ISSN 2070-2051, Protection of Metals and Physical Chemistry of Surfaces © Pleiades Publishing, Ltd., 2018.

Zinc–Nickel Alloy Electrodeposition: Characterization,

Properties, Multilayers and Composites1
N. Lotfia, M. Aliofkhazraeia, *, **, H. Rahmanib, and Gh. Barati Darbanda
aDepartment of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, Tehran, P.O. Box: 14115-143 Iran
bFaculty of Materials Science and Engineering, K.N. Toosi University of Technology, Tehran, Iran
*e-mail: maliofkh@gmail.com
**e-mail: khazraei@modares.ac.ir
Received October 9, 2016

Abstract⎯The alloy coatings such as zinc–nickel are used to improve the lifetime of zinc sacrificial coatings.
zinc–nickel alloy coating has a longer history than other zinc alloy coatings and is considered as the most cor-
rosion resistive zinc alloy. One of the important properties of this type of coatings is the ductility properties
of coated steel pieces; as after thermal treatment and shaping operations, the corrosion resistance is enhanced
up to an optimal level. Because of such properties, this alloy is investigated in coating the pieces such as con-
necting bolts, brake system components, and fuel system. Resistance to heat, ultraviolet light, hydraulic flu-
ids, and fuels are other characteristics of such coatings. The use of zinc–nickel alloy coatings is growing in the
bolts and threaded parts industry. Since these coatings do not prevent galvanic corrosion in contact with alu-
minum, they are widely used in industries that deal with aluminum bodies. However, the zinc–nickel alloys
are considered as the most expensive coatings. These alloys are coated both by acidic and alkaline baths that
provide different coating properties. This paper reviews the studies conducted on zinc–nickel alloy coatings,
analyzing baths and their properties, the effect of different parameters on electrodeposition, as well as Zn–
Ni multilayer and composite coatings and their properties.

Keywords: composite, corrosion resistance, electrodeposition, multilayer, zinc–nickel

DOI: 10.1134/S2070205118060187

OUTLINE 6.1.1. Zinc sulfate 17

1. Introduction 2 6.1.2. Nickel sulfate 17
2. Zinc–nickel alloy coating properties 2 6.1.3. Sodium Sulfate 17
3. Zinc–nickel alloy coating electrochemical 6.1.4. ZnCl2 17
deposition anomalous behavior 4 6.1.5. NiCl2 18
4. Zinc–nickel alloy coating applications 4 6.1.6. Boric acid 18
5. Zinc–nickel alloy coating 6.1.7. Polynitroaniline 18
electrodeposition baths 6 6.1.8. CTAB 19
5.1. Electrodeposition from Acid Baths 7 6.2. Temperature 19
5.1.1. Sulfate bath 7 6.3. pH 21
5.1.2. Chloride bath 9 6.4. Current Density 22
5.1.3. Sulfate, acetate, non-cyanide 6.5. Pulse Current 23
sulfamate, and ammonium baths 11
6.5.1. Ton 24
5.2. Electrodeposition from Alkaline Baths 12
6.5.2. Toff 24
5.2.1. Sulfate bath 12
5.2.2. Chloride bath 14 6.5.3. Toff/Ton ratio 24
5.2.3. Commercial alkaline baths 14 6.5.4. Pulse current density 25
6. Effects of bath parameters 7. Multilayer zinc–nickel alloy coatings 25
on zinc–nickel alloy coatings 17 7.1. Zn–Ni Multilayer Coating
6.1. Compositions and Additives 17 Microstructure 25
7.2. The Properties of zinc–nickel
1 The article is published in the original.
Multilayer Coating 27

1
2 LOTFI et al.
7.3. Zinc–nickel Multilayer
Coating Applications 28
8. Zinc–nickel composite coatings 28
8.1. Zinc–nickel Composite Coatings
Microstructure 30
8.2. Zinc–nickel Coating Composite
Properties 31
8.3. Zinc–nickel Composite Coating
Applications 33
9. Summary and future trend 33
10. References 35
1. INTRODUCTION
Considering the higher corrosion resistance com-
pared to pure zinc and other alloy coatings, electrode-
position of Zn–Ni alloy has recently received a wide-
spread attention. The studies conducted on these
coatings initiated in the early 20th century [1, 2]. In
the early 1980s, the study of zinc–nickel electrodepo-
sition and other properties of this coating was pursued
even more than before [3, 4]. This coating also was
used as an alternative to corrosion protection coatings
especially toxic cadmium coatings in 1983 [5, 6]. D.
Hall [7] reviewed zinc–nickel alloy coatings by exam-
ining the anomalous behavior of the coating, phase,
alloy structures, physical properties, and corrosion
and deposition conditions of zinc–nickel alloy coat-
ings. A large number of works have been conducted in
this area to improve the overall behavior of samples
regarding customer requirements, basic ductility,
weldability, corrosion resistance after the conversion
of the surface and painting [8, 9]. Recently, consider-
able efforts have been done to improve the corrosion
resistance of zinc and zinc alloy coatings for applica-
tion in harsh environments [10, 11]. Nowadays, differ-
ent types of steel sheets with the zinc–nickel coating
are used in large quantities to improve the durability of
car bodies [12, 13]. Based on our knowledge. No com-
prehensive review paper abut zinc– nickel coating by
electrodeposition was not reported in the literatures.
In this review paper, comprehensive discussion about
all aspect of zinc–nickel coating fabricated by electro-
deposition method is reported.
2. ZINC–NICKEL ALLOY
COATING PROPERTIES
Steel is widely used in industry because of its excel-
lent properties. Considering its low corrosion resis-
tance, many protection methods have been developed
to increase its corrosion resistance [14–16]. Among
these methods, electrodeposition of a thin layer of
zinc, nickel, cadmium or deposition of their alloys on
the metal is widely used [17]. Electrodeposition of
zinc–nickel coatings has long been known to provide
better corrosion protection of steel than electro galva-
nized, galvanized and cadmium coatings [7, 18]. Also,
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
the hardness and thermal stability of the coatings are
evaluated and good results have been achieved [19,
20]. These coatings are frequently used in industry
because of their excellent corrosion resistance and the
increased life of the zinc coatings [21, 22]. These alloy
coatings are also used to reduce the thickness of the
zinc coatings [23].
Zinc has a reverse standard potential of –0.76 V/SHE
which is more negative than iron (Fe/Fe2+ – 0.44 V/SHE).
Thus, it is used for sacrificial cathodic protection of
steel against corrosion. Zinc is often used to cover
parts of iron and steel when it is one of the primary
factors for atmospheric and internal corrosion protec-
tion [8]. Commercial electrodeposition of zinc is used
in cyanide, alkaline, cyanide, and acid chloride baths
[24, 25]. In the 1970s, the highest commercial electro-
deposition of zinc was performed in common cyanide
baths but the international pressures for environmen-
tal pollution developed other processes [8].
It has been shown that the zinc alloys can improve
corrosion resistance compared to the pure zinc in pro-
tecting the ferrous based metals [26–28]. Zinc–nickel
alloys have attracted a considerable attention because
of their high corrosion resistance [29–31] and better
mechanical properties than zinc and other zinc alloy
coatings [32]. Although the demand for zinc–nickel
coatings with the improved mechanical and corrosion
properties is increased for industrial applications, the
zinc–nickel alloy layers are commonly used to protect
the steel from corrosion [11, 33, 34]. Zinc–nickel
coating properties depend on composition and pH of
the bath, temperature, current density, electrodeposi-
tion potential, coating application mode (pulse or
DC) [35–37]. Nickel plays a key role in corrosion
resistance of zinc–nickel alloy coating since it reduces
the hydration of Zn(OH)2 into the ZnO-corrosion
product. Hydroxide has a lower electrical conductivity
than the oxide layer, leading to a weaker cathode oxy-
gen reduction reaction than the oxide and conse-
quently a lower corrosion [10]. Qiao et al. [38] studied
the deposition temperature effect on electrodeposition
of zinc–nickel alloy and concluded that when it
increases up to 60°C, the amount of zinc–nickel
deposition is increased most. Wykpis et al. [39] studied
the effect of current density on zinc–nickel electrode-
position and concluded that the surface morphology
and chemical composition of the coatings phase are
dependent on the current density deposition. Many
organic chemical compounds including glycine, tri-
ethylamine, polyamine compounds, and glycerol
[40–43] are reported to improve the surface morphol-
ogy and nickel concentration during the deposition
[44]. Byk et al. [45] studied the zinc–nickel alloy elec-
trochemical deposition in polyligand bath that
includes amino acetic acid and triethylamine as a
ligand for the accession of Ni(II) cations. The alloy
composition is strongly influenced by the
[Zn(II)]/[Ni(II)] ratio in the bath [46]. Besides, the
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
(a) 20 μm (b) 20 μm (c)
Fig. 1. Zinc–nickel alloy coating micromorphology with different nickel contents (a) 6.49, (b) 10.09, (c) 12.25, (d) 95.13, and (e)
15.08 at % nickel [61].
nickel content in the deposition varies between 8 and
75%. To improve the corrosion properties of pure zinc
coatings used in the transportation industry, the zinc
alloy coatings are replaced with the eighth group (Zn–
Ni, Zn–Co, Zn–Fe). Due to the high toxicity and
cost of cadmium coatings, zinc–nickel coatings are
the most successful alloys and are good replacements
for cadmium coatings [47, 48]. It is reported that
zinc–nickel coatings with 10–15 wt % nickel have a
better corrosion resistance, ductility, and weldability.
Although the nickel content reaches 15–22 wt % in the
aviation industry, Barcelo et al. [49] reported that the
alloys containing 10 to 15 wt % nickel play a special
role in corrosion resistance. In addition to the chemi-
cal composition, physical properties of zinc–nickel
coatings depend on their microstructure, phase chem-
ical composition, and structural parameters. Zinc–
nickel anomalous codeposition is highlighted in the
early twentieth century and thoroughly investigated by
Brenner et al. [50] and other researchers [51].
Many studies have been conducted on phases of
zinc–nickel alloys [52]. In a research work, the zinc–
nickel alloy dispositions are analyzed as coatings for
the improved corrosion resistance at low current den-
sities (more than 50 mA/cm2) in sulfate solutions. It
was observed that composition of cathode deposits for
most matrixes has a complex structure called as γ,
which is an alternative to cadmium. In addition,
phase-γ zinc–nickel alloy with approximately 13 wt %
nickel has the best corrosion resistance among the
zinc–nickel alloys. The coating adhesion and weld-
ability are also better and obtaining almost constant
alloy composition in the wide range of deposition con-
ditions is easy [53]. Electrodeposition of zinc–nickel
coating is carried out in acidic and alkaline baths with
sulfate and chloride composition and other different
baths and the properties of each and their comparison
were carried out [54–56].
One of the important properties of zinc–nickel
alloy coating is their corrosion resistance in corrosive
environments and their higher resistance compared to
pure zinc coatings. Moreover, one of the parameters
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
3
20 μm (d) 20 μm (e) 20 μm
affecting the corrosion resistance of zinc–nickel alloy
coating is the nickel content in the coating. The salt
spray test (ASTM B 117) [57] was carried out on alloy
coating and other zinc coatings. The test compares the
corrosion resistance of these coatings with other ones
and also presents the effect of nickel content on alloy
coating. The results of these tests show that the corro-
sion resistance of zinc–nickel alloy coating is far better
than other zinc coatings. Besides, by increasing the
nickel content in the deposition up to 12–15 wt %, cor-
rosion resistance is improved. Exceeding 12–15 wt % of
nickel content, the corrosion resistance is reduced
compared to the previous mode [22, 58].
Many factors affect the properties of zinc–nickel
alloy coating [59]. Corrosion performance of nano-
crystalline electrodeposited zinc–nickel alloy coating
in a chloride bath is analyzed by direct current density
using impedance spectroscopy and polarization
curves and compared with microcrystalline alloy coat-
ings. The corrosion product formed on nanocrystal-
line zinc–nickel alloy coating is more sustainable and
provides a higher protection compared to microcrys-
talline alloy coating. Nanocrystalline zinc–nickel
alloy with 18 wt % and crystal size 37 nm has the best
performance among zinc–nickel alloys. Also, the cor-
rosion resistance of zinc–nickel alloy coating depends
on the chemical composition [60].
Changes in chemical composition with coating
depth in a chloride bath were investigated and found
that chemical composition at the surface has a higher
atoms fraction of the zinc and then the nickel content
is increased in the substrate surface. The micromor-
phology of zinc–nickel alloy coatings with different
amounts of nickel is presented in Fig. 1. It can be
observed that the crystallization during electrochemi-
cal deposition stage is not fine and in the low of nickel,
the coating is loose and rough. By increasing the nickel
content, the crystallization of coatings becomes finer,
brighter, and more uniform [61].
According to ASTM B841 [62], alloy coatings can
be classified as Fig. 2. As it can be observed, these
coatings are classified into three categories in terms of
4 LOTFI et al.

Class 1 5–12 wt % Ni
(Concentration)
Type A (coloriess)

Type B (yellow
iridescent)

Type C (cronze)
Zn-Ni Alloy coating Type (chromate
(ASTM B41) conversion coating)
Type D (black)

Type E (without
topcoat)

Grade 5 (5 μm)

Grade (Thickness) Grade 8 (8 μm)

Grade 10 (10 μm)

Fig. 2. Zinc–nickel alloy coating chart classification according to ASTM B41.

chemical composition, after coating operations and
thickness. In the first group, the nickel concentration
in the deposit varies in the range of 5–12 wt % that is
an optimal nickel content in the deposition for corro-
sion resistance. Moreover, in the second classifica-
tion, the coating is classified based on chromate con-
version after coating based on color. Finally, in the
third classification, the coating is classified into three
groups of 5, 8 and 10 μm based on its thickness [62].
3. ZINC–NICKEL ALLOY COATING
ELECTROCHEMICAL DEPOSITION
ANOMALOUS BEHAVIOR
Zinc alloys obtained by a metal from the iron group
(Ni, Fe, Co) under the condition known as anomalous
codeposition indicate less noble zinc deposits prefer-
entially [63, 64]. Electrodeposition of zinc anomalous
behavior in zinc–nickel coatings is reported and ana-
lyzed in many studies [65, 66]. Recent studies con-
ducted on the reaction mechanism suggest that this
phenomenon is related to the local increase of pH at
the cathode surface due to the hydrogen evolution
which is the result of the type of absorbed zinc hydrox-
ide through slower discharge of iron group [8, 67, 68].
In addition, nickel is nobler than zinc; zinc–nickel
codeposition is anomalous and zinc is more present in
the final deposition. Zinc–nickel deposition is classi-
fied as an anomalous codeposition through which
a less noble zinc metal (active) is deposited preferably
and its percentage in the deposition is more than the
bath. This process follows the deposition on hydroxide
and retention of Ni2+ [69]. Another research carried
out based on underpotential deposition (UPD) of zinc
is on nickel and zinc-rich alloys or on the nickel
nucleus. To protect steel, the investigated alloy might
have either a high amount of zinc which is more active
than steel (sacrificial film) or higher amount of nickel
which is nobler than the steel surface (barrier film)
[70]. Researchers have concluded that the codeposi-
tion of iron-group metals is done as the result of
reduced rate of the nobler compound reaction and the
increased rate of the more active compound reaction
compared to the deposition of a single metal [47, 71].
In other studies, it is confirmed that the anomalous
behavior is attributed to the formation of zinc hydrox-
ide on the cathode surface that prevents the deposition
of nickel and zinc hydroxide formation due to the local
increase in pH as the result of hydrogen evolution [72].
Zinc–nickel alloy properties, especially for corrosion
resistance, are essentially dependent on nickel con-
centration in zinc–nickel depositions. The optimum
amount of nickel for the maximum protection is
within the range of 8–15 wt % and zinc–nickel alloys
with a nickel content of 13 wt % present the highest
corrosion protection [29, 73].
4. ZINC–NICKEL ALLOY
COATING APPLICATIONS
In addition to zinc–nickel alloy coatings used in
steel car bodies [74, 75], they are considered for other

