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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.
1
2 LOTFI et al.
7.3. Zinc–nickel Multilayer the hardness and thermal stability of the coatings are
Coating Applications 28 evaluated and good results have been achieved [19,
8. Zinc–nickel composite coatings 28 20]. These coatings are frequently used in industry
8.1. Zinc–nickel Composite Coatings because of their excellent corrosion resistance and the
Microstructure 30 increased life of the zinc coatings [21, 22]. These alloy
coatings are also used to reduce the thickness of the
8.2. Zinc–nickel Coating Composite zinc coatings [23].
Properties 31
8.3. Zinc–nickel Composite Coating Zinc has a reverse standard potential of –0.76 V/SHE
Applications 33 which is more negative than iron (Fe/Fe2+ – 0.44 V/SHE).
9. Summary and future trend 33 Thus, it is used for sacrificial cathodic protection of
steel against corrosion. Zinc is often used to cover
10. References 35 parts of iron and steel when it is one of the primary
factors for atmospheric and internal corrosion protec-
1. INTRODUCTION tion [8]. Commercial electrodeposition of zinc is used
in cyanide, alkaline, cyanide, and acid chloride baths
Considering the higher corrosion resistance com- [24, 25]. In the 1970s, the highest commercial electro-
pared to pure zinc and other alloy coatings, electrode- deposition of zinc was performed in common cyanide
position of Zn–Ni alloy has recently received a wide- baths but the international pressures for environmen-
spread attention. The studies conducted on these tal pollution developed other processes [8].
coatings initiated in the early 20th century [1, 2]. In
the early 1980s, the study of zinc–nickel electrodepo- It has been shown that the zinc alloys can improve
sition and other properties of this coating was pursued corrosion resistance compared to the pure zinc in pro-
even more than before [3, 4]. This coating also was tecting the ferrous based metals [26–28]. Zinc–nickel
used as an alternative to corrosion protection coatings alloys have attracted a considerable attention because
especially toxic cadmium coatings in 1983 [5, 6]. D. of their high corrosion resistance [29–31] and better
Hall [7] reviewed zinc–nickel alloy coatings by exam- mechanical properties than zinc and other zinc alloy
ining the anomalous behavior of the coating, phase, coatings [32]. Although the demand for zinc–nickel
alloy structures, physical properties, and corrosion coatings with the improved mechanical and corrosion
and deposition conditions of zinc–nickel alloy coat- properties is increased for industrial applications, the
ings. A large number of works have been conducted in zinc–nickel alloy layers are commonly used to protect
this area to improve the overall behavior of samples the steel from corrosion [11, 33, 34]. Zinc–nickel
regarding customer requirements, basic ductility, coating properties depend on composition and pH of
weldability, corrosion resistance after the conversion the bath, temperature, current density, electrodeposi-
of the surface and painting [8, 9]. Recently, consider- tion potential, coating application mode (pulse or
able efforts have been done to improve the corrosion DC) [35–37]. Nickel plays a key role in corrosion
resistance of zinc and zinc alloy coatings for applica- resistance of zinc–nickel alloy coating since it reduces
tion in harsh environments [10, 11]. Nowadays, differ- the hydration of Zn(OH)2 into the ZnO-corrosion
ent types of steel sheets with the zinc–nickel coating product. Hydroxide has a lower electrical conductivity
are used in large quantities to improve the durability of than the oxide layer, leading to a weaker cathode oxy-
car bodies [12, 13]. Based on our knowledge. No com- gen reduction reaction than the oxide and conse-
prehensive review paper abut zinc– nickel coating by quently a lower corrosion [10]. Qiao et al. [38] studied
electrodeposition was not reported in the literatures. the deposition temperature effect on electrodeposition
In this review paper, comprehensive discussion about of zinc–nickel alloy and concluded that when it
all aspect of zinc–nickel coating fabricated by electro- increases up to 60°C, the amount of zinc–nickel
deposition method is reported. 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
2. ZINC–NICKEL ALLOY and chemical composition of the coatings phase are
COATING PROPERTIES dependent on the current density deposition. Many
Steel is widely used in industry because of its excel- organic chemical compounds including glycine, tri-
lent properties. Considering its low corrosion resis- ethylamine, polyamine compounds, and glycerol
tance, many protection methods have been developed [40–43] are reported to improve the surface morphol-
to increase its corrosion resistance [14–16]. Among ogy and nickel concentration during the deposition
these methods, electrodeposition of a thin layer of [44]. Byk et al. [45] studied the zinc–nickel alloy elec-
zinc, nickel, cadmium or deposition of their alloys on trochemical deposition in polyligand bath that
the metal is widely used [17]. Electrodeposition of includes amino acetic acid and triethylamine as a
zinc–nickel coatings has long been known to provide ligand for the accession of Ni(II) cations. The alloy
better corrosion protection of steel than electro galva- composition is strongly influenced by the
nized, galvanized and cadmium coatings [7, 18]. Also, [Zn(II)]/[Ni(II)] ratio in the bath [46]. Besides, the
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 affecting the corrosion resistance of zinc–nickel alloy
75%. To improve the corrosion properties of pure zinc coating is the nickel content in the coating. The salt
coatings used in the transportation industry, the zinc spray test (ASTM B 117) [57] was carried out on alloy
alloy coatings are replaced with the eighth group (Zn– coating and other zinc coatings. The test compares the
Ni, Zn–Co, Zn–Fe). Due to the high toxicity and corrosion resistance of these coatings with other ones
cost of cadmium coatings, zinc–nickel coatings are and also presents the effect of nickel content on alloy
the most successful alloys and are good replacements coating. The results of these tests show that the corro-
for cadmium coatings [47, 48]. It is reported that sion resistance of zinc–nickel alloy coating is far better
zinc–nickel coatings with 10–15 wt % nickel have a than other zinc coatings. Besides, by increasing the
better corrosion resistance, ductility, and weldability. nickel content in the deposition up to 12–15 wt %, cor-
Although the nickel content reaches 15–22 wt % in the rosion resistance is improved. Exceeding 12–15 wt % of
aviation industry, Barcelo et al. [49] reported that the nickel content, the corrosion resistance is reduced
alloys containing 10 to 15 wt % nickel play a special compared to the previous mode [22, 58].
