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Recent work on electrochemical deposition of Zn-Ni (-X) alloys for corrosion

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Article  in  Anti-Corrosion Methods and Materials · November 2018

DOI: 10.1108/ACMM-06-2018-1957

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 Anti-Corrosion Methods and Materials
Recent work on electrochemical deposition of Zn-Ni (-X) alloys for corrosion protection of steel
Simbarashe Fashu, R. Khan,
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Simbarashe Fashu, R. Khan, (2018) "Recent work on electrochemical deposition of Zn-Ni (-X) alloys for corrosion protection of
steel", Anti-Corrosion Methods and Materials, https://doi.org/10.1108/ACMM-06-2018-1957
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 Recent work on electrochemical deposition of
Zn-Ni (-X) alloys for corrosion protection
of steel
Simbarashe Fashu
Department of Materials Science and Technology, Harare Institute of Technology, Harare, Zimbabwe, and
R. Khan
Department of Physics, Abdul Wali Khan University, Mardan, Pakistan

Abstract
Purpose – Thin coatings are of great importance to minimize corrosion attack of steel in different environments. A review of recent work on
electrodeposition and corrosion performance of Zn-Ni-based alloys for sacrificial corrosion protection of ferrous substrates is presented. The review
contains key and outstanding comparisons of references for the period from 2007 to 2017. Binary and ternary Zn-Ni-based alloys were compared
and contrasted to provide a good knowledge basis for selection of best coating system to steel substrates.
Design/methodology/approach – This article is a review article.
Findings – Zn-Ni-(X) alloys show great potential for replacing Cd metal in corrosion protection of steel substrates.
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Practical implications – The research on plating of binary Zn-Ni alloys from aqueous electrolytes is now well advanced and these alloys show
improved corrosion resistance compared to pure Zn. Pulse plated and compositionally modulated multilayer Zn-Ni alloy coatings showed enhanced
corrosion properties compared to direct plated Zn-Ni coatings of similar composition.
Originality/value – The work on electrodeposition of Zn-Ni based alloys from ionic liquids is still scarce, yet these liquids show great promise in
improving corrosion resistance and reducing coating thickness when compared to aqueous electrolytes. Advanced plating techniques in ionic liquids
such as electromagnetic, CMM, pulse plating, ternary alloys and composites should be considered as these electrolytes avoid water chemistry and
associated defects.
Keywords Corrosion, Corrosion science, Cathodic protection
Paper type General review

1. Introduction down corrosion rate of the underlying steel substrate. In

Steel is widely used in many industries due to its good
mechanical strength, but its poor corrosion resistance is the
major limitation. Accordingly, methods for protecting steel in
aggressive environments becomes a research focus. Among the
protective methods, electrodeposition provides a smooth and
hard surface, better bonding between particles and metal
substrate, easy control of the coating thickness and the ability to
deposit metallic alloys. During the past decade, the
development and characterization of coatings with enhanced
protective properties against corrosion has been demanded by
the increased industrial requirements for longer service life
combined with reduced layer thickness. Zn plating is
extensively applied for sacrificial protection of steel
components for general applications like electrical, bridges,
buildings and fasteners due to its low cost and easy of
application (Zhang, 1996). The Zn film sacrificially corrodes
and protects steel and the passive rust layer formed also slow
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sacrificial protection, the corrosion potential of the coating is
more negative than that of the substrate such that it will dissolve
first in the corrosive environment. The challenge in using Zn
for corrosion protection of steel is its high corrosion rate such
that thicker coatings are required for effective protection. High
corrosion rates of Zn emanates from the greater corrosion
potential difference between steel and zinc as shown in Figure 1
which show the corrosion potentials of different metals/alloys in
sea water (3.5 per cent NaCl). This figure show that reactive
metals such as zinc and magnesium have a more negative
potential compared to cast iron and steel, while noble metals
like silver and platinum have a less negative potential. For
sacrificial corrosion protection, thick coatings are not
economical and generate large volumes of corrosion products
which sometimes interfere with components e.g. fasteners.
Thus, the requirement of industry nowadays is to reduce
coating thickness and to increase corrosion resistance at the
same time. In addition, the thin film should have sufficient
mechanical strength to withstand the forces the material will be
exposed to.
The authors would like to thank A. Mukuya, the Lecturer at Harare
Institute of Technology, Zimbabwe, for proof reading this article.