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 ZINC–NICKEL ALLOY ELECTRODEPOSITION
Automotive
Industry
Electronic Aerospace
Industry Industry
Zn-Ni Alloy
Shipbuilding Fastener
coating
Industry Industry
Application
Pipe and
Transportation
profile
Industry
Industry
Other
Industry
Fig. 3. Schematic of applications of zinc–nickel alloy coat-
ings.
applications such as electrical catalysts [76–78],
hydrogen electrode [79, 80], coating for steel wire con-
nections [81] and in aerospace [72] and electronics
[72, 82]. Because of its special corrosion resistance
compared with the zinc coatings, zinc–nickel alloy
coatings are investigated on electrical and building
products [83] and even for aluminum alloy coating
[84]. Also, zinc–nickel alloy coatings are suitable
alternatives for cadmium coatings. Cadmium is highly
toxic and, considering the health and pollution risks,
the environmental regulations are encouraging the use
of alternative protective systems [5]. In a study, zinc–
nickel alloys are sprayed in the ceramic coatings’ inter-
face on the steel substrate to improve the corrosion
and adhesion properties of plasma ceramic coating
[82]. Moreover, zinc–nickel alloy coatings are used for
chromate or other coatings [85–88]. Applications for
zinc–nickel alloy coatings are summarized in Fig. 3.
Zinc protects mild steel from corrosion because of
its sacrificial property. This alloy is used on one or
both side of the galvanized steel sheets with a relatively
heavy coating, galvannealed steel sheets, electrogalva-
nized and steel plates coated with an organic powder
that is commercially used for automobile body panels.
Although corrosion resistant steel sheets do not have
the application of high strength steel sheets to reduce
weight and the heavy painting steel plates, they have
the decorative and hygienic, ductility, weldability and
other properties required for application of corrosion
resistant steel sheet to be used in cars [89]. Ductility
and weldability are important properties for making
car body and producing a corrosion resistant steel
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
5
Corrosion rate coating metals in SST
Red rust on the surface in SST Not-treated
Corrosion weight loss in outdoor exposure test sheets
Delamination of paint film in SST
Delamination of paint film in outdoor Paint
exposure test coated sheets
Delamination of paint film in CST (cross cutted)
Depth of pitting in CST
5 5
Poor
4 4
of corrosion resistance
Relative evaluation
3
3 γ-phase
2 2
1 1
Good
10 20 30 40 50
Concentration of alloying element
Ni in Zn coating layer, wt %
Fig. 4. Zinc–nickel alloy coated sheet design of different
corrosion tests in salt spray test (SST), external revealing
test, and corrosion simulation test (CST) [90].
sheet by electrodeposition process that does not
change the mechanical properties of the base steel. In
order to improve the anticorrosion performance of
typical electrogalvanized steel sheets, although it is
necessary to increase the zinc coating thickness, it
reduces pressure weldability and ductility. The elec-
trodeposited metal coating should provide (1)
enhancing the corrosion resistance of zinc coating
layer [90] and (2) reducing the thickness of the coating
and improving pressure ductility and weldability.
Designing the improved corrosion resistance in elec-
trical deposition based on zinc protection in natural
environments is related to stabilizing Zn(OH)2 in nor-
mal natural atmospheres. The studies conducted on
the stability of Zn(OH)2 synthesized with different
alloys indicate that the alloy elements such as Co, Ni,
Mg, Al, and Mn slow down the conversion of
Zn(OH)2 into ZnO. According to this concept, nickel
and cobalt are selected as alloying elements that can be
electrodeposited [91]. When the real alloy coating
composition stability is performed, the phase γ alloy is
chosen as a good balance of different corrosion tests
that shown as Fig. 4 [90]. Electrodeposited zinc–
nickel alloy steel plates have a good paintability similar
to cold rolled steel and effectively prevent scaling and
color bubbles. Furthermore, the excellent corrosion
resistance of the electrodeposited steel plates is con-
firmed by real cars test in salt coated paths [92].
Currently, zinc is the most widely used corrosion
protective coating investigated either by hot dipping or
6 LOTFI et al.
γ'
(a) α β' γ phology than the pure zinc [101]. The aerospace
(b) α α + β' β' β' + γ' γ' γ γ + δ δ + η
γ' + γ
(c) α γ
γ+η
α+γ
(d) α γ γ γ
0 50 γ + δ δ + η100
Percent Zn, by weight
Fig. 5. Prepared phase diagram based on the composition
of alloys with pyro metallography (a and b) and electro-
chemical (c and d). No phase is determined by the shaded
areas.
electrodeposition processes. However, to achieve high
levels of corrosion protection, the zinc coating should
be thick enough (usually above 25 μm) to improve in
corrosive environments. The most losses associated
with thick coatings are the low ductility and weldabil-
ity. Besides, thick coating causes problems in achiev-
ing the polished surface after painting. Thick coating
problems lead to developed thinner electrodeposition
with improved properties compared with zinc [93].
Zinc alloys with the group VIII metals (iron, nickel,
cobalt, etc.) are the first alternative for this purpose. In
particular, studies show that corrosion resistance of
zinc–nickel alloy coatings with a specific chemical
range composition (12–14 wt % nickel) can be 5–6
times better than pure zinc with an equal thickness. It
has been shown that ductility [90] and weldability of
zinc–nickel alloy coated steel are good [82, 94]. To
improve the efficiency of these zinc–nickel alloy coat-
ings, the ternary alloy coatings have also been analyzed
[95–98].
5. ZINC–NICKEL ALLOY COATING
ELECTRODEPOSITION BATHS
Electrodeposition of binary metal in a special bath
depends on the proximity of their reduction potentials.
Electrodeposition of binary metal occurs when their
reduction potential is close and the concentration of
each of the metals in solution is relatively determined
or when the complexing agent with complex shapes is
added with different equilibrium constants [99].
Zinc–nickel alloy coating is considered as a good
coating to protect the steel corrosion [17, 42, 46]. Fur-
thermore, this coating provides better mechanical
properties and superior temperature stability com-
pared to pure zinc and other zinc alloys [44, 47, 100].
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
δ Zinc–nickel electrodeposited alloy coatings have spe-
cial high corrosion resistance and better surface mor-
industry focuses on zinc–nickel alloy coating as an
alternative to toxic cadmium coatings with high costs.
Efforts are undertaken to replace cadmium due to its
metal poisoning, hydrogen embrittlement, and the
δ prevented use of cyanide bath in cadmium electrode-
position. Zinc–nickel coatings are widely used as an
η alternative for cadmium electrodeposition for its cor-
rosion protective properties, ductility, and improved
γ+η welding characteristics. Zink-nickel coatings 8–14 wt %
Ni has shown a corrosion resistance 4 times more than
cadmium-titanium coatings [102]. However, zinc–
nickel alloys have more negative potential than the
cadmium because of the high zinc content in the
deposition and, then, dissolving faster in corrosive
environments. Conventional nickel deposition in the
alloy is approximately 5–10 wt % and higher nickel is
obtained by using more nickel in the electrodeposition
bath. The increase in nickel in the compounds creates
a more positive phase in the circuit potential that
reduces the driving force for galvanic corrosion. Pro-
hibition characteristics with rich deposits of nickel are
more than other coatings. Zink–nickel alloys prepared
by the pulse and multi-layered process are performed
to obtain alloys with high corrosion resistance [103].
Pyrometallography studies of zinc–nickel alloys in
the balance, at low temperatures, have phase range
similar to that of Figs. 5a, 5b. The phase range at
250°C is indicated in Fig. 5. Brenner [50] reported a
higher perfect equilibrium phase at 200°C in Fig. 5b.
However, a difference between phase range of Zn—Ni
alloys prepared by electrochemical and thermal pro-
cesses is observed. The electrodeposited phases in
zinc–nickel are detected in sulfate bath by the X-ray
diffraction and the results are shown in Fig. 5c. Elec-
trodeposition conditions do not produce the alloy
compounds in the light shaded areas. A very limited
data set based on the X-ray diffraction tests of sulfate
bath are for the ternary electrodeposited compounds
that are presented in Fig. 5d. Electron probe micro-
analysis revealed that nickel and zinc are distributed
homogeneously without any evidence of separation.
The phases of five alloys are presented in Fig. 5d as a
shaded area. Phase β′ is not deposited. Phase δ is con-
firmed in some depositions containing phase γ or η but
it is not observed alone. The data in Fig. 5c, d show the
results of other studies where phase β' is not in the
electrodeposition. In addition, the electrodeposition
of the phase δ is also a question [7, 104].
The zinc–nickel alloy phase diagrams shown in
Fig. 6 [105] indicates the presence of three δ, γ, and β
phases. The various phases of the diagram show the
solubility of the zinc and nickel elements with a differ-
ent chemical composition. As can be seen, γ phase
produced from eutectic reaction at 875°C that liquid
phase transmuted to two solid phases. In addition to,
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
0 10 20 30 40
1600
1455°C
1400
1200
1034°C
Temperature, °C
1000 37.9
815°C
800 (Ni) 35.3
600
400
361°C
Tc
200
0
0 10 20 30 40 50
Ni Atomic Percent Zinc
Fig. 6. Zinc–nickel alloys equilibrium diagram [105].
peritectic reactions at 1040 and 490°C produced β and
δ phases, respectively.
In most cases, the pure zinc is the substrate for
materials coating on the steel. However, over the past
three decades, alloys are presented for a higher quality
of the end product and long lifetime. Major pressures
from the automobile industry and in the aerospace
field are investigated on the demand for faster and
electrical equipment. Today, it is highly recommended
replacing cadmium due to its toxic nature. Electrode-
position of zinc alloy will be discussed more in the
continuous electrodeposition. Zinc–nickel alloys can
be deposit by acidic or non-cyanide alkaline solutions.
The acid bath can have higher nickel content than an
alkaline bath. Corrosion protection of steel with is
increased by raising the nickel content. Apart from this
amount, the deposition is nobler than the substrate
may lose its sacrificial properties. Finally, the deposi-
tion of the acid bath has a low thickness distribution
and alloy changes are observed in low to high-density
areas. Moreover, the speed of alkaline electrodeposi-
tion bath is lower. Therefore, the column structure is
preferred to the sheet structure of the acid bath espe-
cially when the major part of mechanical forming is
done after electrodeposition. One of the differences in
barrel and rack electrodeposition bath is the dilution
of the barrel bath compared to the rack bath and also
its lower operating temperature [8].
Different parameters affect the properties and
characteristics of the electrodeposition coatings. To
analyze these parameters on properties such as corro-
sion resistance, hardness [19, 106], and specifications
such as the components in the deposition and coating
thickness can be mentioned. In deposition baths of
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
7
50 60 70 80 90 100
L
51.6
β 876°C
57.5 70
652°C
56 71.5
491°C
β1 85.2
419.58°C
γ
δ
(Zn)
60 70 80 90 100
Zn
zinc–nickel alloy coatings, according to the con-
ducted surveys, it is possible to classify the deposition
baths into acidic [107, 108] and alkaline [109–111] two
main categories. Each of these baths can be classified
in terms of the chemical composition of sulfate [112–
114], chloride [115, 116] baths and other baths such as
acetate, ammonium [117], and citrate [118]. In order
to the comparison, zinc–nickel alloy coating proper-
ties are evaluated in both acidic and alkaline baths. For
example, the acid bath used has a chemical composi-
tion with a concentration of NiSO4, ZnSO4, NiCl2,
H3BO3 and trisodium citrate with pH = 3–4 and alka-
line bath which has ZnO, NiSO4 and triethanolamine
with the pH = 13–14. Figure 7 presents the effect of
solution ratio in acidic and alkaline baths on zinc–
nickel alloy coatings. As the figure shows, the zinc–
nickel deposits have anomalous behavior because the
nickel ratio is much lower than its ratio in solution. As
the figure suggests, the nickel concentration in the
deposition is lower than the electrodeposition in the
alkaline bath due to the presence of alloying elements
as free ions in solution [119].
5.1. Electrodeposition from Acid Baths
5.1.1. Sulfate bath. Krisha et al. [71] used sulfate
solution containing ZnSO4, NiSO4, H2SO4, Na2SO4,
and H3BO4 to deposit zinc nickel alloy. The alloys are
used with galvanostatic deposition at the investigated
current density of 10 mA/cm2 for the deposition on a
mild steel rod. In this study, the effect of sulfuric acid
and nickel sulfate concentration and deposition time
(from 1 to 20 min) was investigated. Zinc–nickel alloy
phases varied with nickel concentrations and detected
8 LOTFI et al.

wt % nickel in deposits 18 (a)

Intensity, arb. unit

15

δ δ
12 δ
δ
δ δ
γ δ
γ
9 γ γ
γ
γ γ
γ

6 (b)

35 40 45 50 55 60 65

Intensity, arb. unit

wt % nickel in the bath
Fig. 7. The impact of the nickel ratio in the deposition on
its weight percentage in the deposition, full square-acid
bath, full circle-alkaline bath [119].
with X-ray diffraction. Figure 8a (in Ni2+ 0.01 M)
and 8b
(in 0.50 M) indicate that the increased rate of Ni2+
results in an increase in the phase γ and phase reduc-
tion in δ. According to these figures, the relative
amount of phase γ and δ in the depositions (deter-
mined by the height of peaks) depends on the nickel
concentration in the electrodeposition. Voltammetry
curves of this coating include two anodic peaks. The
first anodic peak (in –0.97 V/SHE) is associated with
zinc deposition of the phase δ-(Ni3Zn22) that is trans-
ferred to the positive values. The peak height is
reduced by increasing concentration of nickel. The
second peak appears at –0.67 V/SHE and is related to
zinc dissolution in the phase γ-(Ni5Zn21) and the peak
height increases with the higher concentration of
nickel. Thus, it is concluded that by the increasing
concentrations of nickel in the bath the phase δ
increase and decrease, respectively [71].
Zinc–nickel alloy coating on mild steel substrate is
deposited at different currents of sulfate bath with the
chemical composition ZnSO4, NiSO4, H3BO4, Na2SO4,
and H2SO4. After dipping, the potential is reduced
about –560 mV/SCE and deposition were done with
the additional potential for very low nucleation. Note
that such initial potential amounts are associated with
the mild steel substrate. Next, zinc concentration
increases to produce new phases of ZnNi (Probably
phase γ). At low polarization, nickel deposition is sig-
nificantly reduced due to the presence of zinc and zinc
deposition that is stimulated by the presence of nickel.
The potentiometric test indicates the additional
absorption process possibly related to the middle
+ cally to provide smooth surfaces used for degreasing in
(ZnNi ad ). The cathode current density increases up
leads to the more negative values of the surface poten-
tial. Cyclic voltammetry in Fig. 9 indicates the pres-
ence of four peaks in progressive and reverse scanning.
γ
γ
γ γ γ
γ
γ γ
δ δ
δ
δ
δ δ
δ
0 10 20 30 40 50 60 70 80 90 100
2θ, deg
Fig. 8. Zinc–nickel alloy phases varied with nickel concen-
trations and detected with X-ray diffraction [71].
Mild steel electrode is within the range of –0.7 to
‒1.2 V/SCE in the cycles. The first peak starting from
‒1.07 V/SCE is indexed to the simultaneous reduc-
tion of Ni2+ and Zn2+. Increasing current density in
the negative potentials from –1.15 V/SCE is associated
with hydrogen release reaction and sulfuric acid reduc-
tion. Anode dissolutions of the third and fourth peaks
are related to the zinc and nickel dissolution from the
phases. After the fourth peak, the flow approaches zero
indicating that the deposited zinc–nickel alloy coating
is mostly removed from the surface [120].
The effect of bath parameters and add-on on the
chemical composition of the bath with ZnO, KOH,
and NiSO4 is investigated through the statistical stud-
ies. The nickel value and thickness are 1–6 wt % and
1–8 μm by changing the parameters and adding the
bath [121]. In another study, the sulfate bath is used to
evaluate the effect of the add-on. The compositions of
soluble are ZnSO4, NiSO4, H3BO4, and Na2SO4.
Solution pH is set by 10% sulfuric acid or sodium
bicarbonate solution. The zinc plate is used as the
anode. The anode is activated in the 10% sulfuric acid.
Killed steel plates of cell baths are polished mechani-
boiling Trichloroethylene. The shells and killed steel
plates are removed by immersion in a solution of 10%
sulfuric acid [46].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 ZINC–NICKEL ALLOY ELECTRODEPOSITION 9

PEAK III a Zn only

b Zn–Ni alloy (1st cycle)
c Zn–Ni alloy (20th cycle)
10
I, mA cm2

PEAK IV

0
a
PEAK I
–10 b (a) 50 μm (b) 50 μm
PEAK II
c
–20
–1200 –1000 –800 –600 –400
E, mV SCE

Fig. 9. Pure zinc (a) and zinc–nickel alloy (b, c) deposited

on cyclic voltammetry conditions (maximum current Ic =
15 mA, 0.3 V/min and T = 30 ± 2°C in the electrodeposi- (c) 50 μm (d) 50 μm
tion solution on steel with the cycle –0.7 to –1.2 V/SCE
and return to –0.5 V/SCE) [120].

In order to achieve better properties, the pulse

method is used for depositing of zinc–nickel alloy
[122]. In a study based on pulse coating method, the
sulfate bath ZnSO4, NiSO4, and Na2SO4, and the
pulse current density 60 mA/cm2 with the on time 0.2 ms
and off time 0.0 to 2.0 ms and the total on/off time of
the 60 s were used. The morphology of zinc–nickel
coating described and changed from triangular-pyra-
mid-shaped to pyramidal shaped crystals [123].
In addition to the sulfate baths used by sulfate
chemical composite in zinc and nickel used for coat-
ing, in another study, the nickel sulfate and zinc oxide
were used to create coating alloy. Electrolytic zinc–
nickel coating is obtained by the alkaline bath contain-
ing ZnO, NaOH, ethylenediamine, triethanolamine
and solutions of Ni where ethylenediamine and tri-
ethylamine are complex factors and 20 mL/L of nickel
is combined and is kept constant during the experi-
ment. ZnO and NaOH concentration is varied during
the test. The Ni solution was carried out by combining
ethylenediamine and triethylamine and dissolving
nickel sulfate in the solution. Complexing agents of
ethylenediamine and triethylamine that form a stable
complex with the ion Ni2+ were used as the solvent for
nickel sulfate in an alkaline bath. Electrodeposition
tests were done in the cell equipped with a cathode
made of steel (St12) and nickel anode. Nickel content
and Zn–Ni deposition thickness were used as the
response to changes. The results of this experiment
showed that the concentration of NaOH does not
change the nickel content in the deposition but its high
concentration reduces zinc–nickel coating thickness.
When the concentration of NaOH is increased, a uni-
form compressed deposition is observed. The XRD
results showed that all coatings only present the cubic
phase γ structure (Ni5Zn21). Increasing the concentra-
tion of NaOH shows the grain size reduction. The
results of XRD are confirmed by the SEM observa-
tions of Fig. 10, where perfectly smooth surfaces,
(e) 50 μm
Fig. 10. SEM images of zinc–nickel deposits present the
zinc–nickel coating morphology changes [124].
without cracks, and with the smallest grain size in
NaOH and ZnO concentrations are seen [124].
5.1.2. Chloride bath. The zinc–nickel deposits are
formed from a basic solution ZnCl2 + NiCl2 at KCl +
H3BO3 in a range of concentration of the condensa-
tion products. All chemicals and solutions are pre-
pared. The electrochemical behavior of zinc and nickel
are investigated by cyclic voltammetry. Figure 11 pres-
ents the conventional voltammetry curves obtained
from alloy solutions in the presence or absence of con-
densation products. In the absence of condensation
products, three anode peaks (Ia, IIa, and IIIa) are
observed within the range of –1.095 to 0.0 V/SCE.
The specifications of multiple peaks during the elec-
trochemical oxidation of alloys are related to the dis-
solved metals in the alloys with different intermediate
phases. Three anode dissolution peaks for zinc–nickel
alloy are associated with the dissolution of deposited
phases δ and γ. Reduction potential in the presence of
condensation product is shifted towards the more neg-
ative values. When the potential scan is reversed, the
three anode peaks are less observed within the similar
range with lower current densities. The results show
that condensation product prevents the dissolution of
zinc–nickel alloy and increases the corrosion resis-
tance of the deposition [101].
The chloride bath is used to investigate the mecha-
nism of zinc–nickel deposition. In this study, the elec-
trodeposition solution chemical composition are

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

10
–0.8 IIIa
Ia IIa
–0.4
Current, mA cm–2
0 15
Eco
0.4 a Zn–Ni
Eη b Zn–Ni in presence of CP
c without metal
0.8
–1.6 –1.2 –0.8 –0.4 0
Potential vs. SCE/V
Fig. 11. Voltammetry curves obtained from solution 0.1 M
ZnCl2+ 0.05 M NiCl2 in 2.5 M KCl + 0.32 M H3BO3,
pH 3.5 at different concentrations of CP: (a) 0.0 mM,
(b) 0.2 mM, V = 30 mV/s [101].
ZnCl2, NiCl2, and KCl. The cathode is a gold layer
deposited on teflon. The results showed that zinc
hydroxide is electrodeposited because of an increase
in pH [73].
The chloride bath is used in the early studies con-
ducted on optimizing the electrolytic bath through cell
methods. NiCl2, NH4Cl, boric acid, nitric acid and
Thiamine hydrochloride are used to deposit electro-
lyte containing ZnO. The killed steel plated active sur-
face area of the cathode is used after preparation. By
adding small amounts of thiamine hydrochloride, a
significant improvement is seen on the gloss and
homogeneity of the deposition [125].
To improve the coating properties of the alloys, the
pulsed current density is investigated. In one of these
studies, the chloride bath was used to investigating the
pulsed current density. Zinc–nickel alloy pulsed elec-
trodeposition was carried out on a mild steel plate or
on rotating disc electrodes of chloride bath ZnO,
NiCl2, NH4Cl, and H3BO3. The results showed that
the on-time did not affect the Ni content of deposits
by the pulsed current [26].
In another study, in order to investigating electro-
deposition the chloride base, electrolyte was used by
adding an appropriate amount of compounds ZnCl2,
NiCl2, (Sodium lauryl sulfate) SL, and boric acid by
stirring in distilled. Sodium lauryl sulfate is used as the
wetting agent to reduce the risk of cavities. This special
wetting agent is used for its wide application in the
industry. Boric acid is used to maintain the pH of the
bath. The advantage of using a high amount of metal is
that the high current densities can be used and pro-
duce thick deposits. The setting is performed by add-
ing hydrochloric acid (to decrease pH) or ammonia
(to increase pH). By increasing nickel content, grain
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
LOTFI et al.
30 100
Ni
25 95
Component of Ni, %
Zn
Component of Zn, %
20 90
85
10 80
5 75
0 70
0 0.2 0.4 0.6 0.8 1.0
Magnetic field, T
Fig. 12. The effect of magnetic intensity on zinc–nickel
layers [128].
refinement in the deposits decreases to nanocrystal-
line size [82].
Interesting analyses are performed on the effect of
magnetic field on electrochemical deposition of zinc–
nickel alloy coatings [126, 127]. To study the effect of
this field, the chloride bath including ZnCl2, NiCl2,
KCl, NH4Cl2, and H3BO3 were used. The deposition
was done in the magnetic field parallel to the elec-
trodes. Figure 12 indicates the effect of magnetic field
on the concentration of elements in depositions. As
the figure suggests, nickel concentrations in the
deposit are between 5–10 wt %. Besides, Ni2+ and
Zn2+ ions have an equal positive charge but the mass of
Zn2+ is lower than Ni2+. Thus, at first, the ions are
accelerated under the same electrical power. Zn2+ ions
form the colloids cathode Zn(OH)2 along with zinc.
When a magnetic field is investigated, a force against
the Zn(OH)2 colloids accelerates nickel deposition pro-
cess [128]. In another study, the effect of magnetic field
on the deposition of alloy coating is analyzed in the chlo-
ride bath with the composition ZnCl2, NiCl2, boric acid,
NH4Cl, gelatin, and glycerol and pure zinc anode and
killed steel cathode. The polarization curve in Fig. 13
presents the corrosion resistance of these coatings in a
different magnetic field. The optimal mode is obtained
in the field 0.6 T with 8.5 mm/y [129].
The deposition of zinc–nickel alloy coating in the
chloride bath was used from ZnCl2, NiCl2, H3BO3,
and hexylsulphate for the alloy deposition of nickel up
to 20 wt %. Figure 14 indicates the alloy coating sur-
face with different nickel concentrations in zinc–
nickel alloy coating. As shown in this figure, by
increasing nickel concentration the structure becomes
fine-grained [130].
An example of optimized chloride bath with acidic
pH can refer to the bath with a chemical composition
zinc chloride, nickel chloride, NH4Cl, KCl, glycine,
and gelatin. The deposition was done by pure zinc
anode and the air was used for stirring. Optimization
 ZINC–NICKEL ALLOY ELECTRODEPOSITION 11

–0.7 (Zn–Ni)B = 0 T
(Zn–Ni)B = 0.4 T
–0.8
Potential (V) vs. SCE

(Zn–Ni)B = 0.6 T
–0.9 (Zn–Ni)B = 0.8 T
(Zn–Ni)B = 1.0 T
–1.0

–1.1
(a) 1 μm
–1.2

–1.3
1E-101E-91E-8 1E-7 1E-6 1E-5 1E-41E-3 0.01
Current density, A cm–2

Fig. 13. The behavior of potentiodynamic polarization of

zinc–nickel coatings obtained from the optimal bath at
different magnetic fields [129].

