmaneerat, Y. (2011). Electroless Ni-based coatings for
biodiesel containers. J. Coating Technol. Res. 8: 141–147.
Taheri, R. (2002). Evaluation of electroless nickel-phosphorus (EN)
coatings, Ph.D. thesis. Saskatoon, University of Saskatchewan.
Tamilarasan, T.R., Rajendran, R., Rajagopal, G., and Sudagar, J. (2015).
Effect of surfactants on the coating properties and corrosion
behaviour of Ni–P–nano-TiO2 coatings. Surf. Coating. Technol.
276: 320–326.
Tamilarasan, T.R., Sanjith, U., Shankar, M.S., and Rajagopal, G.
(2017). Effect of reduced graphene oxide (rGO) on corrosion and
erosion-corrosion behaviour of electroless Ni-P coatings. Wear
390: 385–391.
Toloei, A., Atashin, S., and Pakshir, M. (2013). Corrosion rate of carbon
steel under synergistic effect of seawater parameters including
pH, temperature, and salinity in turbulent condition. Corrosion
Rev. 31: 135–144.
Trueba, M. and Trasatti, S.P. (2015). Electrochemical approach to
repassivation kinetics of Al alloys: gaining insight into
environmentally assisted cracking. Corrosion Rev. 33: 373–393.
Uma Rani, R., Sharma, A.K., Minu, C., Poornima, G., and Tejaswi, S.
(2010). Studies on black electroless nickel coatings on titanium
alloys for spacecraft thermal control applications. J. Appl.
Electrochem. 40: 333–339.
Uysal, M. (2019). Electroless codeposition of Ni-P composite coatings:
effects of graphene and TiO2 on the morphology, corrosion, and
tribological properties. Metall. Mater. Trans. 50: 2331–2341.
Vitry, V., Kanta, A.-F., Dille, J., and Delaunois, F. (2012a). Structural
state of electroless nickel–boron deposits (5wt.% B):
characterization by XRD and TEM. Surf. Coating. Technol. 206:
3444–3449.
Vitry, V., Sens, A., Kanta, A.-F., and Delaunois, F. (2012b). Wear and
corrosion resistance of heat treated and as-plated Duplex NiP/
NiB coatings on 2024 aluminum alloys. Surf. Coating. Technol.
206: 3421–3427.
Vitry, V., Delaunois, F., and Dumortier, C. (2008). Mechanical
properties and scratch test resistance of nickel–boron coated
aluminium alloy after heat treatments. Surf. Coating. Technol.
202: 3316–3324.
Vojtěch, D., Novák, M., Zelinková, M., Novák, P., Michalcová, A., and
Fabián, T. (2009). Structural evolution of electroless Ni–P coating
on Al–12wt.% Si alloy during heat treatment at high
temperatures. Appl. Surf. Sci. 255: 3745–3751.
Vuillemin, B., Philippe, X., Oltra, R., Vignal, V., Coudreuse, L.,
Dufour, L.C., and Finot, E. (2003). SVET, AFM and AES study of
pitting corrosion initiated on MnS inclusions by microinjection.
Corrosion Sci. 45: 1143–1159.
Wang, H.-L., Liu, L.-Y., Dou, Y., Zhang, W.-Z., and Jiang, W.-F. (2013).
Preparation and corrosion resistance of electroless Ni-P/SiC
functionally gradient coatings on AZ91D magnesium alloy. Appl.
Surf. Sci. 286: 319–327.
Wang, L., Zhao, L., Zhang, B., Hu, W., Shu, X., Sheng, X., and Fang, Z.
(1999). Crystallization study of electroless Fe–Sn–B amorphous
alloy deposits. J. Alloys Compd. 287: 234–238.
Wapner, K., Schoenberger, B., Stratmann, M., and Grundmeier, G.
(2005). Height-regulating scanning kelvin probe for
simultaneous measurement of surface topology and electrode
potentials at buried polymer/metal interfaces. J. Electrochem.