Anti-Corrosion Methods and Materials Received 25 June 2018

© Emerald Publishing Limited [ISSN 0003-5599] Revised 25 June 2018
[DOI 10.1108/ACMM-06-2018-1957] Accepted 18 September 2018
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
Figure 1 Electrochemical potentials of various metals and alloys in 3.5
Wt.% NaCl sea water (Oriti, 2014)
As its potential is negative and very close to that of steel as
shown in Figure 1, cadmium (Cd) metal has been used as a
replacement for Zn plating showing high effectiveness in
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corrosion protection. However, Cd and its compounds are
toxic in nature and its use are now restricted to special
applications like aerospace industry and it is already banned in
many countries e.g. Europe. In search of non-toxic materials
with better protective ability to steel, alloy coatings have been
reported as a means of surface protection of steel with a
potential to replace Cd metal. Proper alloying of Zn with noble
metals like Ni and Co brings down the corrosion potential of
the alloy close to and at the same time sacrificial to steel as
shown for the Zn-Ni alloy in Figure 1. Such a coating over steel
would corrode less quickly than pure zinc of comparable
thickness. Research on electrodeposition of Zn with Ni and
other iron group metals like Co and Fe was successful and such
elements significantly improve mechanical properties and
corrosion resistance when compared to pure Zn (Suzuki and
Enjuzi, 1993; Abou-Krisha, 2012; Zhang et al., 2001;
Ramanauskas et al., 2001; Roventi et al., 2006; Fei and Wilcox,
2005; Petrauskas et al., 2006; Chassaing and Wiart, 1992;
Petrauskas et al., 2005).
Among the Zn-Ni, Zn-Co and Zn-Fe alloys, Zn-Ni and Zn-
Co coatings offer greater protection to steel compared to Zn-Fe
because they exhibit lower corrosion rates. Between the Zn-Co
and Zn-Ni alloy, the latter is more commercially widespread,
with applications since the beginning of the twentieth century
(Ramanauskas et al., 1997; Ramanauskas, 1999). The Zn-Ni
alloys have a potential to replace Cd metal in special
applications where it can be used in automotive steel
bodies and aerospace industries. The corrosion resistance of
Zn-Ni alloys mainly depends on chemical composition, phases
present and grain size (El Hajjami et al., 2007). The increase in
alloy Ni content generally lead to more positive corrosion
potential which in turn reduces the driving force for galvanic
corrosion. In addition, previous researches have shown that the
morphology of Zn-Ni alloys is refined with increase in alloy Ni
content as shown in Figure 2 and such a refined morphology
enhances corrosion resistance (Kwon et al., 2016; Tsybulskaya
et al., 2008; Tafreshi et al., 2016). High Ni content induces
internal residual stresses resulting in cracking of the deposit as
shown in Figure 2. In addition, Ni forms stable passive
Anti-Corrosion Methods and Materials
corrosion products on its surface that acts as barrier to further
corrosion on fresh surfaces (Visscher and Barendrecht, 1983).
During corrosion, zinc dissolves preferentially, leaving a top
layer enriched with nickel which acts a barrier to further attack.
Abou-Krisha (2005) investigated the influence of chemical
composition on corrosion properties of Zn-Ni alloys and found
that the corrosion resistance of the coatings is strongly
correlated with their Ni content. Byk et al. (2008) have studied
the effects of electrodeposition parameters on chemical
composition, microstructure and corrosion properties on Zn-
Ni films. Their results revealed that electrodeposition
conditions have a great influence on the coatings Ni content
and corrosion behavior. A lower Ni content in the alloy leads to
lower barrier properties and higher corrosion rates. Conversely,
with a higher Ni content, exceeding 25-30 Wt.%, the coating is
no longer sacrificial with respect to the steel substrate and the
corrosion resistance rely only on the barrier properties of the
alloy. Thus, an optimum Ni content for corrosion protection is
required.
Literature show that the best corrosion performance of an
alloy is obtained when it is deposited as a single phase rather
than a mixture of phases. This is because of absence of local
corrosion cells between different phases as a results of one
phase being nobler than the other a situation which occur in
multiple phase alloys. Figure 3 show the Zn-Ni phase diagram
and that the phases present are influenced by the nickel
content. According to the Zn-Ni phase diagram (Figure 3),
electrodeposition of Zn–Ni alloys materializes in three
dominant phases: a, g and h . The a phase is a solid solution of
Zn in Ni with solubility of up to 30 per cent Zn. The h -phase is
a solid solution of Ni in Zn, with a Ni solubility of less than 1
per cent. The diagram depicts how the majority of the g phase
is found when the nickel content ranges between 10-30 Wt.%
(Ramanauskas et al., 2005). It is generally accepted that the Zn-
Ni coating provides the best corrosion resistance when the
composition contains 12-15 Wt.% Ni, when the morphology is
dense and at this composition the structure is a single phase
( g -Ni5Zn21).
In continual search of coatings with better corrosion
properties, researchers added third element metals to the
binary Zn-Ni alloys. Zn-Ni alloys containing Co and Fe
elements were developed to form Zn-Ni-Fe and Zn-Ni-Co
ternary systems (Abou-Krisha, 2012; Tomi
c et al., 2015; Dikici
et al., 2010; Wykpis et al., 2014; Abou-Krisha et al., 2008;
Kumar et al., 2012; Abou-Krisha, 2011; Younan and Oki,
1996; Abou-Krisha et al., 2009b, 2009a). These ternary
systems show better corrosion protection than pure Zn-Ni
alloys (Abou-Krisha et al., 2009a; Younan, 2000). The
improvement in corrosion resistance of ternary alloys when
compared to binary alloys was attributed to grain refinement;
however the refining mechanism is not yet thoroughly
understood.
To extend the applications of the coatings, metal matrix
composite coatings have been developed to improve the
chemical and mechanical properties of Zn-Ni alloys.
Composite coatings have various properties such as dispersion
hardening, self-lubricity, high-temperature oxidation
resistance, excellent wear, and corrosion resistance (Praveen
and Venkatesha, 2011). In general, hard oxide or carbide
particles such as Al2O3, TiO2, ZrO2, SiO2, SiC and WC or
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
Figure 2 SEM micrographs from the surface of as-deposited (a) Zn-0 Wt.%Ni, (b) Zn-11 Wt.%Ni, (c) Zn-14 Wt.%Ni and (d) Zn-17 Wt.%Ni (Tafreshi
et al., 2016)
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even diamond and carbon nanotubes (CNTs) are used as
second phase. Electroplating co-deposition is widely used for
preparing metal matrix composites because of its low cost and
versatility. Typically, solid micro/nano particles are added to
electrodeposition bath under vigorous agitation, air injection or
ultrasonic vibration (Kumar et al., 2011; Wang et al., 2005).
Zn–Ni-(X) coatings have been fabricated by direct current
(DC) plating, pulse plating, and as composition modulated
multilayer alloys (CMMA) and were mostly deposited from
aqueous electrolytes. Electrodeposition of these alloys from
ionic liquids for sacrificial protection is still rare.
Electrodeposition of binary Zn-Ni alloys from ionic liquids was
shown to be normal and alloys produced contained high