(b) 1 μm
criteria are to create a smooth and uniform zinc–
nickel coating on killed steel. For example, Fig. 15 Fig. 14. Zinc–nickel alloy electrodeposition by: (a) 8.5 wt %
presents the effect of current density on the surface of and (b) 14.5 wt % nickel with the current density 5 mA/cm2
deposit, where the resultant deposit has a smoother [130].
surface than the rest of the deposits with different cur-
rent densities [131].
that the coating is investigated selectively on the
5.1.3. Sulfate, acetate, non-cyanide sulfamate, and
intended area. The composition used for all samples is
ammonium baths. One of the baths with chemical
composition is the sulfate–acetate electrolytes. In this zinc acetate, nickel acetate, sodium acetate, and gla-
bath, the [Ni]/[Zn] concentration ratio is analyzed in cial acetic acid. The sponge porous medium and ultra-
the range of 0.1–4 by keeping [Ni] + [Zn] = 0.5 M filtration (UF) membrane are investigated. Figure 17
constant. The potentiodynamic polarization curves of presents the cross section of zinc–nickel by two
the solutions with different combinations demonstrate porous media. It is observed that the known coatings
that the increase in [Ni]/[Zn] concentration ratio with sponge had a lower porosity. Such a lower poros-
increases the inhibition of the alloy deposits [132]. ity is obtained by the effect of investigated pressure in
Zinc–nickel alloy deposition was analyzed in ace- the buffer action that compressed the coatings over the
tate bath. Zn-Ni binary alloys were electrodeposited deposition process [133].
on mild steel sheets of the bath containing zinc acetate
(Zn(CH3COO)2), nickel acetate (Ni(CH3COO)2),
and acetic acid (CH3COOH). Figure 16 presents the (a) (b)
polarization curves for nickel, zinc and zinc–nickel
alloys electrodeposition under similar circumstances.
Curves of polarization for the deposition of zinc and
zinc alloy present small cathode peak C which rep-
resents the H+ ions discharge. The drop of cathode 50 μm c, d, 1 A/dm3 50 μm c, d, 2 A/dm3
current after potential peak C indicates the hydrogen
release prohibition. Such behavior can be due to the (c) (d)
formed and adsorbed zinc hydroxide barrier on the
cathode surface. The hydrogen release areas are possi-
bly occupied by the absorbed by zinc hydroxide [72].
Using the interesting mobile electrodeposition
method for analyzing a similar bath to the acetate bath 50 μm c, d, 3 A/dm3 50 μm c, d, 4 A/dm3
is among the methods that are different from the com-
mon electrodeposition methods that have been ana- Fig. 15. SEM (magnification 500) image of zinc–nickel
lyzed so far. Diffusion environment allows the cations alloy deposit resulting in current densities 10, 20, 30, and
to penetrate into the electrode surface (cathode) so 40 mA/cm2 (all at pH 4) [131].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

12 LOTFI et al.

15 mA/cm2 is 6 and 2.5 μm, respectively. The compar-

Zn ison between the micrographs indicates the reduced
1.0 Ni grain size with increasing current density. Such a
Zn–Ni Zn decrease in grain size might be due to the fact that at
higher current densities deposition rate is higher and
0.8 thus adatoms are largely nonmoving and join the layer
with less surface movement and therefore the grain
i, Adm–2

0.6 size is limited [134].

Ni
0.4
C NiCl2 and NH4Cl is obtained by adding HCl and NH3.
0.2
0
–700 –900 –1100 –1300
E, mV
Fig. 16. Polarization curve calculated (---) and tested (__)
for the electrodeposition of zinc from 0.1 M zinc acetate,
0.1 M nickel acetate and zinc nickel alloy CH3COOH =
0.2 M, scan rate = 1 mV/s and T = 20°C [72].
(a) 50 μm (b) 50 μm
Fig. 17. The zinc–nickel coatings cross section obtained by
selected electrodeposition equipment. Potential with the
reference electrode Ag/AgCl: (a) coating with low porosity
produced by sponge at –0.3 V (b) coating with higher [133].
(a) 50 μm (b) 50 μm
Fig. 18. SEM images of zinc–nickel pulsed electrodeposi-
tion in the mentioned current density at room temperature
for 30 minute [134].
Zinc–nickel alloy electrodeposition with pulsed
electrodeposition was performed by non-cyanide
sulfamate bath. Electrochemical deposition with the
chemical composition includes zinc sulfamate, nickel
sulfamate, boric acid, ammonium chloride, β-naph-
thol, sodium lauryl sulfate. Figure 18 presents the
SEM image of zinc–nickel alloy pulse electrodeposi-
tion at the current densities 5 and 15 mA/cm2. Depos-
ited zinc–nickel alloy layer grain size in 5 and
Zinc–nickel electrodeposition under galvanostatic
conditions at a constant thickness of 10 μm in the
ammonium bath with a chemical compound of ZnCl2,
By adding ammonium, a shell with the chemical com-
position 9.4–14 wt % Ni Was developed [135]. The
summary of results from the acid bath for electrodepo-
sition of Zn–Ni alloy coating is indicated in Table 1.
5.2. Electrodeposition from Alkaline Baths
5.2.1. Sulfate bath. To analyze the effect of current
density of deposition on zinc–nickel alloy coating
properties, the ammonium bath with the sulfate com-
pounds and concentrations of NiSO4, ZnSO4, Na2SO4,
(NH4)2SO4 and NH4OH was investigated. As shown
in Fig. 19, the surfaces resulting from zinc–nickel
coatings are gray and smooth. The coatings are crack-
free and indicate a good adhesion to the substrate.
Small cracks are only observed on the deposited coat-
ing surfaces [39]. Furthermore, in an earlier similar
analysis (by the same researchers), electrochemical
deposition and the analysis of the composite proper-
ties of the zinc–nickel coating with nickel particles was
performed. The deposition was done to obtain a coat-
ing thickness of 20 μm, where the nickel plate was used
as the anode. All zinc–nickel coatings with nickel par-
ticles were detected with the pale and light gray sur-
faces. Similarly, the coatings were crack-free and indi-
cated a good adhesion to the substrate. Figure 20 pres-
ents the images of the surface of these cracks. By
increasing the current density, the impact current and
agglomeration of nickel grains happen [136].
For the electrochemical deposition of phase γ of
zinc–nickel alloy, the alkaline bath with the chemical
composition of ZnSO4, NiSO4, and sodium acetate
was used. Zinc–nickel alloy with 8–15 wt % nickel on
stainless steel deposited for corrosion protection. Fig-
ure 21 presents the X-ray diffraction pattern of phase γ
of zinc–nickel alloy with a molar ratio 3 : 1 (ZnSO4 :
NiSO4). Direction (330) in diffraction pattern pres-
ents phase γ [137].
To optimize zinc–nickel alloy coating and the
release of hydrogen on zinc–nickel alloy, the sulfate
bath was used. The alkaline sulfate bath has a chemical
composition including ZnSO4, NiSO4, Na2SO4, and
NaOH. ZnSO4 concentration is based on the ionic
ratio Zn/Ni and pH of electrodeposition bath is set by
NaOH and H2SO4. Using the experimental strategies,
the optimum deposition is obtained at 50°C, current

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 Table 1. Summary of results of research conducted on zinc–nickel alloy coating in acid bath
Tempera- Time, Current density, Thickness, Ni, icorr, Ecorr, Refe-
Coating composition 2 pH Phase
ture, °C min mA/cm μm wt % μA/cm2 mV vs. SCE rence
ZnCl2–NiCl2–KCl–NH4Cl–H3BO3 30 3 20 6 N.R. 5–21 N.R. 0.1–0.3 –800 to –900 [128]
ZnCl2–NiCl2–H3BO3–NH4Cl N.R. 19 10 2 5 N.R. γ 0–0.15 –1452 [157]
ZnCl2–NiCl2–NH4Cl 10–70 60 15 5 N.R. 11–68 γ N.R. N.R. [38]
ZnCl2–NiCl2–NH4Cl–NaSCN– 23 N.R. 50 5 N.R. N.R. N.R. N.R. N.R. [115]
ZnCl2–NiCl2–H3BO3 35 N.R. 0–100 3.5 N.R. 13–17 γ 0.8 –671 to –1035 [170]
ZnCl2–NiCl2–H3BO3 45 N.R. 70 6.9 N.R. 3–18 N.R. N.R. –890 to –1030 [116]
ZnCl2–NiCl2–H3BO3–NH4Cl 35 20 40 4.8 15 5–15 η + γ + δ N.R. –1066 to –1023 [61]
Ni(CH3COO)2–ZnCl2–KCl–H3BO3 50 N.R. 20–100 5 15 80–87 γ + δ 0.02–0.05 –900 to–1200 [141]
ZnCl2–NiCl2–H3BO3 30 30 0–100 3.5 N.R. 11–17 γ N.R. N.R. [37]
ZnCl2–NiCl2–H3BO3–NH4Cl 20–30 N.R. 15–30 1–4 20 9–10 N.R. N.R. N.R. [152]
ZnCl2–NiCl2–Na2PO4–NH4Cl 20 N.R. 5–40 4.5 6 14–75 γ + δ + α 0.02–0.05 –0750 to –800 [45]
ZnCl2–NiCl2–H3BO3–NH4Cl–SLS– 40 N.R. 30–6000 3.5 N.R. 13–15.5 N.R. N.R. N.R. [35]
Gelatin–Sacaros
ZnCl2–NiCl2–KCl–H3BO3 25–55 N.R. N.R. 4.8 3 17–60 γ+δ N.R. –700 to –900 [202]
ZnCl2–NiCl2–NH4Cl 25 N.R. 0.5 5.5 N.R. 15–45 γ+δ N.R. N.R. [36]
ZnCl2–NiCl2–KCl–H3BO3–NH4Cl 18–58 N.R. 0–40 1.5–5.8 N.R. 10–25 γ+δ N.R. N.R. [166]
ZnCl2–NiCl2–NH4Cl N.R. 3 20 5.6 5–10 N.R. η + γ + δ N.R. –925 to –1120 [52]
ZnCl2–NiCl2–H3BO3–SLS 25–80 30 25 3.5 N.R. 8–22 γ+δ N.R. N.R. [19]
ZnCl2–NiCl2–H3BO3 50 N.R. 5–20 3.5–4 6–12 20 γ+δ N.R. N.R. [130]
NiSO4–ZnSO4–Na2SO4 24–40–60 10 20–50–80–100 2 13 5.5–10.5 γ N.R. N.R. [203]
NiSO4–ZnSO4–Na2SO4 30 10 10–30 3 N.R. 7–19 ∂, γ 7.7–44.8 –717 to –945 [165],
H3BO3–Na3C6H5O7 [204]
NiSO4–ZnSO4–Na2SO4– 30 N.R. 25 2.5 8–9.5 N.R. γ N.R. N.R. [108]

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

H2SO4–H3BO3
NiSO4–ZnSO4–C6H5O7–(NH4)2SO4 25 10 30 4.3 N.R. N.R. N.R. 5.125 –1063 [205]
NiSO4–NiCl2–H3BO3 50 40 50 4–4.5 N.R. 15 N.R. 1.258 N.R. [206,
207]
ZINC–NICKEL ALLOY ELECTRODEPOSITION

NiSO4–NiCl2–H3BO3–ZnSO4 25 N.R. 20 5.5–6 N.R. 11 N.R. N.R. N.R. [208]

NiSO4–ZnSO4–C6H5O7–(NH4)2SO4 25 N.R. 45 5.7 N.R. 12 ∂, γ 11.2 −940 [209]
ZnSO4–NiSO4–H3BO3–NiCl2 N.R. N.R. 30 3–4 N.R. 10–18 η–γ 0.04 −955 [119]
NiSO4–ZnSO4–Na2SO4–H3BO3 20–30 N.R. 10–50 2–5 N.R. N.R. N.R. N.R. N.R. [46]
NiSO4–ZnSO4–H3BO3– 25 N.R. N.R. 4 100–120 N.R. N.R. N.R. N.R. [210]
natrium lauryl sulphate–
NiSO4–ZnSO4–H3BO3–NH4Cl 40–50 10–15 50–150 3–5 N.R. 13 γ N.R. N.R. [85]
NiSO4–ZnSO4–SnSO4 60 N.R. 40 1–2 35 14 γ N.R. N.R. [191]
NiSO4–ZnSO4–Na2SO4–H3BO3 N.R. 20–45 200 3 N.R. N.R. N.R. N.R. N.R. [211]
NiSO4–ZnSO4–Na2SO4 50 N.R. 50 2 1.3 13 γ N.R. N.R. [212]
NiSO4–ZnSO4–Na2SO4–NiSO4 50 N.R. 20–40 2 20 9 η+γ N.R. N.R. [100]
* N.R. = Not reported.
13
14 LOTFI et al.

(a) 5 μm (b) 5 μm (c) 5 μm

(d) 5 μm (e) 5 μm

Fig. 19. The surface morphology of zinc–nickel coatings obtained at different current densities: (a) 20, (b) 30, (c) 40, (d) 50 [39].

density 25 mA/cm2, pH = 13, and the ionic ratio of
Zn/Ni 0.9 [138].
5.2.2. Chloride bath. Chloride baths that are ana-
lyzed in the alkaline range are scarce. To study the fac-
tors affecting the zinc–nickel alloy coating properties
such as temperature, pH, the ratio of components, and
the effect of additives the chloride solution within the
range of pH = 7–8 was used. This bath included the
materials with the concentration of NiCl2, ZnCl2,
KCl, and HEDP (coordinating agent), and other
additives with working conditions and current density
8.5–20 mA/cm2 where the zinc is the anode. Effects of
parameters based on nickel content in the bath are
optimized withvalues 25–150 g/L under the working
conditions 10 mA/cm2 and 25°C [9].
5.2.3. Commercial alkaline baths. An example of
alkali baths containing NaOH, the base solution , pol-
isher, Ni and Zn ions were used in the research con-
ducted by Hajjami et al. [47] zinc–nickel alloy deposi-
tion was carried on plain carbon steel using commer-
cial alkaline electrolyte solution with the dissolution of
the reagent ZnO, NiSO4, NH2CH2CH2NH2 and
NaOH. Copper and platinum sheets were used as the
cathode and anode, respectively. Figure 22 illustrates
the SEM images of zinc–nickel alloy deposition in 50
and 100 mA/cm2. The nickel concentration in the
deposits at 50 and 100 mA/cm2 deposits of the eth-
SS
Gamma (330)

400

300
Intensity, cps

(a) 30 μm (b) 30 μm
200
SS
SS

100
SS

0
(c) 30 μm 40 50 60 70 80 90 100
2θ, deg
Fig. 20. Zinc–nickel coating surface morphology with pre-
cipitated nickel particles at the current density of (a) 30, (b) 50 Fig. 21. The X-ray diffraction pattern of phase γ of zinc–
[136]. nickel alloy coating obtained by alkaline sulfate bath [137].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 ZINC–NICKEL ALLOY ELECTRODEPOSITION 15

50 A m–2 100 A m–2

γ(411) (330)
EDA

γ(442) (600)
Intensity

γ(552)
(a) (b)

γ(332)

γ(811)
γ(444)
γ(510) (431)
γ(422)
TEA

γ(521)

400 nm
(c) (d)
Fig. 22. SEM images of zinc–nickel alloys of zinc solu-
tions containing ethylenediamine and triethanolamine
[83].
ylenediamine solutions is 9.8 and 13.8 wt % while the
deposits are at 50 and 100 mA/cm2 of triethanolamine
solution as 8.4 and 79.2 wt %, respectively. The depo-
sition obtained at 50 mA/cm2 of ethylenediamine
solution presents the smooth surface of the trigonal-
pyramid (Fig. 22a) while at 100 mA/cm2 the dark edge
of the trigonal pyramid is observed (Fig. 22b). In addi-
tion, in the deposition of 100 mA/cm2, small crystals
in the form of the crystalline core are seen above the
inner surface. Furthermore, the deposit at 50 mA/m2
of the solution triethanolamine shown in Fig. 22c has
a smooth surface consisting of fine grains while the
deposit presented in Fig. 22d could be observed as
plane blocks. Surface morphology dependence with a
current density in triethanolamine creates alloy com-
position. The nickel concentration in depositions of
ethylenediamine solutions is almost similar to that of
triethanolamine solution and the surface morphology
of both deposits is compared. In the deposits in eth-
ylenediamine solution, the crystal plate surfaces are
smoother and few cracks are observed between the
Fe
Fe
20 30 40 50 60 70 80 90
Fig. 23. X-ray diffraction patterns of zinc–nickel codepos-
ited coating [41].
sition of zinc oxide, nickel sulfate, sodium hydroxide,
complexing agent (amine), and suitable additives.
Under these circumstances, the coating with nickel
content between 14–17 wt % is obtained. The corro-
sion resistance of the coating is 1000 h in the natural
salt spray without red rust [139].
In the electrodeposition of zinc–nickel composite,
alloy with alumina particles and alkaline bath with
chemical composition NaOH, zincate75 (including
zinc and NaOH), Ni-CPL were used. Deposition cur-
rent density of composite is kept constant at
20 mA/cm2 by potentiostat-galvanostat. Figure 24
presents the X-ray diffraction of composite coatings.
As seen in this figure, the amount of Al2O3 and the
phase γ value increases and the preferential orientation
appears at (330) and (600) [140]. Table 2 presents the
properties of Zn–Ni alloy coating of electrodeposited
from the alkaline bath.
Cr Kα
Zn–Ni (a) λ = 2.2897 nm
Zn–Ni–Al2O3 5 g/L (b)
γNi5Zn21(600)

crystal plates in the deposits obtained by triethanol- Zn–Ni–Al2O3 10 g/L (c)

amine solution [83]. Zn–Ni–Al2O3 15 g/L (d)
Intensity, a.u.