Soc. 152: 114–122.
Wicinski, M., Burgstaller, W., and Hassel, A.W. (2016). Lateral resolution
in scanning Kelvin probe microscopy. Corrosion Sci. 104: 1–8.
Williams, G., Coleman, A.J., and McMurray, H.N. (2010). Inhibition of
Aluminium Alloy AA2024-T3 pitting corrosion by copper
complexing compounds. Electrochim. Acta 55: 5947–5958.
Wu, X., Mao, J., Zhang, Z., and Che, Y. (2015). Improving the properties
of 211Z Al alloy by enhanced electroless Ni–P–TiO2
nanocomposite coatings with TiO2 sol. Surf. Coating. Technol.
270: 170–174.
Wu, Y., Gao, J., Shen, B., Liu, L., Hu, W., and Ding, W. (2005). Process
and properties of electroless Ni-P-PTFE composite coatings. Plat.
Surf. Finish. 92: 38–42.
Xing, F., Zhao, B., and Shi, W. (2013). Study on tunable fabrication of
the ultra-black Ni–P film and its blacking mechanism.
Electrochim. Acta 100: 157–163.
Xu, X., Chen, D., Yi, Z., Jiang, M., Wang, L., Zhou, Z., Fan, X., Wang, Y.,
and Hui, D. (2013). Antimicrobial mechanism based on H2O2
generation at oxygen vacancies in ZnO crystals. Langmuir 29:
5573–5580.
Xu, Y., Zhang, H., Li, X., Wang, W., and Li, J. (2017). Ag-encapsulated
single-crystalline anatase TiO2 nanoparticle photoanodes for
enhanced dye-sensitized solar cell performance. J. Alloys
Compd. 695: 1104–1111.
Yin, Z. and Chen, F. (2013). Effect of nickel immersion pretreatment on
the corrosion performance of electroless deposited Ni–P alloys
on aluminum. Surf. Coating. Technol. 228: 34–40.
Zanella, C., Lekka, M., Rossi, S., and Deflorian, F. (2011). Study of the
influence of sonication during the electrodeposition of nickel
matrix nanocomposite coatings on the protective properties.
Corrosion Rev. 29: 253–260.
Zeller, R.L., III (1991). Electrochemical corrosion testing of high
phosphorus electroless nickel in 5% NaCl. Corrosion 47: 692–702.
 I.A. Shozib et al.: Corrosion resistance of electroless Ni-P based coatings
Zhang, S., Han, K., and Cheng, L. (2008). The effect of SiC particles
added in electroless Ni–P plating solution on the properties of
composite coatings. Surf. Coating. Technol. 202: 2807–2812.
Zhao, G., Wang, R., Liu, S., Wu, D., Zhang, Y., Wang, T., and Zou, Y.
(2020). Study on the role of element Mo in improving thermal
stability and corrosion resistance of amorphous Ni-P deposit.
J. Non-Cryst. Solids 549: 1–11.
Zhao, Q., Liu, Y., and Abel, E.W. (2004). Effect of Cu content in
electroless Ni–Cu–P–PTFE composite coatings on their anti-
corrosion properties. Mater. Chem. Phys. 87: 332–335.
Zheng, C. and Yi, G. (2017). Investigating the influence of hydrogen on
stress corrosion cracking of 2205 duplex stainless steel in
sulfuric acid by electrochemical impedance spectroscopy.
Corrosion Rev. 35: 23–33.
Zhou, P., Cai, W., Yang, Y., Li, X., Zhang, T., and Wang, F. (2019). Effect of
ultrasonic agitation during the activation process on the
microstructure and corrosion resistance of electroless Ni-W-P
coatings on AZ91D magnesium alloy. Surf. Coating. Technol. 374:
103–115.