amounts of Ni such that they cannot be used for sacrificial
protection (Fashu et al., 2015; Fashu et al., 2014; Pereira et al.,
2015). Addition of 3rd element on Zn-Ni alloy when depositing
from ionic liquids may influence the sacrificial properties. Work
Anti-Corrosion Methods and Materials
on electrodeposition of sacrificial Zn-Ni-X ternary alloys from
ionic liquids for steel protection is still scarce.
This review looks at the recent work on electrodeposition of
Zn-Ni-(X) alloys from aqueous electrolytes for corrosion
protection of steel substrates. Plating from aqueous electrolytes
is a developed and mature technology. Influence of important
aspects such as alloy phase composition, chemical composition,
grain size, coating thickness and corrosion medium are
considered. The corrosion test results from potentiodynamic
polarization corrosion tests are used for comparison as they
were found to be readily available in literature for systematic
comparisons. In addition, among the corrosion tests,
potentiodynamic polarization test and electrochemical
impedance spectroscopy have proved to be efficient and
convincing for analyzing corrosion. Although the corrosion
comparison results in this review are not exhaustive, but they
provide an insight and a future direction can be mapped. In the
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
Figure 3 The Zn-Ni phase diagram (Okamoto, 2012)
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potentiodynamic polarization test, Zn-Ni (-X) alloys with the
least corrosion current density, substantially negative potential
than steel are best for sacrificial corrosion protection of steel.
The literature data containing the common saturated calomel
(SCE) referencing were considered for comparisons and 3.5/5
Wt.% NaCl as corrosive medium.
1.1 Zn-Ni plating baths
Zn-Ni alloys can be electrodeposited from acid (Byk et al.,
2008; Fratesi and Roventi, 1992; Barcel
o et al., 1994;
Bachvarov et al., 2012; Pushpavanam and Balakrishnan, 1996;
Zaki, 1989), neutral, alkaline cyanide and alkaline noncyanide
baths (Byk et al., 2008; Zaki, 1989; Lee and Kim, 2000). The
acid bath was the first commercial electrolyte (Kondo et al.,
1995), which displays a high cathode current efficiency and
faster plating speed but poor throwing power and low nickel
content (normally 5-10 At.%) and non-uniform distribution
throughout the coating. Electrodeposition of Zn–Ni coatings is
quite often performed in acidic baths, but such baths have
higher hydrogen evolution causing hydrogen embrittlement in
steel. In contrast, alkaline baths, which can ensure normal
nickel plating, yield more uniform coatings with much higher
nickel content as compared to acid baths (and, therefore, with
enhanced corrosion resistance); however these baths operate at
low current densities (Wilcox and Gabe, 1993).
Electrodeposition of Zn-Ni alloys in neutral or basic baths
reduces the risk of hydrogen evolution (HE), and such baths
were found to be good for coating high strength steel.
Electrodeposition of Zn-Ni alloys can be performed from
sulfate, chloride, sulfamate, pyrophosphate, and cyanide based
baths (Wilcox and Gabe, 1993; Brenner, 1963).
1.1.1 Complexing agents.
Co-deposition of two metals requires that their individual
reversible potentials are reasonably close to each other in the
Anti-Corrosion Methods and Materials
specific bath. The standard electrode potential of Zn is -0.76V
whilst that of Ni is -0.25V and this shows that the gap is quite
significant. To make the potentials close, complexing agents
that forms complexes with different stability constants with ions
are added. The acid bath does not require complexing agents,
leading to less expensive deposition process than alkaline
plating bath. Basic alkaline baths usually contain zinc and
nickel ions, an alkaline metal hydroxide and a complexing agent
for nickel (Schlesinger, 2000; Muller et al., 2002). Studies have
shown that different amines can be used as complexing agents
in alkaline baths (Tsybulskaya et al., 2008; Lee and Kim, 2000;
Muller et al., 2002; Hosseini et al., 2008). Garcia et al. (Garcıa
et al., 2002) have investigated four amine alkaline baths. Their
results showed that all of those amines were good complexing
agents and a homogeneous composition of Zn-Ni alloy can be
obtained. Glycine has also been used as a complexing agent in
the electrodeposition of Zn-Ni (Tsybulskaya et al., 2008)
alloys. These studies have shown that an alkaline bath
containing glycine offers high quality deposits, high deposition
rate and current efficiency, but glycine is expensive. Conrad
et al. (Tsybulskaya et al., 2008) have used sodium acetate as a
complexing ligand to stabilize the Zn21 and Ni21 in weak
alkaline bath.
1.2 Zn-Ni plating parameters
The plating parameters including voltage, current density, bath
Ni21/Zn21 ratio and temperature should be adjusted to get Ni
composition of 12-15 per cent in the alloy, single phase alloy
and fine grained deposit. Many researchers have shown that
decreasing Ni21/Zn21 ratio in the bath, low deposition
potentials/current density and low temperature increased the
Ni content of coatings (Fratesi and Roventi, 1992; Elkhatabi
et al., 1999). The codeposition of Zn with Ni was found to be
normal with proper adjustment of plating parameters. Natural
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
and forced convection were also investigated to be important
parameters that influence alloy composition due to variations in
transport of electroactive species towards the electrode
(Matsushima et al., 2007). Forced convection can be induced
through an immersed rotating disc or a magnetic field applied
onto the electrolytic cell. Higher agitation speed increase the Zn
co-deposition than Ni codeposition. The magnetoelectrolysis is
also found to enhance the surface smoothness of the
electrodeposit (Shannon et al., 1997; Shannon et al., 1999).
Ganesh et al. have observed grain refinement of the nickel
electrodeposited at 10mAcm 2 from nickel sulfamate bath in
the presence of magnetic field up to 1T. It was further observed
that the magnetic convections increased the mass transfer rate
and reduced the concentration polarization (Ganesh et al.,
2005).
1.3 Zn-Ni plating additives
The success of electroplating depends to a large extent on the
type of addition agents introduced in plating electrolytes
(Franklin, 1987). Organic additives are added in small
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quantities (i.e. ppm) for the purposes of grain refinement,
leveling, brightening, internal stress relief, pitting and even
chemical composition control (Mu et al., 2001; Albalat et al.,
1990; Mosavat et al., 2011; Li et al., 2007). Additive molecules
adsorbed on the cathode surface can affect the activation
energy (Kelly and West, 1998) and the rate of charge transfer in
the electrochemical reaction, and may also influence the
mechanism of electrocrystallization. In addition, the adsorbed
additives block part of the electrode surface, thereby reducing
the number of active sites for the formation of nuclei and
causing a decline in the nucleation rate (Bonou et al., 2002;
Moffat et al., 2004). Different kinds of additives have been used
to improve quality, brightness and to obtain grain refinement,
such as amines, sodiumlorylsulphate (SLS), and gelatin
(Soares et al., 2006; Ashassi-Sorkhabi et al., 2001; Alfantazi