In Fig. 23, the X-ray diffraction pattern of code-

γNi5Zn21 (330)

posited zinc–nickel coating is shown. Zinc–nickel

alloy coatings of the non-cyanide commercial alkaline
bath are deposited. Alkaline solution contains zinc
oxide, nickel sulfate, sodium hydroxide, complexing
agent (amine), and suitable additives. The coatings (d)
with the nickel content between 14 wt % (15.4 at %) (c)
and 17 wt % (18.6 at %) are deposited in this bath. The (b)
(a)
coatings presented 1000 h corrosion resistance in salt
spray chamber without any effects of red rust. X-ray 40 50 60 70 80 90 100 110 120
2θ, deg
diffraction lines of this coating presented the phase
γ-Ni5Zn21 without any other phase [41].
Fig. 24. X-ray diffraction image of zinc–nickel coatings
X-ray diffraction spectrum of zinc–nickel coating and zinc–nickel with Al2O3 particles at various concentra-
in commercial alkaline bath has the chemical compo- tions of Al2O3 (5, 10, and 15 g/L) [140].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 Table 2. Summary of results of research conducted on zinc–nickel alloy coating in alkaline bath
16

Current
Tempera- Time, Thickness, Ni, icorr, Ecorr,
Coating composition density, pH Phase Reference
ture, °C min μm wt % μA/cm2 mV vs. SCE
mA/cm2

NiSO4–ZnSO4–Na2SO4–(NH4)2SO4–NH4OH 25 N.R. 20–60 9–10 N.R. 14–18 Ni2Zn11 0.9–0.41 –791 to –802 [39, 136]

NiSO4–ZnO–NaOH–[NH(CH2CH2–NH2)2]– N.R. N.R. 15–35 13.5 12–15 14–16 γ N.R. –990 to –1109 [213]
DETA

ZnO–NaOH–NiSO4–TEA– N.R. N.R. 30 13–14 N.R. 5–10 η-Ni3Zn22–Ni5Zn21 0.0177 −998 [119]

ZnO–NiCl2–Na2PO4–NH4Cl 20 N.R. 5–40 7.5 6 21–89 γ+δ+α 0.03–0.8 –950 to –1300 [45]
LOTFI et al.

ZnO–NaOH–NiSO4–[NH(CH2CH2_NH2)2]– 25 N.R. 5–50 N.R. N.R. 12.5–14 η+γ 0–0.04 –500 to –1500 [54]

NiSO4–ZnO–NaOH– 25 N.R. 20 N.R. 13 14–17 γ N.R. N.R. [41]

NiSO4–ZnO–NaOH-Triethanolamie-ethylene- 18 10 10 N.R. 3 15–20 γ N.R. N.R. [124]

diamie

NiSO4–ZnO–NaOH-Amine-Triethanolamie 25 N.R. 20 N.R. N.R. 14–17 γ N.R. N.R. [139]

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

* N.R. = Not reported.
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
6. EFFECTS OF BATH PARAMETERS
ON ZINC–NICKEL ALLOY COATINGS
Many studies have been conducted on the factors
affecting the electrochemical deposition of zinc–
nickel alloy coating and their results [141, 142]. Tem-
perature, pH, current density, concentration, etc. are
among the electrochemical deposition bath parame-
ters that have a major effect on properties and chemi-
cal composition of the surface [143–145]. Optimiza-
tion of these parameters is studied in several studies
[146–149]. In addition to the chemical composition,
thickness and surface morphology, hardness and cor-
rosion resistance are among determining factors in the
optimal state [150]. In the following, some of these
studies are discussed.
6.1. Compositions and Additives
In an electrodeposition bath, optimizing the vari-
ous concentrations of metal ions in the electrodeposi-
tion solution is important especially when industrial
electrodeposition process of zinc–nickel alloy is
developed [151]. The effect of bath compositions on
characteristics of coatings such as brightness [152] is
considered as a means of a change in its concentrations
[82, 153].
6.1.1. Zinc sulfate. In a conducted survey to under-
stand the zinc ion effect, the sulfate concentration was
altered while the sodium sulfate, boric acid, and
CTAB being kept. At lower zinc sulfate concentra-
tions, the bright deposit was observed. At a lower cur-
rent density range, a thin deposit was observed. It is
noticeable that the cell pattern has no burned deposits
when the zinc sulfate concentration is 200 g/L. At
higher concentrations, there is no change in nature of
the deposit. Zinc concentration at 200 g/L is proven
optimal [46].
6.1.2. Nickel sulfate. To find out the impact of
nickel metal ion, the nickel sulfate was varied by
polynitroaniline, zinc sulfate, sodium sulfite, boric
acid, and CTAB. At lower concentrations of nickel
sulfate, the bright deposition was observed. With the
increase in the concentration of nickel sulfate, the
bright deposition was developed [46]. The effect of
nickel concentrations in solution on the cyclic voltam-
metry cathodic polarization is presented in Fig. 25.
Deposition potentials are shifted to positive values
with increased nickel concentrations. In addition, the
cathode current peak is associated with the release of
hydrogen which consequently is reduced by increasing
Ni2+ concentration. The phenomenon is caused by
adsorption competition between Ni2+ and H+ to
occupy the active sites by which the preferential
adsorption of nickel is increased by increasing Ni2+
concentration [71].
6.1.3. Sodium Sulfate. Sodium sulfate is commonly
added to bath solution for increasing the conductivity
[46, 71, 114]. At lower sodium sulfate concentrations,
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
17
0.010
0.005
i, A cm–2
0
0.10 M
0.20 M
–0.005 0.30 M
0.40 M
0.50 M
–0.010
–1100 –1000 –900 –800 –700 –600 –500
E vs. Ag/AgCl mV
Fig. 25. Cyclic voltammetry curves for steel in different
concentrations of nickel sulfate at the scan rate 5 mV/s at
30°C [71].
the cell patterns present burned deposits. The burned
areas without coatings are reduced when the nickel
sulfate concentration exceeds 80 g/L. When the con-
centration of sodium sulfate reaches 100 g/L, the
bright deposit provides. Thus, increasing the concen-
tration of sodium sulfate had no effect on the nature of
the deposition. Based on these observations, sodium
sulfate concentration is fixed at 100 g/L as the opti-
mum [46].
6.1.4. ZnCl2. In an electrodeposition chloride
bath, ZnCl2 concentrations were studied by keeping
other additives constant. The variations of the ZnCl2
concentration change nickel concentration in the
deposit in the range of 12.2–14 wt %. As expected, the
higher ZnCl2 concentrations in the bath first give
higher zinc amount (lower nickel). However, as Bren-
ner [50] suggested, the alloy composition has an
approximate dependence to increasing the amount of
ZnCl2 in the bath. The results show that the electrode-
position under these conditions is anomalous at the
area above the concentration of ZnCl2. The concen-
tration of nobler metal (nickel) is much lower than its
value in the bath. The changes in nickel percentage
ions in the bath between 26.5 and 68% calculated by
the ratio of Ni/(Zn + Ni) in the bath are presented by
changing the zinc content of the bath (adding ZnCl2)
while nickel concentration in the bath is kept constant.
Using different electrolytes and direct electrodeposi-
tion conditions, similar results were observed in some
studies. The electrodeposit surface morphology is not
significantly affected by the changes in the concentra-
tion of ZnCl2 in the tested range. As a typical example,
the SEM image for zinc–nickel alloy produced in
concentrations of ZnCl2 is shown in Fig. 26. The
deposits have a fine grain structure with average of
18
Current efficiency, % 100
95
90
85
80
0 0.1 0.2 0.3 0.4 0.5
Concentration of formic acid, mol/L
Fig. 26. SEM image of zinc–nickel alloy pulsed electrical
deposition at a concentration of 300 g/dm3 ZnCl2 [82].
grain size of about 0.5–2 μm. This result is expected
because the chemical composition had no specific
changes. Moreover, it was also observed that nickel
concentration in the deposition is an important
parameter in controlling the morphology of the pulse
plated zinc–nickel alloys. All deposits had single
phase γ caused by the XRD experiments. Based on the
above results, it is concluded that the resulting chemi-
cal composition (12–14 wt % Ni) for corrosion pro-
tection is obtained with the input ZnCl2 range. How-
ever, the high levels of ZnCl2 are selected to increase
the electrical conductivity of the bath [82].
6.1.5. NiCl2. A series of tests are done in the chlo-
ride electrodeposition bath to determine the individ-
ual effects of NiCl2 concentration in the bath on the
chemical composition, morphology, and phase struc-
ture distribution in the deposit. The amount of depos-
ited nickel is increased up to 12.5 wt % by increasing
NiCl2 in the electrolyte. These results are consistent
with other studies indicating that by increasing the
nickel ions in the bath the nickel concentration of the
deposition also increases. It is proposed that the linear
relationship observed in the low range of NiCl2 is in
accordance with the theory that the reduction of
nickel ions is controlled by the influence. The mor-
phology of deposition produced show that for deposits
generated at low concentration of NiCl2, the smooth
surface morphology is obtained and the structure
includes both fine-grained γ and coarse η crystals
phase. With increasing NiCl2 concentrations, the
deposit is very smooth and includes the phase γ with
fine grain nodded morphology with a grain size of
about 0.5–2 μm. Besides, there is an additional bene-
fit of using high NiCl2 concentration to produce a
fixed concentration of deposit that even more fluctu-
ations of NiCl2 concentration in the bath do not
change the chemical composition of the deposit. Sim-
ilar effects of fluctuations in the concentration of in
the bath at the lower range result in higher relative
changes in the chemical composition and the phase
presence in the closer control of bath chemistry [82].
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
LOTFI et al.
6.1.6. Boric acid. The effect of boric acid on the
electrochemical deposition of zinc–nickel alloy layers
is highly complicated [71]. The purpose of adding
boric acid in electrodeposition bath is to control the
H+ ion in the bath solution. To see the optimal con-
centration of boric acid, the concentration is varied by
keeping other additives at optimal levels. At lower con-
centrations of boric acid, the deposit is bright in a
higher current range. The bright area is developed by
boric acid. Since the higher concentration of boric
0.6 acid has no effect on the pattern of cell pattern [46].
Experiments show that in most cases boric acid shifts
nickel concentration in the alloy toward the nickel-
rich phases to prevent the deposition (by alloying).
Boric acid also blocks the release of hydrogen. It is
expected that neutral molecules are boric acid are
replaced by the adsorbed anions (sulfates and chlo-
rides) in the negative electrode in an electrochemical
deposition due to more negative electrostatic force.
When boric acid exists electrode surface, it is expected
to affect all the intermediate processes (release of
hydrogen, zinc, and nickel deposits) [154]. Boric acid
either forms a complex with Ni2+ and is used as a
homogeneous catalyst or absorbed on the electrode
surface. This acid has a special role in the morphology
and composite characteristics. The presence of boric
acid increases the efficiency of the deposition process,
the amount of zinc in the deposited alloy and nucle-
ation density. These effects are attributed to the
absorption reactions at the electrode surface. More-
over, boric acid is a buffer to hold electrolyte pH. Sim-
ilar effects of boric acid are observed during zinc–
nickel alloy deposition in sulfate baths [155]. It also
indicated that the impact of boric acid at different
ratios of Ni/Zn is due to the discharge reaction of H+
[156]. Boric acid at different concentrations is used in
a chloride bath for galvanostatic coating of zinc–
nickel alloy with different concentrations of H3BO3.
Figure 27 presents the corrosion rate of zinc–nickel
coatings obtained by measuring the weight loss in
NaCl solution. As shown in this figure, by increasing
the formic acid in solution, the corrosion rate is and
does not change thereafter. This behavior is attributed
to the reduction of nickel content in the deposition
[157]. Figure 28 presents summary of effect of compo-
sitions Zn–Ni alloy coating bath.
6.1.7. Polynitroaniline. The effect of polynitroani-
line deposition was investigated in Hall Cell bath with
the basic components of zinc sulfate, sodium sulfate,
CTAB and rough dark boric acid deposition. To
improve the deposition nature, polynitroaniline was
dissolved in ethyl alcohol and a certain amount of this
solution was added to the bath. The bright deposition
is developed between the current density of 10 and
30 mA/cm2. The deposit is dark at a lower density,
while it is burned at high current densities. With
increasing the concentration of polynitroaniline has
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
10 μm
Fig. 27. Corrosion rate obtained by measuring the weight
loss of electrodeposited zinc–nickel weight [157].
no effect on the deposition nature exceeding which a
darker deposit is achieved [46].
6.1.8. CTAB. In a study conducted in the single
sulfate bath, at low CTAB concentrations, the nature
of deposit is semi-bright. The burned deposit is
observed at the high concentration. By increasing the
1. There was a co-relation between
the ammonium chloride content
and appearance of plating layer
2. At lower concentrations than
150 g/L, bright deposit appeared
3. At content higher than 200 g/L,
NH4Cl could easily crystallized
NH4Cl
4. 1. The amount of deposited nickel
is increased up to 12.5 wt.% by increasing
NiCl2 in the electrolyte
2. At low concentration of NiCl2,
NiCl3
the smooth surface morphology is obtained
ZnCl2
1. The electrodeposition is anomalous at
the area above the concentration of ZnCl2
2. The electrodeposit surface morphology
is not significantly affected by the changes in
the concentration of ZnCl2 in the tested range
3. The high levels of ZnCl2 are selected to
increase the electrical conductivity of the bath
Fig. 28. The schematic of effect of compositions on Zn–Ni alloy coating electrodeposited.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
19
CTAB concentration, the burned area is reduced.
Exceeding this concentration, no change is observed
in the deposit nature. Thus, the concentration of
CTAB at 2 g/L is recorded as the optimum in the bath
solution [46]. Figure 29 presents summary of effect of
additives on Zn–Ni alloy coating bath.
6.2. Temperature
To optimize bright zinc–nickel alloy bath, tem-
perature plays an important role in the chemical com-
position and appearance of the deposition as other
zinc alloys (Co, Fe) [158]. Analysis of electrodeposi-
tion indicates that the black deposit is formed with
higher zinc ratio at a lower temperature and the bright
deposit is formed with higher nickel ratio at a higher
temperature. This product may be attributed to the
fact that at higher temperatures simpler deposition of
zinc causes fast filling of the cathode, leading to the
higher nickel content in the deposit [125].
Temperature is one of the important factors the
changes of which affecting the zinc–nickel alloy coat-
ing properties. The effect of temperature on coating is
studied while keeping constant the other electrodepo-
sition variables. Bath temperature changes the chemi-
cal composition (nickel content) of the deposits. It has
1. At lower concentrations, a bright 3. 1. Complexes with Ni2+
deposit was observed 2. Acting as a homogeneous catalyst, or
absorbs on the electrode surface
2. At higher concentrations there was
3. Perfect crystal growth, uniform
no appreciable change in the deposit arrangement of crystals, refinement
nature in crystal size and hence
bright deposit is obtained
4. Act as a buffer to maintain pH
of the electrolyte bath
ZnSO4
H3BO3
Effect of basic bath
composition
in Zn-Ni alloy
NaSO4
1. Increased the conductance of
the bath solution
2. The concentration of sodium sulfate
reaches 100 g/L,
the bright deposit provides
NiSO4
1. With increase in the concentration
the bright deposit was extended
2. With the increase in
the concentration of nickel sulfate,
the bright deposition was developed
20 LOTFI et al.

The composite film had

different phases and Smaller average size of
surface morphologies the crystallites than Smooth, uniform and fine-
when different the nanostructured Zn-Ni
concentrations of TEOS coatings prepared in grained,
and used in surface the presence of coumarin the surface structure included
coating industry the delta Ni3Zn22 phase
Tetraethylorthosilicate
(TEOS)

Benzyl triethanol
Coumarin ammonium
bromide
The deposition of bright
Zn-Ni alloy
Improving homogeneity Thiamine
and grain size hydrochloride Glycerol, gelatin
(THC) veratraldehyde,
p-amino benzoic
Additives of acid
electrolyte for
Zn-Ni
Polyetyleneglicol Electroplating
Grey, uniform, semi (PEG) + Vanillin
bright
obtaining more Saccharin
corrosion resistant

Triethanolamine,
CTAB, EDTA
diethanolamine Decreased
the residual stress level,
improved corrosion
Normal codeposition at resistance
low current densities, Decrease the effective
increasing Zn content metal ion concentration,
in the deposite bright, depositions
uncoated area was
reduced

Fig. 29. The schematic of effect of additives on Zn–Ni alloy coating electrodeposited.

been observed that nickel concentration, in the begin-
ning, is increased by raising the temperature and then
increases much faster with the high temperature. This
behavior is attributed to a decrease in cathodic polar-
ization and increased the kinetic parameters related to
temperature. Moreover, similar behaviors were
observed in the studies on zinc–nickel coatings for
electrical deposition and for pulsed and direct current
electrodeposition. The effect of temperature on sur-
face morphology revealed that for the deposits pro-
duced the smooth surface morphology is obtained and
the structure containing the γ-phase fine grain and
coarse crystals of η phase are confirmed. At high tem-
peratures, the deposition included α phase with mir-
rored morphology. In addition, the structure includes
a relatively high number of micro-cracks that are a sign
of the highly bright deposit. XRD pattern line width
analysis for this deposit indicates that the structure is
either the nanocrystalline (almost 2 nm according to
Scherrer formula) or amorphous. It should be noted
that the transfer from nanocrystalline to amorphous in
electrodeposited alloys is not understandable now and
X-ray diffraction and electron tests are not suitable to
determine the structure from peak widths diffraction
with crystal size lower than 3 nm. However, the results
are in agreement with recent studies of Fratesi et al.
[159] who reported that the electrodeposition of
amorphous produced is similar to chemical compo-
sition using direct current electrodeposition. The
morphological changes observed in this study are due
to the changes in nickel concentration. The bath
temperature in direct current electrodeposition had
no effect on both the crystal structure and on zinc–
nickel deposit texture. Similar results have been
reported by Fellion et al. [130] for direct current elec-
trodeposition of zinc–nickel alloys with comparable
nickel values [82].
Figure 30 presents the effect of temperature on the
nickel content of the coating. It can be observed that
the nickel amount of coating increases by 5–10 wt %
by increasing the temperature. The higher nickel con-
tent with increasing temperature can be attributed to
cathodic polarization and temperature dependence of
kinetic parameters. The observations presented some
small holes on the surface of the electrodeposition at
high temperatures due to the release of hydrogen gas
that is not eliminated. Making holes could be due to
the fact that higher temperatures activate hydrogen
release at low polarizations. Therefore, more nickel is
presented compared to the lower temperature and a
better surface quality is achieved compared to the
higher temperature [160].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 ZINC–NICKEL ALLOY ELECTRODEPOSITION 21

10 Nidep (%)
c
9

8 20 60°C
% Ni

7
50°C
6 15

L
Ni2+/Zn2+ ratio = 1

CR
5 j = 50 mA/cm2
R = 600 rpm
4 40°C
20 40 60 10
Temperature, °C

Fig. 30. The effect of temperature on nickel content in the

electrodeposition of zinc–nickel alloy [160]. 5

The temperature effect on zinc–nickel alloy coat-

ing of chloride bath can be seen in Fig. 31. As the fig-
ure suggests, nickel percentage in the deposit at con-
stant current density increases by raising the tempera-
ture at varying amounts of nickel content in the bath.
This observation implies the importance of the effect
of temperature on the kinetic parameters [130].
The effect of temperature is observed in corrosion
resistance properties of the zinc–nickel coatings
obtained from sulfate bath. Deposition is performed at
different temperatures. Figure 32 presents the result-
ing polarization curves at different temperatures. As
the results show, by increasing the temperature, corro-
sion current density and corrosion rate decreases, cor-
rosion potential becomes nobler, and corrosion resis-
tance increases. Since by increasing the temperature
nickel content of the deposit is increased, the increase
in the amount of corrosion resistance is related to
nickel increase in the deposit [161]. In order to pro-
duce zinc–nickel alloy film and the chloride bath, the
compound with zinc and nickel chloride was used. In
this study, the effect of temperature on the alloy coat-
ing deposition is investigated. Figure 33 illustrates the
effect of temperature on the concentration and depo-
10 20 30 Nisol (%)
Fig. 31. Effect of temperature on nickel concentration in
zinc–nickel alloy coating deposited in the bath with vary-
ing nickel percentage and 10 mA/cm2 current density
[130].
At lower pH between 2 and 2.5, the Hall cell pat-
tern presented burned deposition within the high cur-
rent density and presented uncoated area at low current
density. Guaranteed results were obtained at pH 3 and
the specimens were without burned and uncoated
areas. By increasing the pH to above 4, the deposition
becomes dull and dark. In these observations pH is
kept constant at 3 in the bath solution [46].
–2.0
–2.5
–3.0
logi, A cm–2

sition rate of zinc–nickel films. In order to evaluate

the effect of deposition temperature on the corrosion –3.5
resistance of zinc–nickel deposits, polarization test –4.0
was performed [162]. –4.5 25°C
30°C
35°C
–5.0 40°C
6.3. pH –5.5
50°C