Zuleta, A.A., Galvis, O.A., Castaño, J.G., Echeverría, F., Bolivar, F.J.,
Hierro, M.P., and Pérez-Trujillo, F.J. (2009). Preparation and
characterization of electroless Ni–P–Fe3O4 composite coatings
and evaluation of its high temperature oxidation behaviour.
Surf. Coating. Technol. 203: 3569–3578.
Bionotes
Imtiaz Ahmed Shozib
Mechanical Engineering Department,
Universiti Teknologi PETRONAS, Seri
Iskandar, Perak 32610, Malaysia
imtiazshozib87me@gmail.com
https://orcid.org/0000-0001-8562-9569
Imtiaz ahmed Shozib received his B.Sc. degree in Mechanical
Engineering in 2017 from Rajshahi University of Engineering and
Technology (RUET), Bangladesh. He is currently a M.Sc. student at
Universiti Teknologi PETRONAS, Malaysia. His research interests
include biomaterials, antimicrobial activity on medical devices,
corrosion properties, statistical optimization, and materials property
prediction by machine learning. His area of expertise includes design
of experiments, Minitab, High score plus, NOVA, programming
language C. He has several journal publications to his credit.
Azlan Ahmad
Mechanical Engineering Department,
Universiti Teknologi PETRONAS, Seri
Iskandar, Perak 32610, Malaysia
Azlan Ahmad is currently a lecturer in Universiti Teknologi PETRONAS,
Malaysia. He received his Ph.D. degree in Mechanical Engineering
from Universiti Tun Hussein Onn Malaysia (UTHM), Malaysia. His
research area includes manufacturing, aluminium recycling, metal
forming, hot press forging, design of experiments. He has published
37
in several high impact journals. He received a couple of awards during
his academic life.
Ahmad Majdi Abdul-Rani
Mechanical Engineering Department,
Universiti Teknologi PETRONAS, Seri
Iskandar, Perak 32610, Malaysia
Ahmad Majdi Abdul-Rani is currently an associate professor at
Universiti Teknologi PETRONAS, Malaysia. He received his Ph.D.
degree from Loughborough University, UK. His area of expertise
includes advanced manufacturing of biomedical implants; additive
manufacturing of biomedical devices, reverse engineering, CAE/CAD/
CAD/CAM/CNC, PDC bit design. He has published in more than 140
high impact journals and holds 4 patents. He received a lot of awards
during his academic life.
Mohammadali Beheshti
Mechanical Engineering Department,
Universiti Teknologi PETRONAS, Seri
Iskandar, Perak 32610, Malaysia
https://orcid.org/0000-0003-4884-1127
Mohammadali Beheshti is a researcher at Universiti Teknologi
Petronas, Malaysia. He holds a Bachelor’s degree in Materials
Science and Engineering from Bu-Ali Sina University, Iran, and a
Master’s degree in Materials Science and Engineering (Corrosion &
Electrochemistry) from University of Tehran, Iran. He obtained his
Ph.D. in Mechanical Engineering (Center for Corrosion Research) from
Universiti Teknologi PETRONAS, Malaysia. His research interests
include metallic and alloy coatings, corrosion, advanced materials,
electrocatalysts and electrochemistry. He has published in several
high-impact refereed journals and attended many conferences.
Abdul’Azeez Abdu Aliyu
Mechanical Engineering Department, Bayero
University, Kano, Nigeria
Abdul’Azeez Abdu Aliyu is a lecturer at Bayero University Kano,
Nigeria. He completed his Master’s degree in Advanced
Manufacturing Technology at Universiti Teknologi Malaysia. He
obtained his Ph.D. in Mechanical Engineering from Universiti
Teknologi PETRONAS, Malaysia. His research interests include
advanced manufacturing of biomedical implants, additive
manufacturing of biomedical devices, advanced materials,
synthesis of bulk metallic glasses, CAD/CAM, advanced machining
processes, modelling and simulation. He has published in several
high impact journals and attended many conferences. He is
currently a post-doctoral fellow at Chulalongkorn University of
Bangkok, Thailand.