et al., 1996). However, some additives may also affect cathodic
efficiency of deposition and decrease it. Moreover, some
additives such as different types of amines and gelatin may
decrease Ni content of Zn–Ni coatings and as a result decrease
the barrier corrosion resistance of the coatings. The reason
could be that the presence of strong chelating ligands bind Ni
ions in very stable complexes and deposition of Ni is difficult
from these complexes(Muller et al., 2002; Roev et al., 2001;
Eliaz et al., 2010).
The addition of mannitol to a boric acid bath promotes the
formation of a Zn–Ni deposit that is highly compact and
composed of globular crystallites that are smaller than 1 m m.
The addition of mannitol leads to an increase in the Ni content
of the Zn–Ni deposit in the potential range of 1.26 to 1.40 V
(De Oliveira and Carlos, 2009). Gelatin has been found to
increase the electrochemical efficiency for galvanostatic
deposition and improves the corrosion resistance of the Zn–Ni
deposit (Soares et al., 2006; Soares et al., 2005). A cyclic
voltamogram study demonstrated that a combination of gelatin
and sulphanilic acid improved the homogeneity and brightness
of the Zn–Ni multilayer coating (Venkatakrishna and
Chitharanjan Hegde, 2010). Pedroza et al. (2012) investigated
the influence of glycerol on Zn-Ni grain refinement and found
that the grains are refined with increase in glycerol content up
to a peak value as shown in Figure 4. However, additives
Anti-Corrosion Methods and Materials
generally affects the quality of coatings as impurities, reduces
conductivity and ductility of coatings, and may cause cracks.
1.4 Zn-Ni plating mechanism
The standard electrode potential of Zn is -0.76 V, whilst that of
Ni is -0.25 V. This shows that Ni is nobler than Zn and should
be deposited in higher contents during Zn-Ni co-deposition.
However, the opposite occurs, the less noble metal Zn deposits
preferentially and its percentage in the deposit is higher than
that in the bath. This is the characteristic of deposition of Zn
with iron group metals such as Ni, Co and Fe from aqueous
electrolytes and the phenomenon is termed “anomalous
codeposition” according to Brenner (Brenner, 1963). Under
such deposition conditions, typical Ni contents of the Zn-Ni
alloy will be approximately as low as 5-10 Wt.%Ni due to this
phenomena and such Ni contents are low for optimum
corrosion protection. Nevertheless under particular conditions
a normal codeposition can be provided. The anomalous Zn–Ni
codeposition has been deeply investigated by Brenner
(Brenner, 1963) and other authors (Zech et al., 1999). These
studies have shown that normal or anomalous codeposition can
take place depending on bath composition, value of applied
potential or cathodic current. Landolt demonstrated that
anomalous codeposition of iron group metals involves both
inhibiting and accelerating effects (Zech et al., 1999; Landolt,
2006/2004). Many attempts have been made to explain the
anomalous codeposition of alloys, but there is still no
universally accepted theory. Four main models have been
suggested to explain the anomalous deposition of Zn metal with
iron group metals.
1.4.1 Hydrogen suppression mechanism
This model suggest that due to hydrogen evolution and pH
increase at the cathode surface, a zinc hydroxide film
precipitates and adsorbs and lead to the inhibition of the more
noble metal Ni21 discharge (Hall, 1983). As the critical pH for
precipitation of iron-group metal hydroxides is significantly
higher than that for precipitation of zinc hydroxide, the former
may not form so that Ni-deposition requires direct discharge of
Ni21 ions through the zinc hydroxide film. At sufficiently high
current densities, the high resistance of this hydroxide film
favors Zn reduction while inhibiting Ni-deposition. Thus, the
model is termed the Hydroxide Suppression Mechanism
(Lichušina et al., 2008; Higashi et al., 1981; Yan et al., 1996;
G
omez and Vallés, 1995; Mathias and Chapman, 1987).
1.4.2 Underpotential deposition mechanism
A second model suggests that underpotential deposition
(UPD) of Zn provides an alloy surface that is different from the
parent metal for the continuous codeposition, thus making the
deposition of the less noble component preferable (Lichušina
et al., 2008; Swathirajan, 1987; Ohtsuka et al., 1995;
Swathirajan, 1986). However, if this was the case, once a
monolayer is deposited, the UPD should be terminated and the
ions in solution should “sense” only the last layer deposited on
the surface. Hence, such a model is valid only if an alternating
multilayer coating is formed.
1.4.3 Exchange current density model
According to the third model, the great difference between the
exchange current densities of Zn and the iron-group metal
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
Figure 4 SEM micrographs of Zn–Ni deposits obtained from a deposition bath containing (a) no glycerol; (b) 0.07 mol/L glycerol; and (c) 0.14 mol/L
glycerol (Pedroza et al., 2012)
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results in a significant difference between the thermodynamic
and the practical nobility. In this regard, the magnitude of the
exchange current density is generally much greater for Zn
compared to Ni, Co and Fe (Lichušina et al., 2008; G
omez and
Vallés, 1995; Mathias and Chapman, 1987; Ortiz-Aparicio
et al., 2007).
1.4.4 Kinetics mechanism
The fourth model for the Zn-Ni anomalous co-deposition is
simply attributed to the slow kinetics of nickel deposition
(Felloni et al., 1987; Lin and Selman, 1993) when compared to
Zn such that Zn is preferentially electrodeposited.
2. Zn-Ni (-X) alloys/composites for corrosion
protection
Comparisons of corrosion properties of Zn-Ni (-X) alloys
commercially produced from aqueous electrolytes where X
maybe the metal Co or Ni or oxide Fe2O3, Al2O3 or SiO2 is
presented in this section. The comparisons were made for the
alloys produced from the period of 2007-2017.
Anti-Corrosion Methods and Materials
2.1 Direct current (DC) electrodeposited Zn-Ni alloys
Comparisons of corrosion resistances of sacrificial Zn-Ni alloys
electrodeposited on steel substrates in different corrosive
mediums is shown in Table I. Zn-Ni alloys tested in 3.5-5 Wt.
% NaCl using the common saturated calomel electrode (SCE)
referencing system are considered here. The alloy Ni content,
phases present, grain sizes and coating thickness are reported.
A look at Table I show that generally to obtain low corrosion
rate alloy, the nickel content should be high, grain size should
be small and the alloy should be a single phase. Thin films
generally show excellent corrosion protection than thick films
of the same composition due to improved morphological
uniformity and chemical composition in thin layers. However,
the optimum nickel content should be adjusted such that the
corrosion potential of the alloy will be substantially higher than
that of steel substrate to avoid loss of sacrificial properties due
to dealloying or dezincification. The corrosion potentials of
many steels in seawater are less than 0.73V as shown in
Table II. Thin coatings shown in reference Sriraman et al.
(2013), Kwon et al. (2016), Rao et al. (2013) exhibit the best in
sacrificial properties with corrosion currents of 0.20-
0.997 m Acm 2 and potentials of -0.78 to -1.03 V. These
 Electrochemical deposition of Zn-Ni (-X) alloys Anti-Corrosion Methods and Materials
Simbarashe Fashu and R. Khan