In a study conducted on deposition bath of zinc– –1050 –1000 –950 –900 –850 –800 –750
nickel alloy, the pH was adjusted within the range of E vs. Ag/AgCl/mV
2–5. At lower pH, the deposit was semi-bright and
with a slight increase in pH, it is formed as a powder
Fig. 32. Polarization curves for the steel plated in sulfate
after electrodeposition. It was observed that the bath including ZnSO4, NiSO4, H2SO4, Na2SO4, and
appearance and concentration of nickel did not H3BO3 at 10 mA/cm2 the current density for 10 minutes at
change significantly with the pH variations [125]. different temperatures [161].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

22
120
Deposition rate, mg h–1 Deposition Rate
110
Ni Component
100
90
80
70
60
293 303 313 323
Temperature, K
Fig. 33. The effect of temperature on composition and
deposition rate of zinc–nickel film in bath chloride with
pH 6, the current density of 20 mA/cm2 deposition time of
the 1800 s [162].
6.4. Current Density
Hall cell tests were investigated for 5 min by opti-
mized bath solution. The bright area is reduced and
the high current density area is coated with burned
deposition. It is concluded from these observations
that the optimized bath produces bright deposit within
the current density of 3–40 mA/cm2 [46].
To optimize zinc nickel alloy bath for better corro-
sion resistance, the effect of current density is evalu-
ated. Zinc–nickel alloys (with a different composi-
tion) formed on the Hall cell panel showed that the
cathode current density plays an important role in sed-
iment properties. The deposit range was from semi-
bright to bright and then porous bright within the cur-
rent density range of 20–80 mA/cm2. Zinc–nickel
alloy coatings were investigated at different current
densities and in different physical tests. The effect of
current density on nickel wt %, hardness, thickness
and resistance to corrosion are were investigated. Cor-
rosion data show that the corrosion current density
decreases with the increased corrosion protection
[125]. It is observed that nickel wt % increases in the
current density. Since at high current density zinc
metal deposition occurs more easily on the surface of
the cathode, an anomalous behavior of electrodeposi-
tion is noticed in Zn–M (the Fe and M = Ni, Co)
alloys. However, the nickel wt % increases at low cur-
rent density probably due to less hydrogen which pre-
vents the effects of high alkaline (hydroxide saturated
mechanisms). The hardness of zinc–nickel coatings
changes within different current densities. It is con-
cluded that the hardness of the coatings is reduced by
increasing the cathodic current. The reduced hardness
is related to the metal hydroxide obstacle in the crystal
lattice due to the excessive release of hydrogen during
electrodeposition. Thus, through thick deposit formed
at high current density, porosities with less hardness
are reported. Thus, the coatings at a high current den-
sity become bright shiny deposits. The effect of cath-
LOTFI et al.
20 20 96
18
18.9
Ni component, %
16 93.3 wt % Nickel
14 wt % Zinc
91.6
16 92
12 15.4
10 88.9
wt % Nickel
wt % Zinc
8
6 12 88
4 11.1
84.6
333
8 8.4 84
wt % Nickel
6.7 wt % Zinc
81.1
4 80
5 10 15 20 25 30 35
Deposition current density, mA cm–2
Fig. 34. Nickel concentration and zinc in coatings based
on deposition current density [165].
ode current density on the coating thickness is linear.
Linear dependence of thickness on the current density
might be due to metal hydroxide absorbed in the cath-
ode (induced by the constant increase in pH due to the
release of hydrogen gas). Zinc–nickel alloy coatings
adhesion was also investigated at different current
densities and found that all coating, except those at
high current density, have high adhesion to the
smooth cut edges and no part of the deposit is isolated
from the substrate, implying that the coatings have
excellent adhesion [163, 164].
Figure 34 presents the effect of current densities on
the electrodeposition of zinc–nickel in sulfate bath.
This figure presents atomic absorption spectroscopy as
weight percentage. With increasing current density, the
weight percentage of nickel concentration increases up to
7–19 wt %. The average grain size decreases with
increasing current density. Dislocation density and
microstrain increased by reducing the grain size. By
increasing the current density to 30 mA/cm2 corrosion
resistance improved [165].
The effect of electrodeposition of current density in
an acid-sulfate bath on nickel content at 40°C is pre-
sented in Fig. 35. As shown in the figure, the nickel
content is almost doubled by increasing the current
density range. Increasing nickel concentration in the
coating is associated with the hydrogen prevention in
the anomalous deposition mechanism of zinc–nickel
coatings. Based on this mechanism, the activity of
nickel (less noble ion) in the bath is reduced by the for-
mation of a stable complex [160]. The effect of depo-
sition current density on the topography of the depos-
ited coatings obtained in Kelvin probe alkaline sulfate
bath is presented in Fig. 36. It is observed that the
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
 ZINC–NICKEL ALLOY ELECTRODEPOSITION 23

11 ages. Under the investigated working conditions, it is

d observed that by increasing nickel content the deposi-
10 tion is decreased at a constant current density of the
nickel bath [130]. Furthermore, in another study, dif-
9 ferent zinc–nickel concentrations were observed in
chloride bath (Fig. 37). The reduced nickel percentage
8
was also observed in this study [166].
% Ni

6 6.5. Pulse Current

Ni2+/Zn2+ ratio = 1
T = 40°C
5 applications improve pulsed electrodeposition includ-
R = 600 rpm
4
40 60 80
Current density, mA/cm2
Fig. 35. The effect of deposition current density on the
nickel content of zinc–nickel alloy coating [160].
coatings obtained by the current densities have a more
uniform surface than the coatings obtained at current
densities [39].
Deposition current density was used for the depo-
sition of zinc–nickel alloy coating in the chloride bath.
The effect of current density on the percentage of
nickel in the zinc–nickel alloy electric deposition of
the bath was investigated for different nickel percent-
It is well known that pulsed electrodeposition
ing flat depositions with reduced porosity, the better
100 flexibility, hardness and controlled deposition. It is
constantly attempted to find the pulse electrodeposi-
tion parameters leading to the formation of zinc–
nickel alloy coating with the best corrosion properties.
Three variables can be changed in pulse electrodepo-
sition, in contrast with a single variable (current den-
sity) that is changed in direct current electrodeposi-
tion. These variables are pulse current density (jp),
pulse time (Ton), and off time (Toff) [26, 167]. Pulsed
electrodeposition has obtained significant progress
with several electrodeposition variables and a larger
peak of current density compared to direct current
electrodeposition over the last 20 years and reached
the right direction to provide the materials [168].
Phase structure of the alloy with anodic linear sweep
voltammetry is investigated in a solution containing

0
(a) 0
10
(b) 0
5
(c) 5
20 10 10
μm

μm

μm

30 15 15
40 20 20

30 15 15
20 10 10
10 5 5
200 200 200
0 0
μm

100 0
μm
100
μm

200 200 100 200 100

μm 100 0 μm 100 μm
0 0

0 0
10
(d) 5 (e) 20
10
μm

15 30
μm

20 40

15 30
10 20
5 10
200 200
0 0
μm

100
μm

200 200 100

μm 100 0 μm 100 0

Fig. 36. The topography images generated by Kelvin probe for the coated depositions at the current densities (a) 20, (b) 30, (c) 40,
(d) 40, and (e) 60 mA/cm2 [39].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

24
25 Ni/Zn = 0.5
Ni/Zn = 1.5
20
Ni, %
15
10
0 10 20 30 40
i, mA/cm2
Fig. 37. Nickel percentage in the deposit as a function of
current density at different concentrations [166].
complex agents. Anodic linear sweep voltammetry is a
convenient electrochemical method for detecting the
alloy phase structure. Two dissolution peaks are
observed in the anodic linear sweep voltammetry that
shows the presence of two different phase structure. In
all tested cases the current peak related to less noble
potential peak is more than other current peaks and
charging from this peak to another one is higher. The
increased stop to pulse ratio shift the potential to less
noble amounts. Compared with direct current electro-
deposition, pulse electrodeposition can improve the
deposition process and some properties such as poros-
ity, ductility, hardness and surface roughness. For
alloy codeposition, the pulse electrodeposition can
produce the structures that are not possible to be pro-
duced by direct current electrodeposition [26]. For
most systems, electrodeposition speed that is deter-
mined by current density and current efficiency in
pulsed electrodeposition is usually higher than direct
current electrodeposition. Although a large number of
works has investigated zinc–nickel alloys electrodepo-
sition, less attention has been paid to pulse electrode-
position of these materials [82].
6.5.1. Ton. The effect of on time on microstructural
characteristics of deposition is studied. This tempera-
ture is set for the best alloy compound with the best
corrosion resistance (12–14 wt % Ni) obtained a this
temperature. It is observed that Ton in the tested range
has a slight effect on the composition and nickel con-
tent is around 12–14 wt %. Also, the previous studies
conducted by Knodler et al. [169] on the effect of Ton
on the chemical composition of the Zn-Ni alloy deposi-
tion indicate that nickel content is highly dependent on
Ton. The present results suggest that Ton has a special
effect on the surface morphology of the deposits such
that all deposits had fine grain. The deposit produced at
Ton 75 ms indicates the normal morphology of deposits
for the range of Ton. X-ray diffraction patterns only indi-
cate the presence of γ phase for all deposits with preferred
orientation (330) and (411) [82].
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
LOTFI et al.
80
Ton/ms
70
100
60 10
50 1
j, mA cm–2
40 0.1
DC
30
20
10
0
–10
–0.9–0.8–0.7–0.6–0.5–0.4–0.3–0.2–0.1 0 0.1
E/V vs. SCE
Fig. 38. The linear sweep voltammetry curves in Na2SO4 +
EDTA solution, dissolution of zinc–nickel alloys in direct
current, and pulsed current with Toff : Ton = 1 at different
values of Ton [26].
In a study, chloride bath is used to deposit the
zinc–nickel alloy, using pulsed current and square
wave cathode pulses. Pulsed deposition time as the
alloy chemical composition resulting in constant cur-
rent density is presented in Fig. 38, where the nickel
content is analyzed within the time, Ton. The increased
ratio of stop to pulse results in reduced amount of
nickel in the alloy; however, all zinc–nickel alloys
require nickel concentration of 10–15 wt % to have a
good corrosion protection [26].
6.5.2. Toff. Similar to Ton, Toff has little impact on
nickel concentration deposition. The surface mor-
phology resulting from Toff values did not present a
considerable difference; however, grain refinement is
slightly increased when Toff is increased. Possibility,
the Ton is increased as a result of a small increase in
nickel concentration. X-ray diffraction patterns indi-
cate a change in the context based on Toff. The results
show that all the deposition produced at different Toff
values have various γ structures. At the relatively low
Toff, the deposit had a strong preferred orientation
(330), (411). With increased levels of Toff, peak inten-
sities (600) and (422) were increased [82].
6.5.3. Toff/Ton ratio. The Toff/Ton ratios were ana-
lyzed over similar cathodes for all deposits. A potential
shift to less noble values is consistent with the observa-
tion on the nickel content dependency of Toff/Ton ratio
which indicates that by increasing the amount of
Toff/Ton nickel content is reduced in the alloy. Since it
is assumed that the higher values of nobler nickel in
the deposit presents nobler dissolution potential, it is
concluded that by increasing Toff/Ton the nickel con-
tent is reduced and the current peaks in anode linear
sweep voltammetry curves shift to more negative val-
ues. The corrosion results show that the nickel content
of the alloy is not the only factor responsible for corro-
sion protection since nickel concentration in deposits
in this analysis is mostly the result of direct current
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
electrodeposition; however, the deposits had a lower
corrosion resistance. Different surface morphologies
obtained by different deposition parameters affect
corrosion deposition characteristics. Since the rough-
ness of the deposit increases with Ton, it can be con-
cluded that among all explored deposits in this study,
the deposit obtained by Ton = 1 ms and Toff/Ton of
1 presents the best result [26].
6.5.4. Pulse current density. In another study, to
examine the characteristics of pulsed electrodeposi-
tion, the chloride bath was used and the pulse param-
eters were studied. To study the effect of peak current
density (iP) on the deposit microstructure, the current
density was changed within the range of 10 to 30 mA/cm2
by setting the current average density and keeping Ton
and Toff constant. The increase in ip changes the Ni
between 12 and 14 wt %. Based on the results of
Knodler et al. [169] the nickel content of deposits has
higher or lower dependence on the current density
peak versus the higher zinc content in the bath. How-
ever, they proved that in the bath with 2 and 5 g/dm3
zinc the increased nickel content occurs with the
increased current density peak. Based on the SEM
images, as ip increases a substantially modified grain is
observed. This behavior is confirmed by the report of
other deposited metals. Grain size reduction is the
result of higher additional potential and the establish-
ment of nucleation. Also, the higher ip increases the
electric strength of deposit of nickel-molybdenum
alloy. X-ray diffraction patterns of zinc–nickel alloy
deposition obtained indicate that the crystalline struc-
ture of all deposits is the single γ phase. The XRD
results show that the preferred orientation is (330) and
(411). It should be noted that the copper peak in a
spectrum (in ip 10 mA/cm2) appears in the copper sub-
strate partially in scanning X-ray diffraction [82].
The effect of pulsed reverse current density on the
zinc–nickel alloy coating is analyzed by marking the
specimens as A, B, C, D, and E with respectively
pulsed reverse current densities of 0–100 mA/cm2 in a
chloride bath. The substrate is made of copper.
Impedance spectroscopy curves of Fig. 39 presents the
corrosion behavior of the coating. As shown in this fig-
ure, the specimen A has weaker corrosion resistance
compared to other specimens [170]. The effect of var-
ious parameters for electrodeposition of Zn–Ni alloy
coating presents in Fig. 40.
7. MULTILAYER ZINC–NICKEL
ALLOY COATINGS
Production and properties of several layers made of
zinc and iron have many interesting aspects, but there
is limited information for them [171, 172]. The electro-
deposition method of manufacturing the Z–M multi-
layer coatings with the combined setting (the M Met-
als such as iron Ni, Co, and Fe), has obtained the
highest attention in surface engineering because of
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
25
120
110
100
W
90
–Im Z (Ω cm2)
80
b
70
60
50 d
a
40
30 c
20
10
0
20 40 60 80 100 120
Re Z (Ω cm2)
Fig. 39. Nyquist curve of zinc–nickel alloy coating soaked
in NaCl solution of 3.5% for 24 h [170].
their good corrosion resistance [173]. Manufacturing
multilayer coating of zinc to protect the iron substrates
against corrosion is progressed significantly. In multi-
layer coatings, each layer has its own role and the type
and form of the layers are designed based on a number
of goals. Multiple coating systems including zinc and
other elements such as Zn–Co, Zn–Mn, Zn–Fe, and
Zn–Ni are recently developed to protect against cor-
rosion of metal substrates [174].
In zinc multilayer coatings such as the multilayer
zinc–nickel coatings, the noble layer of nickel has a
protection against the aggressive ions and the zinc
layer protects the substrate against the corrosion the
damaged areas in the coating [174]. Kalantary et al.
[175, 176] and Chawa et al. [177], have deposited mul-
tilayer zinc–nickel coatings from pure zinc, sulfate,
and nickel sulfamate electrolytes and measured their
corrosion resistance. The improvement in the corro-
sion properties of multilayered coatings appears versus
pure zinc coatings [171, 173, 178, 179]. In addition, ini-
tial electrochemical evaluation by salt spray indicates a
good improvement by multilayered zinc–nickel coat-
ings compared to the single-layer zinc–nickel coating
with the same thickness [172, 180].
7.1. Zn–Ni Multilayer Coating Microstructure
Multilayer coatings are manufactured by a number
of coating techniques such as electrodeposition, elec-
troless deposition, physical vapor deposition (PVD),
chemical vapor deposition (CVD), etc. [181]. Among
the methods for producing multilayer coatings, the
electrodeposition method has advantages over the rest
of them. This method can be deposited in a wide area
of substrate at low prices [182]. Due to lack of neces-
26 LOTFI et al.

Compact morphology, single
phase and no-crack could
be obtained at 30–40°C
The decrease in
The weight percentage the pH results in
The nickel content increases slowly of nickel in the deposit increased corrosion
until the temperature reaches 50°C increases with increasing resistance
pH at values up to 5.5

Enhances the hydrogen

The potential of cathode evolution with
increase sharply at 60°C and pH decrease pH
the current efficiency Temperature 1.5–14
decreases when temperature 25–140°C
is higher 40°C

Pulse plated has an Effect on morphology

increased nickel and crack on coating
content in the The effect of
deposit the bath parameters
on Zn-Ni coatings
The lower
the current density,
Shifted the more compact
the polarization curve the morphology of
the coating
to positive potential

Current density The thickness of

Pulse (Ton, Toff, Effect 4–80 mA/cm2 the deposit was found
Refined nodular grains of current a pulse ratio) The developed bath
gamma phase and produces good deposit to increase with increasing
increased nickel contents over the current density the current density
are obtained from
the reverse-pulse range of 4–35 mA/cm2
processing The increase in
Increasing the current
gamma phase density results
with increasing in increased Ni
Best corrosion current density content
resistant obtained
with pulse technique

Fig. 40. The parameters of electrodeposition of Zn–Ni alloy coating.

sary to powerful vacuum system and its related costs,
formation of nanoscale multilayer systems by electro-
deposition method to be more interesting than PVD
and CVD procedures. Through this method, it is pos-
sible to deposit smoother layers as every other one;
deposition of layer occurs at room temperature, there-
fore the possibility of diffusion between the layers is
severely reduced. The layer thickness can be con-
10 μm
Fig. 41. Cross-section image of zinc–nickel multi-layer
coating with 12 layers [184].
trolled by the amount of charge transferred, it has the
ability of deposition of layers with complicated forms,
the combination, and chemical defect is controlled by
controlling the over potential. Although unstable
phases can be also deposited, using one bath it is pos-
sible to deposit several alloys and crystalline layers are
created with minimal defects. The disadvantages of
this method are that the substrate and film should be
electrically conductive and there is the possibility of
film contamination by the solution. The dual bath tech-
nique and single bath technique are two main ways to
produce multilayered electrodeposition [99, 173].
Figure 41 presents the zinc–nickel multilayer coat-
ing. Cross section morphology of zinc–nickel multi-
layer coating with 12 layers with the single layer thick-
ness of 3 μm presents a flake-like crystalline structure.
In this regard, the grain size becomes smaller by
increasing the number of layers. It is observed that as
the layers become thinner the grain size becomes more
appropriate.
Figure 42 presents a cross-section of zinc–nickel
coating with 11 substrates where the final layer is
nickel. The sample of cracks between the layers is
associated with the preparation of the cross-section
using mechanical methods [171].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 ZINC–NICKEL ALLOY ELECTRODEPOSITION 27

Also, in Fig. 43 the image of the cross section with

12 zinc–nickel alloy layer and the single nickel layer is
presented. This morphology presents a separate layer
structure that is etched in the dark borders due to the
removal of the zinc–nickel layer by vital solution and
presents the transparent border of nickel layers [183].

7.2. The Properties of zinc–nickel Multilayer Coating

Corrosion resistance performance of the compos-
ite multilayer coated samples of zinc and zinc–nickel
is analyzed by salt spray test. The results of salt spray
test are presented in Fig. 44. Red rust corrosion prod- 10 μm
ucts are seen on the steel surface after four h. The first
rust appears on zinc and zinc–nickel alloy coated steel Fig. 42. The cross section image of zinc–nickel multilayer
plane at 48 and 288 h, respectively. All multilayered coating [171].
zinc and zinc–nickel alloy coatings have a longer
destruction time than the single layered coatings with
the same thickness (12 μm). However, the steel sub-
strates coated by Zn–Ni/Zn multilayered coating
presents a longer time than the multilayer Zn/Zn–Ni
coating [29].
In another study, salt spray test was conducted on
several layers of zinc–nickel. On the mild steel surface
without coating, the first rusts appeared after 4 h. For
zinc and nickel, the rusts appeared after 24 and 48 h.
Multilayer zinc–nickel coatings with zinc coating on
nickel presented longer period than the nickel on zinc.
The morphologies of zinc single layers, nickel depos-
its, and zinc–nickel multilayer coatings after the cor-
rosion test indicate that the solution of pure zinc coat-
10 μm
ing is done completely and little amount of zinc
remains. Ni deposition is corroded from zinc by differ-
ent ways. Local restoring corrosion appears in the Fig. 43. Cross-section morphology of the zinc–nickel
places that have the possibility of porosity in nickel multilayer coating with 12 layers [183].
deposits and penetrates to the mild steel sublayer when
the deposits are in contact with active ions. Polariza- 1000
tion curves of multilayers zinc–nickel coating with 1 Zn12 5 Zn12
nickel on zinc showed that the corrosion potential of 2 Zn–Ni12 6 Zn–Ni3/Zn3
800
the multilayers is more negative than the nickel single- 3 Zn3/Zn–Ni3 7 Zn–Ni2/Zn2
Time to red rusl/h

layer and it is close to zinc layer. A sharp increase in 4 Zn2/Zn–Ni 8 Zn–Ni/Zn1

current in the early stages is due to the solution of zinc 600
through higher nickel layer porosity because the
potential is more negative than the nickel layer or 400
nickel deposited specimens. The increase in current in
positive potential is attributed to the dissolution of 200
mild steel substrates because no oxygen release is
detected at this stage. The schematic of corrosion
mechanism for multilayer Zn–Ni coatings during the 0
corrosion process is presented in Fig. 45. Figures 45a, 1 2 3 4 5 6 7 8
45b present the multilayer coating structure binary of Fig. 44. Corrosion resistance of Zn/Ni, Zn–Ni multilayer
Ni/Zn with different thicknesses. First, the upper zinc coatings with different structures [29].
layer is corroded completely that cause a peak in the
anodic polarization curve then the bottom layers of zinc
are dissolved by nickel layer porosities. Figures 45c, 45d coatings that have zinc layer as the upper layer have
present the structure of Zn/Ni multilayer coating with better corrosion resistance than the multilayered coat-
different thicknesses. The zinc layer under the top zinc ings with Ni layer as the toplayer. The better corrosion
layer is dissolved by the porosities in the nickel depos- resistance of the zinc top layer is attributed to the pores
its during the corrosion process. It is observed that the and microcracks in nickel layer [184].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

28 LOTFI et al.

Time to first red rust, hr

(a) 1200
Ni/Zn–Ni(6L)
Zn Ni/Zn–Ni(4L)
Ni
1000
Zn–Ni/Ni(6L)
Zn Zn–Ni/Ni(4L) Ni/Zn–Ni(2L)
Ni
800 Zn–Ni/Ni(2L) Ni/Zn–Ni(12L)
Fe Zn–Ni
600
Zn–Ni/Ni(12L)
(b) 400
Zn
Ni
Zn 200
Ni Ni
Zn
Ni 0
Fe
CMM coatings
(c)
Ni Fig. 46. Effect of number and arrangement of layers on
Zn corrosion resistance of multilayer coatings [183].
Ni
Zn
Fe
netic properties than conventional alloys. Zinc–nickel
(d) multilayer coatings are among the zinc coatings that
Ni
Zn are addressed in many studies for its good corrosion
Ni
Zn
Ni
protection performance on the steel substrates [178].
Zn
Fe
The results of corrosion studies present the most satis-
factory performance of zinc–nickel multilayer coat-
ings compared to a single layer of zinc with similar
thickness [174, 179, 186].
Fig. 45. The potential corrosion mechanisms for Ni/Zn
and Zn/Ni coatings [184].
8. ZINC–NICKEL COMPOSITE COATINGS
In recent years, composite coatings have attracted
Among the factors affecting the multilayer are substantial attention because of having chemical and
coating properties, the chemical composition of the mechanical properties together. Composite coatings
layer, number of layers, their arrangement, and thick- have special specifications such as high hardness, self-
ness. Figure 46 presents the results of salt spray on the lubricating, high-temperature oxidation resistance,
multilayer coating with the mentioned changes. As it excellent coverage, and corrosion resistance [187].
can be observed, the coating with 6 layers and Ni/Zn– The electrodeposition method is widely used for the
Ni arrangement has the highest corrosion resistance. preparation of composite metal matrix coatings
In comparison, the coating with top nickel layer has because of the low adaptation cost. Generally, hard
lower corrosion resistance due to porosity and defects oxide or carbide particles such as Al2O3, TiO2, ZrO2,
than the zinc–nickel alloy coating [183]. SiO2, Fe2O3, SiC, and WC or even diamond and car-
Improved corrosion resistance of the coatings is bon nanotube are used as the second phase [17, 188–
caused by multilayer coating because of the changes in
the electrical properties of the change in intrinsic elec-
tric value and the binary electric level and the micro 7E + 008 Linear regression for Zn–Ni CMM
and nanometric layer. Detecting the semiconductor Y=A+B*X
surface layer which improves the corrosion resistance Parameter Value Error

is confirmed in Mott-Schottky and polarization 6E + 008 A 6.77471E9 1.67193E8

B 5.44643E9 1.43486E8
curves. Detecting multilayer deposition and corrosion
(1/C2)/F–2

R SD N P
reduction mechanism by SEM also confirms this 5E + 008 0.99792 9.29894E6 8 <0.0001
issue. Figure 47 presents the Mott-Schottky curve of
the improved multilayered coating (Zn–Ni). The
straight line indicates the protective semiconductor 4E + 008
layer of n-type [185]. The properties and structure of
several Zn–Ni multilayer alloy coating are presented 3E + 008
in Table 3.
2E + 008
–1.20 –1.18 –1.16 –1.14 –1.12
7.3. Zinc–nickel Multilayer Coating Applications Voltage, V vs. Ag, AgCl/KClsat
The multilayer coatings are the coatings with two or
more component layers. These coatings have better Fig. 47. The mott-Schottky curve for (Zn–Ni)2.0/4.0/
corrosion resistance, physical, mechanical and mag- 300 multilayer coating [185].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 Table 3. Summary of results of research conducted on zinc–nickel multilayer coating

Current
Tempera- Negative Number icorr, Ecorr, Thickness, Hardness,
Composition density, Refrence
ture, °C potentials, V layers μA/cm2 mV vs. SCE μm HV
mA/cm2

ZnCl2–NiCl2–H3BO3–NH4Cl N.R. N.R. –1.5...–0.85 4 2.4–140 –700 to –1000 12 134–184 [128]

ZnSO4–H3BO3–NiSO4–NiCl2–(NH4)2SO4 25–50 30 –1.25...–0.75 5–12 N.R. –800 to –1400 0.7–6 N.R. [214]

ZnSO4–NiSO4–Na2SO4 60 50 N.R. 4–12 10–100 800 to –1009 12 N.R. [29]

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

ZnSO4–Na2SO4–H3BO3–NiSO4–NH4Cl 20–30 30–105 –1.3 2–8 N.R. –1000 to –1250 9 N.R. [215]
ZINC–NICKEL ALLOY ELECTRODEPOSITION

ZnO–NiSO4–NaOH-triethanolamine 10–40 20–100 N.R. 6 N.R. N.R. 8–30 N.R. [216]

ZnSO4 –Al2(SO4)–H3BO3–NiSO4-tri-ammonium citrate- 20–30 35–55 N.R. 4–12 N.R. –566 to –1049 12 N.R. [217]
55–65 10–20

* N.R. = Not reported.

29
30
10 000
Zn–NI
Background
Background
Zn–Ni–Al2O3
Al intensity/counts per sec
1000
100
10
1 cracks. In addition, zinc–nickel alloy presents a non-
0 50 100 150
Time, s
Fig. 48. LA-ICP-MS Aluminum results for the nickel-alu-
mina deposited the coating. The zinc–nickel alloy results
are presented for comparison. The deposition current den-
sity 80 mA/cm2, T = 80°C and pH 2 for 10 min [188].
190]. Zinc–nickel composite coating including Zn-
Ni–Al2O3 [191], Zn–Ni–TiO2 [192], Zn–Ni–SiO2
[193, 194], Zn–Ni–CNT [195], Zn–Ni–SiC [196],
and Zn–Ni–Fe2O3 [17] are synthesized by adding
micro/nano- ceramic particles to the electrodeposi-
tion solution as a suspension during the electrodeposi-
tion that the suspension allows the particles to be
added to the coating matrix. However, the proper
nano- or micro-suspension of particles to obtain the
wider surface area of the particles has been always dif-
ficult. The high surface energy of nanoparticles causes
nano- or microparticles agglomeration of the compos-
ite coatingsn. Nevertheless, the agglomeration might
be reduced by simulation, air injection, or ultrasonic
vibration. As the result of agglomeration, the effective
unification and uniform distribution of the nanoparti-
cles will not be achieved [190].
8.1. Zinc–nickel Composite Coatings Microstructure
Study on the structure of the zinc–nickel compos-
ite coatings is conducted considering the importance
and application of these coatings. Zinc–nickel with
alumina particles is one of the composite coatings of
zinc–nickel alloys. X-ray diffraction is used to study
the phase structure of coating for both deposited coat-
ings under the same deposition parameters on the steel
substrate in acid sulfate bath. It can be seen that all
deposits had single-phase structure γ-Ni5Zn21.
According to X-ray fluorescence results, the nickel
content of the alloy coating and composite are 10.9
and 11.5 wt %, respectively. Zn–Ni γ phase can be
present in various compounds (Ni 10–14 wt %). Alloy
and composite coating thickness and deposition cur-
rent efficiency are ~12–15 μm and ~61.5%, respec-
tively. No Al2O3 peak appeared in the fluorescence
analysis of X-ray diffraction of the composite coating
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
LOTFI et al.
due to the small size of the particle and the relatively low
amount that is under the X-ray fluorescence detection.
Figure 48 presents the Laser Ablation Inductively Cou-
pled Plasma Mass Spectrometry (LA-ICP-MS) of alu-
minum for the composite coating and zinc–nickel coat-
ing for comparison. Test results show the incorporation
of alumina in the coating. It is also clear that there is no
aluminum in zinc–nickel alloy coating [188].
The morphologies of zinc–nickel and zinc–nickel
with alumina alloy coated surface were analyzed and
observed that the compressed coatings can appear for
both alloy and composite samples without surface
200 uniform surface with fine ridge as the matrix with a
developed ridge in the substrate. However, the com-
posite coating is pressed and uniform with fine grain
morphology. Thus, the presence of alumina in the
electrodeposition bath and adding alumina to zinc–
nickel coating increases the crystal size modification
[188]. In addition, in the earlier studies, these authors
confirmed the presence of alumina nanoparticles in
the zinc–nickel matrix with SEM and diffraction pat-
tern for the composite coating. The grain size is calcu-
lated based on Scherrer linear equation that well deter-
mined the crystal diameter as less than 100 nm, which
was is widely used for zinc–nickel deposition. The
grain size D is calculated by the width of the highest
peak by Scherrer equation as D = 0.9λ/βcosθ than λ is
the wavelength (0.154 nm), β is the total width of the
maximum half peak, and θ is the peak position. The
crystal size of the whole coatings is in nanometer (nm)
that confirms the crystalline structure of the coatings.
Zn–Ni–alumina alloy coating has smaller grain size
than a zinc–nickel coating. The average crystal sizes of
30 ± 0.2 nm and 19 ± 0.2 nm are determined for alloy
and composite coatings. The grain size is one of the
factors determining the mechanical properties of the
coating. Basically, the coating hardness depends on its
grain size. This relationship is known as Hall-Petch
relationship which states the coating hardness
increases with the increase in the size of smaller grains.
The finer grains in zinc–nickel-alumina composite
coating are due to nucleation of smaller grains that
prevent the dislocation and increase the microhard-
ness, which is presented in the studies conducted by
the same researchers [11].
In a research conducted by Praveen et al. [189] the
zinc–nickel–carbon nanotube were characterized.
Zinc–nickel matrix in composite coating had the
average crystal size 18 nm which is much smaller than
29 nm related to zinc–nickel alloy. Thus, it can be
concluded that reducing the grain size of zinc–
nickel–carbon nanotube composite coating is associ-
ated with adding carbon nanotubes to the electrode-
position bath that is provided by calculating the aver-
age grain size of the width of the diffraction peak by
Scherrer equation from X-ray diffraction pattern. The
presence of particles with nano size in the metal
deposits might alter the crystal structure of the metal
 ZINC–NICKEL ALLOY ELECTRODEPOSITION 31

(a) (b)

(a) 10 μm (b) 10 μm
1 μm ×5000 1 μm ×5000

Fig. 49. SEM images of the composite coating (a) and

alloy coating (b) [189].

(c) 10 μm (d) 10 μm
coating. Figures 49a, 49b represent the SEM images of
the specimens coated by composite and zinc–nickel,
respectively. The grain size of the composite-coated
specimen is almost uniform and smaller than that of
zinc–nickel alloy. The alloy coating presented the ran-
dom crystal and rod and sheet grains. These results
suggest that the carbon nanotubes are uniformly dis- 10 μm
(e)
tributed in the coating and provide more nucleation
places and the crystal growth is delayed due to the for-
mation of uniform grain size [189]. Fig. 50. SEM images of zinc, nickel, and alumina nanocom-
posite coating produced on different ultrasonic power [190].
Figure 50 presents the surface images of zinc,
nickel, and alumina nanocomposite coating under dif-
ferent ultrasonic conditions. The chloride bath con- shows different values that are the interface between
taining zinc and nickel chloride is used by adding deposit and substrate. Composite thickness is also
α-Al2O3 powder with the particle width of 100 nm for determined by this test [198].
electrodeposition. By comparing the images produced
without ultrasonic nanocomposite coating (Fig. 50a)
and the images produced under ultrasonic conditions 8.2. Zinc–Nickel Coating Composite Properties
(Figs. 50b–50e) it is clarified that the ultrasonic vibra-
tion leads to a higher distribution of alumina in the Figure 53 presents the impedance curve of pure
coating. Analyzing the alumina amount reveals that by zinc–nickel coating and zinc–nickel and alumina
increasing the ultrasonic power the amount of code-
posited alumina is increased from 4.5 to 9 wt % [190].
γ(330) (b)
For the composite coating of zinc–nickel with SiC
particles, the electrodeposition bath containing ZnO,
NiSO4, NaOH, and diethylnutramin were used. Fig-
ure 51 displays the XRD pattern related to zinc–nickel
alloy without SiC particles, where only γ phase of
zinc–nickel alloy was observed. When SiC is added to
Fe(211)
Fe(200)

the bath, no change is observed in the chemical com- Fe(110)

position of the phase. The difference is that in the

presence of SiC particles the orientation of crystal (a)
γ(222)
plates is changed (Fig. 51). The change in the context
is observed when SiC is added to the nickel coatings. γ(444)
In this case, the particles prevent the reduction of cur-
rent efficiency and change in context is related to the γ(330)
hydrogen absorption to atom pages [197].
γ(332)
The effect of the presence of SiO2 particles on the γ(552)
γ(600)
surface morphology of Zn–Ni composite coating is
presented in Fig. 52. Composite coating surface has 30 40 50 60 70 80 90
poled and smooth grains. Energy dispersive spectros- 2θ, deg
copy test of the composite coating surface presents the
silica. The weight percentage of the profile is the Fig. 51. X-ray diffraction chart for the coating obtained in
GDOES depth of selected elements of zinc, nickel, sil- 20 and 500 mA/cm2: (a) zinc–nickel alloys without SiC
icon, and iron to cover the zinc–nickel composite and (b) zinc–nickel composite with 8 wt % SiC [197].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

32 LOTFI et al.

(a) (b) (c)

Zn
Zn

Intensity, CPS
Ni

Ni
Zn
5 μm 5 μm O Si Fe
Ni

0 10
Energy, keV

Fig. 52. SEM and energy dispersive spectroscopy images of steel surface coated by zinc–nickel in 25 mA/cm2 for 15 min in the
electrodeposition bath: (a) zinc–nickel alloy coating (b) zinc–nickel alloy composite (with 5 g/L SiO2) [198].

composite coatings containing two rings with a larger
capacity ring at higher frequency and conductor rings
at a lower frequency. Nyquist curve values indicate
that the amounts of electrochemical parameters are
lower for the composite coating. Thus, by adding alu-
mina no certain impact is seen on the double layer
capacity at the interface between the electrode and the
electrolyte. Charge transfer resistance in the codepo-
sition of alumina was 50% lower than pure electrode-
position of pure zinc–nickel coating. In addition, hav-
ing a smaller ring diameter of the composite coating
indicated a higher corrosion resistance compared to
pure alloy coating [188].
The effect of composite particles on the micro-
hardness of the zinc–nickel composite coating with
SiO2 particles presents the increased hardness from
140 HV for the pure zinc–nickel alloy to 360 HV for
the specimens prepared by SiO2 particles. It can be
concluded with the addition of this type of nanoparti-
1.5
Zn–Ni Rs
Zn–Ni–Al2O3
Fit results
1.0
Zim, Ω cm2
cles to the deposit affects the microhardness. In fact,
crystals with a smaller size produce greater grain
boundaries that prevent the dislocation movement
and increase the material’s hardness. Electrochemical
impedance spectroscopy (EIS) for pure and compos-
ite zinc–nickel coatings after 24 h of immersion to
measure polarization resistance indicates that polar-
ization resistance (Rp) for zinc–nickel alloy coating is
lower than composite zinc–nickel alloy coating. As it
can be observed, the polarization resistance of the
composite coating is better than pure alloy. The
reduced corrosion severity is related to structural and
electronic properties of passive oxide [198].
In the study conducted by Praveen et al. [192], the
corrosion resistance properties of Zn–Ni–carbon
nanotube coatings were analyzed. The presence of
carbon nanotube provides a higher corrosion resis-
tance for Zn–Ni–carbon nanotube coatings. The
trend of anodic polarization of the composite speci-
mens coated in the optimized bath and Zn–Ni in the
base bath indicates that the composite potential is
shifted to more positive values in all current densities.
Rct
CPE The shifting indicates that Zn–Ni–carbon nanotube
L1 R1 composite has more satisfactory reducing power.
Thus, the corrosion behavior is improved. The results

1 kHz of Tafel extrapolation and Nyquist curve of the coat-

0.5 100 kHz 1 kHz
ings and their average circuit indicate that the zinc–
nickel composite coating has a lower corrosion rate
100 kHz
than pure zinc–nickel film. In addition, carbon nano-
0.1 Hz 0.1 Hz
0 tubes in the deposition process of the zinc–nickel
alloy increase corrosion resistance. Basically, the
metal surface includes possible defects, cracks, gaps,
5.0 5.5 6.0 6.5 7.0 7.5 8.0 grooves, and pores that are usually higher than micron
Zre, Ω cm2 size. It can be observed that the nanoparticles easily
fill these defects. Most of the micron pores are active
sites for metal dissolution during corrosion. Naturally,
Fig. 53. Nyquist test curve and simulated impedance curve these cavities are covered by the carbon nanotubes of
for zinc–nickel alloy deposition and zinc–nickel and alumina
composite on killed steel in the bath solution E = –1.5 V, T = the composite film and reduce corrosion rate in the
40°C and pH 2 [188]. method of weight loss [64].