Table I DC Plated Zn-Ni coatings

Corrosion test Corrosion Corrosion
Alloy Ni Phase Grain Coating solution/wt.% potential current/m A
content/wt% content size/nm thickness/m m NaCl (-V vs SCE) cm 2 References
14 g -Ni5Zn21 * 12 3.56 0.990 20 (Conde et al., 2011)
17.62 g -Ni5Zn21 37 * 3 0.972 23.2 (Mosavat et al., 2012)
15 g -Ni5Zn21 * 15–20 3.5 0.78, 0.77 0.627, 0.997 (Sriraman et al., 2013)
15.4, 18.9 Mixture ( g -Ni5Zn21 1 26,28 * 3.5 0.715-0.746 7.7, 9.4 (Tozar and Karahan,
Ni3Zn22) 2014)
1.6-20.7 Ni 1 g -Ni5Zn21 25-100 6 3 0.88-0.85 2-2.5 (Byk et al., 2008)
12 g -Ni5Zn21 * 29.33 3 1.02 – (Hammami et al., 2009)
3.5 g g -Ni5Zn211 h -Ni3Zn22 * 20.5 5 1.142 14.9 (Eliaz et al., 2010)
13.31 g -Ni5Zn21 20.7-27.2 * 3.5 0.792 40.14 (Feng et al., 2015)
6 h -Ni3Zn22 * * 3.5 1.03 0.25 (Kwon et al., 2016)
10.4 g -Ni5Zn21 23 12-15 3.5 1.048 6 (Ghaziof and Gao, 2015)
* h -Ni3Zn221 g -Ni5Zn21 * 29 3.5 1.02 100 (Gnanamuthu et al.,
2012)
5-13 h -Ni3Zn221 g -Ni5Zn21 * * 3 1.38-1.91 100-150 (Chouchane et al., 2010)
11.45 h - Ni5Zn211 g -Ni5Zn21 38.5 20 3.5 1.2972 158 (Chang et al., 2009)
2.62-8.07 h -Ni3Zn221 g -Ni5Zn21 * * 5 1.019-1.162 10.88-17.62 (Rao et al., 2013)
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8 MHD h -Ni3Zn221 g -Ni5Zn21 * 13.4 5 1.023 0.20 (Rao et al., 2013)

7.95 g -Ni5Zn211Zn1 Zn3Ni22 * 17.8 5 1.105 10.88 (Rao and Hegde, 2013)
* Zn3Ni8 1 Zn3Ni7 1ZnNi2 * * 3.65 1.067 54.3 (Fayomi et al., 2015)
4.2 Zn Phases ( g 1 h ) * 15 5 1.142 14.91 (Venkatakrishna and
Chitharanjan
Hegde,2010)
2.5 g -Ni5Zn211 d 80 10 3.5 1.023 1.03 (Basavanna and
-Ni3Zn221 h -phase Zn Arthoba Naik, 2011)
4.5 h -phase Zn 35 3.1 3.5 1.036 4.876 (Nayana and
Venkatesha, 2014)
* g -Ni5Zn211 h -Zn1 22 * 5 1.2345 1.63 (Kumar et al., 2012)
d -Ni
4.62 g -Ni5Zn211 d -Ni3Zn22 46-54nm 6 5 1.04 11.3 (Rashmi et al., 2017)
* g -Ni5Zn211 d -Ni3Zn22 * 20 5 1.005 12.23 (Ullal and Chitharanjan
Hegde, 2013)
Note: *Data not reported

Table II Corrosion potentials of different steels from literature data

Steel type Electrolyte/ wt% NaCl Corrosion potential/-V(vs SCE) References
4340 3.56 0.668 (Conde et al., 2011)
Cold rolled carbon steel 3 0.600 (Mosavat et al., 2012)
low carbon steel 3.5 0.737 (Kwon et al., 2016)
* 3 0.55 (Tsybulskaya et al., 2008)
St37 steel * 0.44 (Tafreshi et al., 2016)
Note: *Data not reported

corrosion potentials are sacrificial to all steels (<-0.73V) shown
in Table II. Table I also show that the use of electromagnetic
field (Rao et al., 2013) greatly improves the corrosion resistance
of the Zn-Ni alloys. The use of electromagnetic field decrease
the corrosion current to 0.25 m Acm 2 whilst the corrosion
potential is as high as 1.023 V, such alloys are always sacrificial
to steel substrates. The alloy electrodeposited using the
electromagnetic field consists of two phases, but still show the
best corrosion resistance. Future research should attempt to
electrodeposit single phase Zn-Ni alloys using electromagnetic
field as such alloys are likely to possess better corrosion
properties. Alloys produced in Kwon et al. (2016) and Rao et al.
(2013) have low Ni content and are of low corrosion rates.
Such alloys are good for sacrificial protection of steel and will
maintain sacrificial properties for a long time. An alloy in ref 90
will likely lose its sacrificial properties in a short time due to
dezincification because its corrosion potential is much close to
steel.
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
2.2 Pulse electrodeposited Zn-Ni alloys
Pulse electrodeposited Zn-Ni alloys have shown to be of better
corrosion resistance that direct plated alloys. In pulse
electrodeposition, the current or potential is imposed in a
periodic manner with a rectangular waveform (many wave
forms are possible) such that nucleation of discharged ions and
desorption of impurities occur during current off periods. Each
pulse consists of an ON-time (TON) during which potential
and/current is applied, and an OFF-time (TOFF) during which
zero current is applied as shown in Figure 5. In direct current
(DC) electroplating, a negatively charged layer is formed
around the cathode as the process continues and this layer
charges to a defined thickness and obstructs the ions from
Figure 5 Typical pulse-current waveform (Pagotto et al., 1999)
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Figure 6 Surface morphologies of alloy coatings deposited by DC, PC and PRC methods (Chang et al., 2009)
Anti-Corrosion Methods and Materials
reaching the part. In PED, the output is periodically turned off
to cause this layer to discharge somewhat. This allows easier
passage of the ions through the layer and onto the part. Thus, it
is possible to control the deposited film composition and
thickness in an atomic order by regulating the pulse amplitude
and width. The process improves homogeneity of morphology,
refine grains and reduces defects such as pinholes as shown for
the DC, PC and PRC morphologies in Figure 6. Thus, quality
coatings with decreased porosity, better ductility and hardness
are achieved (Ashassi-Sorkhabi et al., 2001; Pagotto et al.,
1999; Bajat and Miškovi, 2002). Regarding Zn-Ni coatings,
investigations showed that pulse plating provided smaller grain
size and better corrosion resistance compared to the coatings
produced by DC electroplating. Moreover, the deposits
prepared by using a smaller on time and high pulse peak current
density present a more refined grains and high Ni content
(Ramanauskas et al., 2005; Ashassi-Sorkhabi et al., 2001;
Alfantazi et al., 1996). It has been reported that by increasing
the Ni content, grain refinement of coatings down to nanoscale
is possible (Alfantazi et al., 1996). Ramanauskas et al. studied
the effects of the pulse parameters on the surface morphology,
grain size and corrosion properties of Zn-Ni alloy coatings
(Ramanauskas et al., 2005). Compared with coatings deposited
by DC plating, the grain size became smaller, the coating
 Electrochemical deposition of Zn-Ni (-X) alloys Anti-Corrosion Methods and Materials
Simbarashe Fashu and R. Khan

surface became denser and smoother, the crystal grains evenly
distributed and the number of lattice lacuna also increased,
which led to the improvement of the corrosion resistance. Bajat
et al. found that the influences of the pulse parameters on the
corrosion resistance of alloy coatings resulted from the changes
of the phase structure and chemical components, and studied
the relation of the pulse parameters to the current efficiency and
the Ni content in the coating (Bajat et al., 2005). In addition,
Hadian and Gabe reported that pulse plating mode could
reduce the residual stress of the alloy coatings and cracking to a
certain degree (Hadian and Gabe, 1999). The properties of
alloy coatings greatly depended on the structure and the
composition (Ashassi-Sorkhabi et al., 2001), while the
structure and the composition of the alloy coatings were
determined by the pulse plating mode.
Alternatively, Zn-Ni alloys may be electrodeposited under a
reverse pulse (RP) mode, in which the cathodic pulse waveform
is coupled with periodic anodic pulse. In PRC technique
(Figure 7), plating current is interrupted and a stripping time is
introduced into the plating cycle. PRC have the same effect of
Downloaded by 103.255.6.88 At 07:59 30 November 2018 (PT)
the protrusions of the metal surface to ensure a uniform
deposit. The introduction of high frequency PRC reduces the
use of additives, which limits the deposit ductility and electrical
conductivity. During anodic pulsing periods, the deposited
species may be dissoluted into a plating bath at different rates,
and re-nucleation of the deposit may also be well-promoted.
Furthermore, the limiting current is relatively high under the
RP mode. Reverse pulsing could, therefore, serve as a potential
strategy to tailor both the chemical composition and structure
of Zn-Ni alloys synthesized from single bath chemistry. As for
Zn-Ni alloys, limited studies on reverse pulse plating, solely
conducted on the alkaline (Ramanauskas et al., 2005) and
sulfate electrolyte (Popov et al., 1996) systems, have suggested
that increment of Ni content in the deposits is induced upon
application of pulse anodic current. Chang et al. (2009) studied
the effects of different plating modes on the microstructure and
corrosion resistance of Zn-Ni alloys. The results showed that
the crystal grains of the alloy coatings prepared by DC, PC and
PRC, respectively, became smaller and smaller in that order,
and the coating surface became compacter and smoother