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

 ZINC–NICKEL ALLOY ELECTRODEPOSITION
Polarization potentiodynamic test was performed
on zinc–nickel coated steel obtained by the bath con-
taining additives and TiO2 nanoparticles at different
concentrations. TiO2 nanoparticles (21 nm) were
added to the electrodeposition bath to obtain a com-
posite coating with different concentrations. As it can
be observed, adding polyethyleneglicol (PEG) and
vanillin to the electrodeposition bath has reduced cor-
rosion current density compared to the zinc–nickel
coating without the additive. Furthermore, the addi-
tion of TiO2 reduces corrosion current density com-
pared with pure zinc–nickel coating [199].
8.3. Zinc–nickel Composite Coating Applications
In order to develop the application of coatings,
metal matrix composite coatings are recently devel-
oped to improve the chemical and mechanical proper-
ties. Composite coatings have various properties such
as uniform hardness, self-lubricating, high-tempera-
ture oxidation resistance, excellent coverage, and cor-
rosion resistance [187]. Generally, oxide and carbide
components such as Al2O3, TiO2, ZrO2, SiO2, Fe2O3,
SiC, and WC or even diamond and carbon nanotube
are used as the second phase. Coelectrodeposition is
widely used to prepare metal matrix compounds
because of the low cost and versatility. Usually, the
solid micro/nanoparticles are added to the electrode-
position bath under severe agitation, air injection, or
ultrasonic vibration [200]. Table 4 presents a summary
of the properties and various types of Zn–Ni compos-
ite alloy coatings.
9. SUMMARY AND FUTURE TREND
Because of its low price, favorable properties, and
abundance, steel has found widespread applications in
industry. One of the major problems of this alloy is its
low corrosion resistance in corrosive environments,
especially in the atmospheric environment. One of the
methods of improving corrosion resistance is a surface
improvement by coating through electrodeposition
and cadmium coating. Toxicity of cadmium coatings
has inspired an international attention toward an alter-
native for this coating. Zinc based coating with sacrifi-
cial properties and low electrode potential is considered
as a suitable alternative coating for toxic cadmium. Elec-
trodeposition of zinc coating is investigated in industries
such as automotive, aerospace, electronics, etc. To
achieve corrosion resistance and increase long life
these coatings are investigated with a higher thickness
which reduces ductility and weldability.
Zinc-based alloy coating with an iron group (iron,
cobalt, and nickel) is an example of a zinc alloy coat-
ing that improves ductility, weldability, and paintabil-
ity of the specimen. Among these coatings, zinc–
nickel alloy has higher corrosion resistance and better
properties than other alloys groups. This coating with
8–15 wt % nickels has better corrosion resistance in
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
33
zinc–nickel alloy coating compared to other chemical
compositions of the alloy and increases the life length
of the specimens. The more satisfactory corrosion
resistance mechanism of zinc–nickel coating com-
pared to zinc and cadmium can be divided into two
stages. In the first stage of immersion better corrosion
resistance is because of desenfication speed. Dezenfi-
cation is related to surface morphology and wettability
of zinc–nickel alloy. After the passage of immersion
time, the corrosion performance of zinc–nickel alloy
is related to the combination of corrosion products.
The corrosion product formed on the alloy has the
high and low amount of simonkolleite and zinc oxide,
respectively. This product reduces corrosion rate com-
pared to zinc and cadmium coatings. Zinc–nickel
alloy coating has lower internal stress at the concentra-
tions below 10 wt %. An important property of this
alloy is the anomalous behavior that increases the
fractional zinc content in coating compared to its
amount in deposition bath. Electrodeposition of
zinc–nickel alloy coating is done in a variety of acidic
and alkaline baths. The chemical composition of these
baths is often as sulfates, chlorides, and other materials
and additives. The selected bath and the presence and
type of additives have a great effect on the zinc–nickel
alloy coating deposition properties that have been
studied with a variety of analyses. The reports indicate
the presence of γ-phase of one of zinc–nickel alloy
phases in most phases appeared in the XRD analysis.
In zinc–nickel alloy coating, deposition parameters
such as materials and additives, bath pH, temperature,
deposition current, and pulsed and direct deposition
are effective on the quality and coating properties.
Reports of resistance to corrosion, composition and
grain size of the coating and surface morphology
influenced by the parameters in the report reflect the
improved properties by forming the phase γ in the
coating.
Zinc–nickel alloy coating as composite and multi-
layered are also being investigated. These coatings
incorporated a variety of oxide and non-oxide parti-
cles are reported to improve corrosion and wear resis-
tance. Different types of particles like Al2O3, TiO2,
ZrO2, SiO2, and WC or even diamond and carbon
nanotubes have been used in this method. Zinc–
nickel multilayer coating is another coating that is
widely studied in these analyses. The studies con-
ducted on these coatings indicate their importance
and the future applications. It is predicted that these
coatings are suitable alternatives to zinc–nickel coat-
ings to improve the properties and corrosion resistance
more importantly. It is reported that the corrosion
resistance of the coatings is 35 times more than the
corrosion resistance of single layer coatings with simi-
lar thickness. Multilayered zinc–nickel coatings are
both as periodic pure zinc–nickel coating and in the
form of alloy layers. With the increase in the number
of layers in the coatings, the corrosion resistance of the
coatings is increased. Another parameter affecting the
 Table 4. Summary of results of research conducted on zinc–nickel composite coating
34

Particle, Particle Particle, icorr, Ecorr, Thickness, Hardness,

Composition Ref.
wt % size, nm wt % μA/cm2 mV vs. SCE μm HV

ZnSO4– NiSO4–Na2SO4 Al2O3 10 N.R. 0.8–6 –1013 to –1048 12–15 235–323 [203]

ZnCl2–NiCl2–H3BO3 KCL–ammonium acetate CeO2 20–30 7 1.5–5.3 –119 to –168 N.R. N.R. [218]

ZnSO4–NiSO4–Na2SO4–H3BO3 CNTs 200–800 1.3–4.4 1.9–1 –1039 to –1081 12–14 220–280 [219]

ZnO–NaOH–TEA–Ni2SO4 TiO2 20 N.R. 0.05 –601 to –717 N.R. N.R. [199]

LOTFI et al.

ZnSO4–Na2SO4–NaCl–NiSO4 CNTs 10–20 N.R. 0.02–0.01 –500 to –1200 20 120–160 [195]

ZnCl2–NiCl2–KCL–NH4Cl–NaAc Al2O3 100 7 N.R. N.R. N.R. N.R. [220]

ZnSO4–NiSO4–H3BO3Na3C6H5O7 SiC–Al2O3 N.R. 4,7 N.R. N.R. 9.5 N.R. [196]

ZnSO4–NiSO4–Na2SO4 SiO2 20, 2000 1–12 N.R. –550 to –1050 N.R. N.R. [193]

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES

* N.R. = Not reported.
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
Other
4%
Defense
industries
8%
Aerospace industries
8%
Automotive industries
Fastener industries
50%
15%
Electronic industries
15%
Fig. 54. Estimating the relative costs in different industries
using zinc–nickel alloy coating.
properties of the multilayer coating is the arrangement
of the layers. The improved corrosion resistance prop-
erties are related to the formation of more obstacles in
the way of load transfer. The test results indicate the
formation of larger interfaces on the way to the surface
of the specimen, the corrosive environments, and
improved corrosion protection. Moreover, the
improved corrosion resistance is explained by the
effect of the time-dependent electric field; i.e., fre-
quency response. The corresponding inherent electri-
cal properties are determined by Mott-Schottky and
dielectric spectroscopy curves. The low corrosion rate
is related to the semiconductor property of the coating
with the n-type nature at the interface of the layers. In
addition, the inherent permeability is reduced by
increasing the number of layers and confirms
improved corrosion. The reduced inherent permeabil-
ity is related to the homogeneous intersection created
by electron charge density. Because of the superior
corrosion resistance of the multilayer zinc–nickel
alloy coating, they are expected as more efficient alter-
native instead of pure zinc and cadmium coatings for
applications in automotive industry, in fluid transfer
tubes, corrosion protection applications, electrical
transmission industry for anchors, cleats bolts, coaxial
cables and plate connector, fastener industries in hood
and chassis joints, for improving corrosion protection,
bearings, reducing galvanic corrosion in contact with
stainless steel and aluminum and defense, and aero-
space industries in joining components. Considering
coating applications in different industries, it is possible
to estimate the relative cost of the coating as Fig. 54. An
example is the abrasion and creation of hole on the car
bodies in areas exposed to frost and the roads that are
cleared by salt as a anti-freeze injection. It is expected
that the multilayer zinc–nickel alloy coatings provide
proper corrosion resistance for the car body in such
corrosive environment. It is also predicted that the
multilayer coatings have excellent adhesion and corro-
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
35
sion resistance in the environment with high-tempera-
ture conditions. Thus, these coatings might have good
results in hydrogen embrittlement (ASTM F519)
[201], fatigue, and SO2 corrosion tests as well.
REFERENCES
1. Jacobs, C.B., J. Am. Chem. Soc., 1905, vol. 27, p. 972.
2. Schoch, E.P. and Hirsch, A., J. Am. Chem. Soc., 1907,
vol. 29, p. 314.
3. Shibuya, A., Kurimoto, T., Hoboh, Y., and Usuki, N.,
Trans. Iron Steel Inst. Jpn., 1983, vol. 23, p. 923.
4. Siitari, D.W., Sagiyama, M., and Hara, T., Trans. Iron
Steel Inst. Jpn., 1983, vol. 23, p. 959.
5. Hsu, G.F., Proc. 19th Annual Airline Plating and Metal
Finishing Forum, San Antonio, TX, 1983.
6. Sriraman, K.R., Brahimi, S., Zpunar, J.A., et al.,
Electrochim. Acta, 2013, vol. 105, p. 314.
7. Hall, D.E., Plat. Surf. Finish., 1983, vol. 70, p. 59.
8. Mordechay Schlesinger, M.P., Modern Electroplating,
Pennington, NJ: Electrochemical Society, 2010.
9. Yang, Z.L., Yang, Y.X., Zhang, J.B., et al., Russ. J.
Electrochem., 2006, vol. 42, p. 22.
10. Wilcox, G.D. and Gabe, D.R., Corros. Sci., 1993,
vol. 35, p. 1251.
11. Ghaziof, S. and Gao, W., J. Alloys Compd., 2015,
vol. 622, p. 918.
12. Wen, X., Yang, Z., Xiao, X., et al., Electrochim. Acta,
2016, vol. 187, p. 65.
13. Kwon, M., Jo, D.-h., Cho, S.H., et al., Surf. Coat.
Technol., 2016, vol. 288, p. 163.
14. Praveen, B.M. and Venkatesha, T.V., Appl. Surf. Sci.,
2008, vol. 254, p. 2418.
15. Lin, C.C. and Huang, C.M., J. Coat. Technol. Res.,
2006, vol. 3, p. 99.
16. Baldwin, K.R., Robinson, M.J., and Smith, C.J.E.,
Corros. Sci., 1994, vol. 36, p. 1115.
17. Praveen Kumar, C.M., Venkatesha, T.V., Vathsala, K.,
and Nayana, K.O., J. Coat. Technol. Res., 2011, vol. 9,
p. 71.
18. Gavrila, M., Millet, J.P., Mazille, H., et al., Surf. Coat.
Technol., 2000, vol. 123, p. 164.
19. Alfantazi, A.M. and Erb, U., Mater. Sci. Eng., A, 1996,
vol. 212, p. 123.
20. Bories, C., Bonino, J.P., and Rousset, A., J. Appl.
Electrochem., 1999, vol. 29, p. 1045.
21. Fratesi, R. and Roventi, G., Surf. Coat. Technol., 1996,
vol. 82, p. 158.
22. Baldwin, K.R., Robinson, M.J., and Smith, C.J.E.,
Corros. Sci., 1993, vol. 35, p. 1267.
23. Reumont, G., Perrot, P., and Foct, J., J. Mater. Sci.,
1998, vol. 33, p. 4759.
24. Pfiz, R. and Strube, G., Trans. Inst. Met. Finish., 1996,
vol. 74, p. 158.
25. Lee, H.Y. and Kim, S.G., Surf. Coat. Technol., 2000,
vol. 135, p. 69.
26. Bajat, J.B., Maksimović, M.D., and Radović, G.R., J.
Serb. Chem. Soc., 2002, vol. 67, p. 625.
36 LOTFI et al.
27. Swathirajan, S., J. Electrochem. Soc., 1986, vol. 133,
p. 671.
28. Ravindran, V. and Muralidharan, V.S., Bull. Mater.
Sci., 2006, vol. 29, p. 293.
29. Fei, J.Y., Liang, G.Z., Xin, W., L., and Wang, W., J.
Iron Steel Res. Int., 2006, vol. 13, p. 61.
30. Wykpis, K., Popczyk, M., and Budniok, A., Bull.
Mater. Sci., 2011, vol. 34, p. 997.
31. Coleman, D.H. and Popov, B.N., J. Appl. Electro-
chem., 1998, vol. 28, p. 889.
32. Watkins, K.G., Jones, R.D., and Lo, K.M., Mater.
Lett., 1989, vol. 8, p. 21.
33. Hegde, A.C., Venkatakrishna, K., and Eliaz, N., Surf.
Coat. Technol., 2010, vol. 205, p. 2031.
34. Eliaz, N., Venkatakrishna, K., and Hegde, A.C., Surf.
Coat. Technol., 2010, vol. 205, p. 1969.
35. Ashassi-Sorkhabi, H., Hagrah, A., Parvini-Ahmadi, N.,
and Manzoori, J., Surf. Coat. Technol., 2001, vol. 140,
p. 278.
36. Elkhatabi, F., Benballa, M., Sarret, M., and Müller,
C., Electrochim. Acta, 1998, vol. 44, p. 1645.
37. Boonyongmaneerat, Y., Saenapitak, S., and Saengki-
ettiyut, K., J. Alloys Compd., 2009, vol. 487, p. 479.
38. Qiao, X., Li, H., Zhao, W., and Li, D., Electrochim.
Acta, 2013, vol. 89, p. 771.
39. Wykpis, K., Popczyk, M., Niedbala, J., et al., Coat.,
Mater. Sci., 2012, vol. 1, p. 10.
40. Pedroza, G.A.G., de Souza, C.A.C., Carlos, I.A., and
de Andrade Lima L.R.P., Surf. Coat. Technol., 2012,
vol. 206, p. 2927.
41. Magagnin, L., Nobili, L., and Cavallotti, P.L., J. Alloys
Compd., 2014.
42. Hosseini, M.G., Ashassi-Sorkhabi, H., and Ghi-
asvand, H.A.Y., Surf. Coat. Technol., 2008, vol. 202,
p. 2897.
43. Soares, M.E., Souza, C.A.C., and Kuri, S.E., Mater.
Sci. Eng., A, 2005, vol. 402, p. 16.
44. Fashu, S., Gu, C.D., Wang, X.L., and Tu, J.P., Surf.
Coat. Technol., 2014, vol. 242, p. 34.
45. Byk, T.V., Gaevskaya, T.V., and Tsybulskaya, L.S.,
Surf. Coat. Technol., 2008, vol. 202, p. 5817.
46. Sachin, H.P., Achary, G., Arthoba Naik, Y., and Ven-
katesha, T.V., Bull. Mater. Sci., 2007, vol. 30, p. 57.
47. El Hajjami, A., Gigandet, M.P., De Petris-Wery, M.,
et al., Appl. Surf. Sci., 2007, vol. 254, p. 480.
48. Sriraman, K.R., Brahimi, S., Szpunar, J.A., et al.,
Surf. Coat. Technol., 2013, vol. 224, p. 126.
49. Barceló, G., García, E., Sarret, M., et al., J. Appl.
Electrochem., 1998, vol. 28, p. 1113.
50. Brenner, A. and Brenner, N., Electrodeposition of
Alloys, New York: Academic Press, 1963, vol. 2.
51. Miranda, F.J.F., Barcia, O.E., Diaz, S.L., et al., Elec-
trochim. Acta, 1996, vol. 41, p. 1041.
52. Elkhatabi, F., Sarret, M., and Müller, C., J. Electro-
anal. Chem., 1996, vol. 404, p. 45.
53. Seki, A. and Kamei, K., J. Iron Steel Inst. Jpn., 1991,
vol. 77, p. 892.
54. Müller, C., Sarret, M., and Benballa, M., J. Electro-
anal. Chem., 2002, vol. 519, p. 85.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
55. Conrad, H.A., McGuire, M.R., Zhou, T., et al., Surf.
Coat. Technol., 2015, vol. 272, p. 50.
56. Chassaing, E. and Wiart, R., Electrochim. Acta, 1992,
vol. 37, p. 545.
57. ASTM B.117: Standard Practice for Operating Salt
Spray (Fog) Apparatus, West Conshohocken, PA:
ASTM Int., 1997.
58. Alfantazi, A.M. and Erb, U., Corrosion, 1996, vol. 52,
p. 880.
59. Baldwin K.R., Smith C.J.E., and Robinson M.J.,
Trans. Mater. Heat Treat., 1995, vol. 51, p. 932.
60. Mosavat, S.H., Shariat, M.H., and Bahrololoom, M.E.,
Corros. Sci., 2012, vol. 59, p. 81.
61. Tian, W., Xie, F.Q., Wu, X.Q., and Yang, Z.Z., Surf.
Interface Anal., 2009, vol. 41, p. 251.
62. ASTM B841-99: Standard Specification for Electrode-
posited Coatings of Zinc Nickel Alloy Deposits, West
Conshohocken, PA: ASTM Int., 2010.
63. Swathirajan, S., J. Electroanal. Chem., 1987, vol. 221,
p. 211.
64. Vaes, J., Fransaer, J., and Celis, J.P., J. Electrochem.
Soc., 2002, vol. 149, p. C567.
65. Abd El Rehim, S. and Ibrahim, M., J. Metall., 1998,
vol. 52, p. 304.
66. Kawano, S., Ohgai, T., Kobayashi, S., et al., Proc. 2nd
Int. Conference on Processing Materials for Properties,
San Francisco, CA, 2000, p. 769.
67. Rizwan, R., Mehmood, M., Imran, M., et al., Mater.
Trans., 2007, vol. 48, p. 1558.
68. Roev, V. and Gudin, N., Trans. Inst. Met. Finish.,
1996, vol. 74, p. 153.
69. Baldwin, K., Smith, C., and Robinson, M., Trans.
Inst. Met. Finish., 1994, vol. 72, p. 79.
70. Stein, M., Owens, S.P., Pickering, H.W., and Weil, K.G.,
Proc. AESF Annual Technical Conference, Cleveland,
OH, 1996, p. 83.
71. Abou-Krisha, M.M., Assaf, F.H., and Toghan, A.A.,
J. Solid State Electrochem., 2007, vol. 11, p. 244.
72. Abd El Rehim, S.S., Fouad, E.E., Abd El Wahab, S.M.,
and Hassan, H.H., Electrochim. Acta, 1996, vol. 41,
p. 1413.
73. Vasilache, T., Gutt, S., Sandu, I., et al., Alloy Electro-
deposition.
74. Sonntag, B., Dingwerth, B., Vogel, R., and Scheller, B.,
Galvanotechnik, 2010, vol. 101, p. 992.
75. Townsend, H., Mater. Perform., 1991, vol. 30, p. 60.
76. Divisek, J., Malinowski, P., Mergel, J., and Schmitz, H.,
Int. J. Hydrogen Energy, 1988, vol. 13, p. 141.
77. Giz, M.J., Machado, S.A.S., Avaca, L.A., and Gonza-
lez, E.R., J. Appl. Electrochem., 1992, vol. 22, p. 973.
78. Sheela, G., Pushpavanam, M., and Pushpavanam, S.,
Int. J. Hydrogen Energy, 2002, vol. 27, p. 627.
79. Müller, C., Sarret, M., and Benballa, M., Electrochim.
Acta, 2001, vol. 46, p. 2811.
80. Raj, I.A. and Vasu, K.I., J. Appl. Electrochem., 1992,
vol. 22, p. 471.
81. Giridhar, J. and van Ooij, W.J., Surf. Coat. Technol.,
1992, vol. 53, p. 35.
82. Alfantazi, A.M., Page, J., and Erb, U., J. Appl. Electro-
chem., 1996, vol. 26, p. 1225.
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
83. Nakano, H., Arakawa, S., Oue, S., and Kobayashi, S.,
ISIJ Int., 2013, vol. 53, p. 1864.
84. Alexis, J., Adrian, D., Masri, T., and Petit, J.A., Surf.
Eng., 2004, vol. 20, p. 121.
85. Sohi, M.H. and Jalali, M., J. Mater. Process. Technol.,
2003, vol. 138, p. 63.
86. Wharton, J.A., Wilcox, G.D., and Baldwin, K.R.,
Trans. Inst. Met. Finish., 1996, vol. 74, p. 210.
87. Flis, J., Tobiyama, Y., Shiga, C., and Mochizuki, K.,
J. Appl. Electrochem., 2002, vol. 32, p. 401.
88. Kitayama, M., Odashima, H., Saito, T., and Hirano, Y.,
Trans. Iron Steel Inst. Jpn., 1986, vol. 26, p. 557.
89. Abdel Hamid, Z., Anti-Corros. Methods Mater., 1998,
vol. 45, p. 31.
90. Nobutaka Miura, T.S., Tatsuya Kanamaru Yoshio
Shindo, and Yoshio Kitazawa, Trans. Iron Steel Inst.
Jpn.,1966, vol. 23, p. 913.
91. Watson, S.A., Trans. Inst. Met. Finish., 1992, vol. 70,
p. 28.
92. Wakano, S., Shibuya, A., Hobo, Y., and Nishihira, M.,
Trans. Iron Steel Inst. Jpn., 1983, vol. 23, p. 967.
93. Lehmberg, C.E., Lewis, D.B., and Marshall, G.W.,
Surf. Coat. Technol., 2005, vol. 192, p. 269.
94. Nomura, S., Sakai, H., Nishimoto, H., et al., Trans.
Iron Steel Inst. Jpn., 1983, vol. 23, p. 930.
95. Durairajan, A., Haran, B.S., White, R.E., and
Popov, B.N., J. Electrochem. Soc., 2000, vol. 147,
p. 1781.
96. Abou-Krisha, M., Assaf, F., and El-Naby, S., J. Coat.
Technol. Res., 2009, vol. 6, p. 391.
97. Krishniyer, A., Ramasubramanian, M., Popov, B.,
and White, R., Plat. Surf. Finish., 1999, vol. 86, p. 99.
98. Abou-Krisha, M.M., Mater. Chem. Phys., 2011,
vol. 125, p. 621.
99. Thangaraj, V., Eliaz, N., and Hegde, A., J. Appl. Elec-
trochem., 2009, vol. 39, p. 339.
100. Ishihara, M., Yumoto, H., Akashi, K., and Kamei, K.,
Mater. Sci. Eng., B, 1996, vol. 38, p. 150.
101. Basavanna, S. and Arthoba Naik, Y., J. Appl. Electro-
chem., 2009, vol. 39, p. 1975.
102. Safranek, W.H., The Properties of Electrodeposited
Metals and Alloys. Handbook, Orlando, FL: American
Electroplaters and Surface Finishers Society, 1986,
vol. 1986, p. 550.
103. Ganesan, P., Kumaraguru, S.P., and Popov, B.N.,
Surf. Coat. Technol., 2007, vol. 201, p. 7896.
104. Bruet, H., Bonino, J.P., and Rousset, A., J. Mater.
Sci., 1999, vol. 34, p. 881.
105. Ni–Zn (Nickel-Zinc). Section III: Supplemental Lit-
erature Review. Okamoto, H.J., J. Phase Equilib. Dif-
fus., 2013, vol. 34, p. 153. https://doi.org/10.1007/
s11669-012-0154-5.
106. Fayomi, O.S.I., Tau, V., Popoola, A.P.I., et al., Appl.
Phys. A: Mater. Sci. Process., 2015, vol. 121, p. 749.
107. Hino, M., Murakami, K., Muraoka, K., et al., J. Jpn.
Inst. Met., 2014, vol. 78, p. 31.
108. Hammami, O., Dhouibi, L., Berçot, P., et al., Can. J.
Chem. Eng., 2013, vol. 91, p. 19.
109. Nakano, H., Arakawa, S., Takada, Y., et al., Mater.
Trans., 2012, vol. 53, p. 1946.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
37
110. Telli, E., Döner, A., and Kardaş, G., Electrochim.
Acta, 2013, vol. 107, p. 216.
111. Elsherief, A. and Shoeib, M., Corros. Prev. Control,
2003, vol. 50, p. 25.
112. Praveen, B.M. and Venkatesha, T.V., Chem. Eng.
Commun., 2012, vol. 199, p. 812.
113. Fabri Miranda, F.J., Barcia, O.E., Mottos, O.R., and
Wiart, R., J. Electrochem. Soc., 1997, vol. 144, p. 3449.
114. Giridhar, J. and van Ooij, W.J., Surf. Coat. Technol.,
1992, vol. 52, p. 17.
115. Nakano, H., Kataoka, S., Oue, S., and Kobayashi, S.,
J. Iron Steel Inst. Jpn., 2013, vol. 99, p. 709.
116. Khan, R., Mehmood, M., Rizwan, R., et al., Corros.
Eng. Sci. Technol., 2011, vol. 46, p. 755.
117. Rodriguez-Torres, I., Valentin, G., and Lapicque, F.,
J. Appl. Electrochem., 1999, vol. 29, p. 1035.
118. Pushpavanam, M. and Balakrishnan, K., J. Appl. Elec-
trochem., 1996, vol. 26, p. 1065.
119. Chandrasekar, M.S., Srinivasan, S., and Pushpava-
nam, M., J. Solid State Electrochem., 2009, vol. 13,
p. 781.
120. Hammami, O., Dhouibi, L., and Triki, E., Surf. Coat.
Technol., 2009, vol. 203, p. 2863.
121. Ramazan, K. and U ur, Y., Trans. Inst. Met. Finish.,
2014, vol. 92, p. 245.
122. Llayaraja, M., Mohan, S., Gnanamuthu, R.M., and
Saravanan, G., Trans. Inst. Met. Finish., 2009, vol. 87,
p. 145.
123. Kondo, K., Yokoyama, M., and Shinohara, K., J.
Electrochem. Soc., 1995, vol. 142, p. 2256.
124. Katirci, R., Trans. Indian Inst. Met., 2010, vol. 63,
p. 841.
125. Yogesha, S., Hegde, A.C., Trans. Indian Inst. Met.,
2010, vol. 63, p. 841.
126. Chouchane, S., Levesque, A., Zabinski, P., et al., J.
Alloys Compd., 2010, vol. 506, p. 575.
127. Levesque, A., Chouchane, S., Douglade, J., et al.,
Appl. Surf. Sci., 2009, vol. 255, p. 8048.
128. Yu, Y.D., Cao, Y., Li, M.G., et al., Mater. Res. Innova-
tions, 2014, vol. 18, p. 314.
129. Rao, V.R., Bangera, K.V., and Hegde, A.C., J. Magn.
Magn. Mater., 2013, vol. 345, p. 48.
130. Felloni, L., Fratesi, R., Quadrini, E., and Roventi, G.,
J. Appl. Electrochem., 1987, vol. 17, p. 574.
131. Thangaraj, V. and Chitharanjan Hegde, A., Indian J.
Chem. Technol., 2007, vol. 14, p. 246.
132. Beltowska-Lehman, E., Ozga, P., Swiatek, Z., and
Lupi, C., Surf. Coat. Technol., 2002, vol. 151, p. 444.
133. Bhatnagar, P. and Free, M.L., Surf. Coat. Technol.,
2006, vol. 200, p. 6083.
134. Mohan, S., Ravindran, V., Subramanian, B., and Sarava-
nan, G., Trans. Inst. Met. Finish., 2009, vol. 87, p. 8.
135. Barceló, G., García, J., Sarret, M., et al., J. Appl. Elec-
trochem., 1994, vol. 24, p. 1249.
136. Wykpis, K., Niedbała, J., Popczyk, M., et al., Russ. J.
Electrochem., 2012, vol. 48, p. 1123.
137. Conrad, H., Corbett, J., and Golden, T.D., J. Electro-
chem. Soc., 2012, vol. 159, p. C29.
38 LOTFI et al.
138. Hu, C.C., Tsay, C.H., and Bai, A., Electrochim. Acta,
2003, vol. 48, p. 90.
139. Ieffa, S., Bernasconi, R., Nobili, L., et al., Trans. Inst.
Met. Finish., 2014, vol. 92, p. 321.
140. Blejan, D. and Muresan, L.M., Mater. Corros., 2013,
vol. 64, p. 433.
141. Petrauskas, A. and Grincevičiene, L., J. Appl. Electro-
chem., 2009, vol. 39, p. 1579.
142. Abibsi, A., Dennis, J., and Short, N., Trans. Inst. Met.
Finish., 1991, vol. 69, p. 145.
143. Albalat, R., Gómez, E., Müller, C., et al., J. Appl.
Electrochem., 1991, vol. 21, p. 44.
144. Mathias, M.F. and Chapman, T.W., J. Electrochem.
Soc., 1990, vol. 137, p. 102.
145. Tsybulskaya, L.S., Gaevskaya, T.V., Purovskaya, O.G.,
and Byk, T.V., Surf. Coat. Technol., 2008, vol. 203,
p. 234.
146. Albalat, R., Gomez, E., Müller, C., et al., J. Appl.
Electrochem., 1990, vol. 20, p. 635.
147. Nawrat, G., Piotrowski, J., Maciej, A. et al., Arch.
Metall. Mater., 2010, vol. 55, p. 255.
148. Muresan, L.M., Eymard, J., Blejan, D., and Indrea, E.,
Stud. Univ. Babes-Bolyai, Chem., 2010, vol. 1, p. 37.
149. Katirci, R., Surf. Rev. Lett., 2015, vol. 22, p. 1550015.
150. Mathias, M.F. and Chapman, T.W., J. Electrochem.
Soc., 1990, vol. 137, p. 102.
151. Mathias, M.F., Villa, C.M., and Chapman, T.W., J.
Appl. Electrochem., 1990, vol. 20, p. 1.
152. Muralidhara, H.B., Arthoba Naik, Y., Sachin, H.P.,
and Venkatesha, T.V., Indian J. Chem. Technol., 2008,
vol. 15, p. 155.
153. Lin, Z.F., Li, X.B., and Xu, L.K., Int. J. Electrochem.
Sci., 2012, vol. 7, p. 12507.
154. Karwas, C. and Hepel, T., J. Electrochem. Soc., 1988,
vol. 135, p. 839.
155. Shivakumara, S., Manohar, U., Arthoba Naik, Y., and
Venkatesha, T.V., Bull. Mater. Sci., 2007, vol. 30,
p. 455.
156. Pushpavanam, M. and Balakrishnan, K., J. Appl. Elec-
trochem., 1996, vol. 26, p. 283.
157. Pedroza, G.A.G., de Souza, C.A.C., de Jesus, M.D.,
et al., Surf. Coat. Technol., 2014, vol. 258, p. 232.
158. Abou-Krisha, M.M., Assaf, F.H., and El-Naby, S.A.,
J. Solid State Electrochem., 2009, vol. 13, p. 879.
159. Fratesi, R. and Roventi, G., J. Appl. Electrochem.,
1992, vol. 22, p. 657.
160. Ghaziof, S. and Gao, W., Appl. Surf. Sci., 2014,
vol. 311, p. 635.
161. Abou-Krisha, M.M., Appl. Surf. Sci., 2005, vol. 252,
p. 1035.
162. Yu, Y.D., Zhao, X.X., Li, M.G., et al., Surf. Eng.,
2013, vol. 29, p. 743.
163. Lin, C.S., Lee, H.B., and Hsieh, S.H., Metall. Mater.
Trans. A, 1999, vol. 30, p. 437.
164. Lee, E., Ahn, J., and Ma, C., Plat. Surf. Finish., 2001,
vol. 88, p. 124.
165. Tozar, A. and Karahan, I.H., Appl. Surf. Sci., 2014,
vol. 318, p. 15.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
166. Wu, Z., Fedrizzi, L., and Bonora, P.L., Surf. Coat.
Technol., 1996, vol. 85, p. 170.
167. Bajat, J.B., Petrović, A.B., and Maksimović, M.D., J.
Serb. Chem. Soc., 2005, vol. 70, p. 1427.
168. Chen, C.J. and Wan, C.C., J. Electrochem. Soc., 1989,
vol. 136, p. 2850.
169. Knodler, A., Raub, C., and Raub, E., Metallober-
flache, 1985, vol. 39, p. 21.
170. Boonyongmaneerat,Y., Saengkiettiyut, K., Saenapi-
tak, S., and Sangsuk, S., J. Mater. Eng. Perform., 2014,
vol. 23, p. 302.
171. Ivanov, I., Valkova, T., and Kirilova, I., J. Appl. Elec-
trochem., 2002, vol. 32, p. 85.
172. Jingyin, F., Guozheng, L., Wenli, X., and Jianghong, L.,
J. Wuhan Univ. Technol., Mater. Sci. Ed., 2006, vol. 21,
p. 40.
173. Thangaraj, V., Ravishankar, K., and Chitharanjan
Hegde, A., Chin. J. Chem., 2008, vol. 26, p. 2285.
174. Rahsepar, M. and Bahrololoom, M.E., Surf. Coat.
Technol., 2009, vol. 204, p. 580.
175. Kalantary, M.R., Wilcox, G.D., and Gabe, D.R.,
Electrochim. Acta, 1995, vol. 40, p. 1609.
176. Kalantary, M.R., Wilcox, G.D., and Gabe, D.R., Br.
Corros. J., 1998, vol. 33, p. 197.
177. Chawa, G., Wilcox, G., and Gabe, D., Trans. Inst.
Met. Finish., 1998, vol. 76, p. 117.
178. Lin, C.S., Lee, H.B., and Hsieh, S.H., Metall. Mater.
Trans. A, 2000, vol. 31, p. 475.
179. Ivanov, I. and Kirilova, I., J. Appl. Electrochem., 2003,
vol. 33, p. 239.
180. Fei, J., Liang, G., Xin, W., et al., J. Univ. Sci. Technol.
Beijing, 2005, vol. 12, p. 545.
181. Gabe, D.R. and Green, W.A., Surf. Coat. Technol.,
1998, vol. 105, p. 195.
182. Kaneko, Y., Mizuta, Y., Nishijima, Y., and
Hashimoto, S., J. Mater. Sci., 2005, vol. 40, p. 3231.
183. Chen, J.L., Liu, J.H., Li, S.M., and Yu, M., Mater.
Corros., 2012, vol. 63, p. 607.
184. Fei, J.Y. and Wilcox, G.D., Surf. Coat. Technol., 2006,
vol. 200, p. 3533.
185. Subbaiah, Y., Kaje, V., and Hegde, A.C., Anti-Corros.
Methods Mater., 2011, vol. 58, p. 84.
186. Chang, L.M., Chen, D., Liu, J.H., and Zhang, R.J., J.
Alloys Compd., 2009, vol. 479, p. 489.
187. Praveen, B.M. and Venkatesha, T.V., Int. J. Electro-
chem., 2011, vol. 2011, p. 1.
188. Ghaziof, S., Kilmartin, P.A., and Gao, W., J. Electro-
anal. Chem., 2015, vol. 755, p. 63.
189. Praveen, B.M. and Venkatesha, T.V., J. Alloys Compd.,
2009, vol. 482, p. 53.
190. Zheng, H.-Y. and An, M.-Z., J. Alloys Compd., 2008,
vol. 459, p. 548.
191. Panagopoulos, C.N., Georgarakis, K.G., and Agatho-
cleous, P.E., Tribol. Int., 2003, vol. 36, p. 619.
192. Blejan, D., Bogdan, D., Pop, M., et al., Adv. Mater.,
2011, vol. 5, p. 25.
193. Tuaweri, T.J. and Wilcox, G.D., Trans. Inst. Met. Fin-
ish., 2007, vol. 85, p. 245.
 ZINC–NICKEL ALLOY ELECTRODEPOSITION
194. Hino, M., Murakami, K., Muraoka, K., et al., in
Materials Science Forum, Trans Tech Publ., 2014,
p. 1420.
195. Praveen, B.M. and Venkatesha, T.V., J. Alloys Compd.,
2009, vol. 482, p. 53.
196. Tulio, P.C., Rodrigues, S.E.B., and Carlos, I.A., Surf.
Coat. Technol., 2007, vol. 202, p. 91.
197. Müller, C., Sarret, M., and Benballa, M., Surf. Coat.
Technol., 2002, vol. 162, p. 49.
, N., J. Optoelec-
198. Hammami, O., Dhouibi, L., Berçot, P., et al., Int. J.
Corros., 2012, vol. 8, p. 1.
199. Blejan, D., Marconi, D., Pop, A., and Muresan, L.M.,
Stud. Univ. Babes-Bolyai, Chem., 2011, vol. 95. Blejan, D.,
Marconi, D., Pop, A., and Muresan, L.M., Stud. Univ.
Babes-Bolyai, Chem., 2011, vol. 56, no. 1, p. 95.
200. Kumar, M.K.P., Venkatesha, T.V., Pavithra, M.K.,
and Shetty, A.N., Phys. Scr., 2011, vol. 84, p. 035601.
201. ASTM 519: Standard Test Method for Mechanical
Hydrogen Embrittlement Evaluation of Plating. ASTM
Book of Standards, West Conshohocken, PA: ASTM
Int.
202. Roventi, G., Fratesi, R., Della Guardia, R.A., and
Barucca, G., J. Appl. Electrochem., 2000, vol. 30,
p. 173.
203. Ghaziof, S. and Gao, W., J. Alloys Compd., 2015,
vol. 622, p. 918.
204. Karahan, I.H. and Tozar, A., Trans. Inst. Met. Finish.,
2014, vol. 92, p. 262.
205. Chandrappa, K.G. and Venkatesha, T.V., Mater. Cor-
ros., 2013, vol. 64, p. 831.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES
39
206. Hosseini, M., Abdolmaleki, M., and Ashrafpoor, S.,
Chin. J. Catal., 2012, vol. 33, p. 1817.
207. Hosseini, M.G., Abdolmaleki, M., and Ashrafpoor, S.,
J. Appl. Electrochem., 2012, vol. 42, p. 153.
208. Herraiz-Cardona, I., Ortega, E., and Pérez-Herranz, V.,
Electrochim. Acta, 2011, vol. 56, p. 1308.
209. Szczygieł, B., Laszczyńska, A., and Tylus, W., Surf.
Coat. Technol., 2010, vol. 204, p. 1438.
210. Suliţanu, N., Pîrghie, C., and Brînz
tron. Adv. Mater., 2006, vol. 8, p. 1889.
211. Ramasubramanian, M., Popov, B.N., and White, R.E.,
J. Electrochem. Soc., 1998, vol. 145, p. 1907.
212. Hino, M., Nishida, N., Hiramatsu, M., et al., Mater.
Lett., 1998, vol. 34, p. 81.
213. Conde, A., Arenas, M.A., and de Damborenea, J.J.,
Corros. Sci., 2011, vol. 53, p. 1489.
214. Ivanov, I., Valkova, T., and Kirilova, I., J. Appl. Elec-
trochem., 2002, vol. 32, p. 85.
215. Rahsepar, M. and Bahrololoom, M., Corros. Sci.,
2009, vol. 51, p. 2537.
216. Jiang, Y., Liu, L., Zhai, C., et al., Thin Solid Films,
2005, vol. 484, p. 232.
217. Fei, J.-Y. and Wilcox, G., Surf. Coat. Technol., 2006,
vol. 200, p. 3533.
218. Zheng, Z., Li, N., Wang, C.Q., et al., J. Power Sources,
2013, vol. 222, p. 88.
219. Sudhakar, R. and Venkatesha, V.T., Ind. Eng. Chem.
Res., 2013, vol. 52, p. 6422.
220. Zheng, H.-Y., An, M.-Z., and Lu, J.-F., Appl. Surf.
Sci., 2008, vol. 254, p. 1644.