replenishing the diffusion layer like PC and selectively dissolves
Figure 7 A typical pulse reverse waveform where, Ip1, Ip , Iav, T, tc
and ta,st and for positive peak current density (Ip1), reverse peak current
density (Ip ), average current density (Iav), cycle time (T), cathodic time
(tc) and anodic time (ta) (Fei and Wilcox, 2005)
correspondingly as shown in Figure 6. Using PRC,
Boonyongmaneerat et al. (2014) found that deposits with much
higher nickel content are obtained by prolonging the
dezincification period with increased pulse reverse duration.
The challenge of the PC and PRC plating methods is low
current efficiency of the processes besides uniform deposition
of coatings (Müller et al., 2003).
The comparisons of corrosion results for different pulse
plated Zn-Ni-(X) alloys for the period of 2007-2017 are shown
in Table III. When comparing the corrosion resistances of these
alloys with the DC plated ones of the same thickness and
corrosion potential (>0.95 V) shown in Table I, it show that
PC and PRC produce superior coatings than those produced
by DC plating. The pulse electrodeposited alloys produced
here are of lower Ni content however. Future work should aim
at using pulse electrodeposition to fabricate high Ni content
alloys. Such high Ni content alloys will likely have better
corrosion properties than those produced by direct plating
which are shown in Table I. Pulse electrodeposition improves
corrosion resistance mainly through grain refinement and this
minimize cracking such that the use of additives can be
completely avoided. Additives affect the quality of alloys and

Table III Pulse plated Zn-Ni coatings

Plating Corrosion test Corrosion Corrosion
Grain Coating current solution/ wt. potential current/
Ni content Phase size/nm thickness/ m m density % NaCl (-V vs SCE) m Acm 2 References
10.4-10.9 g -Ni5Zn21 23 12-15 PC 3.5 1.015 2 (Ghaziof and Gao,
2015)
12 g -Ni5Zn21 600 29 PC 3.5 0.95 10 (Gnanamuthu et al.,
2012)
11.28 h - Ni5Zn211 g 32.7 20 PC 3.5 1.014 40.2 (Chang et al., 2009)
-Ni5Zn21
11.68 h - Ni5Zn211 g 28.6 20 PRC 3.5 1.181 3.62 (Chang et al., 2009)
-Ni5Zn21
14 g -Ni5Zn21 25 * PRC 3.5 0.908 6.00 (Boonyongmaneerat
et al., 2014)
Note: *Data not reported
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
act as impurities in the deposit. Pulse plating of ternary alloys
like Zn-Ni-Co and Zn-Ni-Fe and composite alloys is still an
open area for research.
2.3 Compositionally modulated multilayer Zn-Ni
electrodeposited alloys
Corrosion resistance of Zn-Ni-(X) alloys can be enhanced by
the application of compositionally modulated multilayer
(CMM) coatings. The coatings are composed of various
alternating thin alloy/metal layers, and each layer plays its own
distinctive role in achieving preferred performances. Due to the
multilayer structure of these coatings, they often exhibit better
mechanical properties and/or corrosion resistance in
comparison with simple (monolithic) coatings because the
composition and specific structure have significant effect on the
corrosion process (Rahsepar and Bahrololoom, 2009; Ivanov
et al., 2002; Fei and Wilcox, 2006; Kalantary et al., 1995;
Krastev and Zielonka, 2002; Yin Fei et al., 2006). This arises
from the alternating (anodic/cathodic) mechanism of the
corrosion process and from the influence of the formed
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corrosion products. These coatings are effectively made using a
single bath technique. In this case, the layers are simply
obtained by changing the cathodic current density or electrode
rotation speed (or bath agitation rate) to get layers with
different compositions. The composition can be better
controlled, with a great degree of accuracy and reproducibility
using microprocessor controlled power sources (Cohen et al.,
1983). In principle, this technique is straightforward to design
and fabricate. The Ni content in CMM coatings are generally
low, but the corrosion resistance of the films is superior.
The results for comparison of corrosion resistance of Zn-Ni
alloys produced by CMM are shown in Table IV. The alloy
produced with a large number of layers in Venkatakrishna and
Chitharanjan Hegde (2010) show the highest corrosion
resistance. Such layers have low Ni content, but are of very high
corrosion resistance as explained before. Further research using
layers with high Ni content maybe necessary. The corrosion
resistance of these coatings is higher than DC and pulse plated
coatings of the same Ni content and thickness. The advantage
of such coatings are that they will always remain sacrificial to
steel due to low Ni content and at the same time they exhibit
low corrosion rates.
Table IV CMM Plated Zn-Ni alloys
Ni content Total coating
wt% Phase present thickness/ m m(layers) solution/ wt.% NaCl
12.2/13.9 * 16(4)
30 g -Ni5Zn21 12(7)
3.4/5.4 Zn Phases ( g 1 h ) 15(120)
6.62/7.91 g -Ni5Zn21 1Zn- 6 (60)
Phase
4.62/7.91 g -Ni5Zn21 1Zn- 6(30)
Phase
Note: *Data not reported
Anti-Corrosion Methods and Materials
2.4 Ternary and composite Zn-Ni-X electrodeposited
alloys
Ternary and composite Zn-Ni-X alloys were reported to be
superior to Zn-Ni alloys. A comparison of their corrosion
properties is compiled and shown in Table V. The corrosion
currents of many of these alloys are lower than those of Zn-Ni
alloys of comparable corrosion potential shown in Table I. In
addition, Ternary Zn-Ni-SiO2 alloys produced by CMMA
show the best corrosion resistance with a very small corrosion
current of 0.071 m Acm 2 and high corrosion potential of
1.072V, which is good for sacrificial protection. Work on
CMM plating of other ternary and composite Zn-Ni-X alloys
for corrosion protection of steel is still scarce and they deserve
researching.
2.5 Comparisons between DC, DC with
electromagnetic, PC, PRC and CMM Zn-Ni-(X)
corrosion properties
Table VI compares the best system in terms of corrosion
resistance from DC, PC, PRC and CMM. The Table clearly
show that CMM of binary Zn-Ni and Zn-Ni-X composites
produced sacrificial alloys of the best corrosion resistance.
3. Challenges and future direction
Zn-Ni-(X) alloys/composites show great potential for sacrificial
protection of steel substrates. Among the electrodeposition
techniques, comparison show that CMM of Zn-Ni, ternary and
composite Zn-Ni-X alloys show better corrosion properties
than DC, PC and PRC plated coatings. CMM alloys show
better promise in that low Ni alloys produced maintain
sacrificial properties and will not quickly lose sacrificial
properties due to dezincification. These low Ni content alloys
are not susceptible to cracking and high internal stresses. The
use of electromagnetic field is also a potential research area and
greatly improves the corrosion resistance of the Zn-Ni alloys.
However, there are still challenges to be resolved and these are:
 The electrodeposition of multicomponent alloys with
constant composition is still a challenge and the problem
is there even when using multicomponent anodes; and
 The study of the optimum coating thickness for best
corrosion protection is still scarce.
Corrosion Corrosion
Corrosion test potential current/ m A
(-V vs SCE) cm 2 References
5 0.940 2.16 (MacIej et al., 2012)
5 0.783 2.4 (Ganesan et al.,
2007)
5 1.049 0.253 (Venkatakrishna and
Chitharanjan
Hegde,2010)
5 1.03 4.3 (Rashmi et al., 2017)
5 1.03 4.3 (Rashmi et al., 2017)
 Electrochemical deposition of Zn-Ni (-X) alloys Anti-Corrosion Methods and Materials
Simbarashe Fashu and R. Khan

Table V Plated ternary and composite Zn-Ni-X alloys

Corrosion Corrosion
Alloy content Total coating Corrosion test potential current/ m A
Wt%/Method Phase present Grain size/nm thickness/ m m solution/wt.% NaCl (-V vs SCE) cm-2 References
14.25Ni h -Ni3Zn22 1 g * 22.2 5 0.687 1.4 (Eliaz et al., 2010)
6.35Co(DC) -Ni5Zn21
19.5Ni h -Ni3Zn221 g * 20.6 5 0.812 1.8 (Hegde et al.,
5.7Co(DC) -Ni5Zn21 2010]
10.2Ni g -Ni5Zn21 * 12-15 3.5 1.013 0.8 (Ghaziof and Gao,
-Al2O3(DC) 2015)
Zn-Ni- g -Ni5Zn211 16 * 5 1.199 0.682 (Kumar et al.,
Fe2O3(DC) h -Zn1 d -Ni 2012)
Zn-Ni- g -Ni5Zn211 * 20(300 layers) 5 1.072 0.071 (Ullal and
SiO2(CMM) h -Zn1 d -Ni Chitharanjan
Hegde, 2013)
Zn–Ni– g -Ni5Zn21 * 12-15 3.5 1.013 1 (Ghaziof and Gao,
Al2O3(10.8) 2015)
(PC)
Note: *Data not reported
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Table VI Comparisons of best alloys from different plating methods

Corrosion current Corrosion potential
Alloy Plating method ( m Acm 2) (-V vs SCE) Ni content/wt% References
Zn-Ni DC 0.62 0.78 15 (Sriraman et al., 2013)
DC 0.25 1.048 6 (Kwon et al., 2016)
DC-MHD 0.2 1.023 8 (Rao et al. (2013)
Zn-Ni PC 2 1.015 10.4 (Ghaziof and Gao, 2015)
Zn-Ni PRC 3.62 1.181 11.68 (Chang et al. (2009)
Zn-Ni-SiO2 PRC 1 1.013 10.8 (Ghaziof and Gao, 2014)
Zn-Ni CMM 0.253 1.049 3.4/5.4 (Venkatakrishna and
Chitharanjan Hegde, 2010)
Zn-Ni-SiO2 CMM 0.071 1.072 * (Ullal and Chitharanjan
Hegde, 2010)
Zn-Ni-Fe2O3 DC 0.682 1.199 * (Kumar et al., 2012)
Note: *Data not reported

The Future work should focus on:
 CMM electrodeposition of ternary and composite Zn-Ni-
(X) alloys;
 Research on Zn-Ni-(X) alloys electrodeposition from
ionic liquids;
 Increase the Ni content in PC and PRC plating; and
 Use electromagnetic stirring in plating of ternary/
composite Zn-Ni-(X) alloys.
4. Conclusions
Zn-Ni-(X) alloys show great potential for replacing Cd
metal in corrosion protection of steel substrates. The field of
electroplating is experiencing rapid change and use of
advanced plating technologies like electromagnetic, PC,
PRC, CMM significantly improve the corrosion properties
of the Zn-Ni-(X) films compared to DC plating. CMM
plating of ternary or composite Zn-Ni-(X) alloys show
greater potential for corrosion protection because alloys of
low nickel content and low corrosion rates are possible. The
process is simple to use. Such alloys are beneficial because
they will always remain sacrificial to steel even if dealloying
and dezincification of Zn from the Zn-Ni matric occur. Zn-
Ni alloys of higher Ni content produced by DC, PC and
PRC may be affected by dezincification such that the
corrosion potential may increase and they will end up not
being able to sacrificially protect the underlying steel
substrate. Zn-Ni-(X) alloys produced by electromagnetic,
PC and PRC show better corrosion protection than DC
plated alloys and this is mainly due to grain refinement of the
morphology of coatings. It is difficult to produce very high
Ni content alloys using the pulse electrodeposition
techniques. In addition, the setup of this process is
expensive compared to DC plating.
 Electrochemical deposition of Zn-Ni (-X) alloys
Simbarashe Fashu and R. Khan
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Corresponding author
Simbarashe Fashu can be contacted at: sfashu04@gmail.
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