role in corrosion resistance. In addition to the chemi- Many factors affect the properties of zinc–nickel
cal composition, physical properties of zinc–nickel alloy coating [59]. Corrosion performance of nano-
coatings depend on their microstructure, phase chem- crystalline electrodeposited zinc–nickel alloy coating
ical composition, and structural parameters. Zinc– in a chloride bath is analyzed by direct current density
nickel anomalous codeposition is highlighted in the using impedance spectroscopy and polarization
early twentieth century and thoroughly investigated by curves and compared with microcrystalline alloy coat-
Brenner et al. [50] and other researchers [51]. ings. The corrosion product formed on nanocrystal-
Many studies have been conducted on phases of line zinc–nickel alloy coating is more sustainable and
zinc–nickel alloys [52]. In a research work, the zinc– provides a higher protection compared to microcrys-
nickel alloy dispositions are analyzed as coatings for talline alloy coating. Nanocrystalline zinc–nickel
the improved corrosion resistance at low current den- alloy with 18 wt % and crystal size 37 nm has the best
sities (more than 50 mA/cm2) in sulfate solutions. It performance among zinc–nickel alloys. Also, the cor-
was observed that composition of cathode deposits for rosion resistance of zinc–nickel alloy coating depends
most matrixes has a complex structure called as γ, on the chemical composition [60].
which is an alternative to cadmium. In addition, Changes in chemical composition with coating
phase-γ zinc–nickel alloy with approximately 13 wt % depth in a chloride bath were investigated and found
nickel has the best corrosion resistance among the that chemical composition at the surface has a higher
zinc–nickel alloys. The coating adhesion and weld- atoms fraction of the zinc and then the nickel content
ability are also better and obtaining almost constant is increased in the substrate surface. The micromor-
alloy composition in the wide range of deposition con- phology of zinc–nickel alloy coatings with different
ditions is easy [53]. Electrodeposition of zinc–nickel amounts of nickel is presented in Fig. 1. It can be
coating is carried out in acidic and alkaline baths with observed that the crystallization during electrochemi-
sulfate and chloride composition and other different cal deposition stage is not fine and in the low of nickel,
baths and the properties of each and their comparison the coating is loose and rough. By increasing the nickel
were carried out [54–56]. content, the crystallization of coatings becomes finer,
One of the important properties of zinc–nickel brighter, and more uniform [61].
alloy coating is their corrosion resistance in corrosive According to ASTM B841 [62], alloy coatings can
environments and their higher resistance compared to be classified as Fig. 2. As it can be observed, these
pure zinc coatings. Moreover, one of the parameters coatings are classified into three categories in terms of
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)
chemical composition, after coating operations and bath. This process follows the deposition on hydroxide
thickness. In the first group, the nickel concentration and retention of Ni2+ [69]. Another research carried
in the deposit varies in the range of 5–12 wt % that is out based on underpotential deposition (UPD) of zinc
an optimal nickel content in the deposition for corro- is on nickel and zinc-rich alloys or on the nickel
sion resistance. Moreover, in the second classifica- nucleus. To protect steel, the investigated alloy might
tion, the coating is classified based on chromate con- have either a high amount of zinc which is more active
version after coating based on color. Finally, in the than steel (sacrificial film) or higher amount of nickel
third classification, the coating is classified into three which is nobler than the steel surface (barrier film)
groups of 5, 8 and 10 μm based on its thickness [62]. [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
3. ZINC–NICKEL ALLOY COATING increased rate of the more active compound reaction
ELECTROCHEMICAL DEPOSITION compared to the deposition of a single metal [47, 71].
ANOMALOUS BEHAVIOR In other studies, it is confirmed that the anomalous
behavior is attributed to the formation of zinc hydrox-
Zinc alloys obtained by a metal from the iron group ide on the cathode surface that prevents the deposition
(Ni, Fe, Co) under the condition known as anomalous of nickel and zinc hydroxide formation due to the local
codeposition indicate less noble zinc deposits prefer- increase in pH as the result of hydrogen evolution [72].
entially [63, 64]. Electrodeposition of zinc anomalous Zinc–nickel alloy properties, especially for corrosion
behavior in zinc–nickel coatings is reported and ana- resistance, are essentially dependent on nickel con-
lyzed in many studies [65, 66]. Recent studies con- centration in zinc–nickel depositions. The optimum
ducted on the reaction mechanism suggest that this amount of nickel for the maximum protection is
phenomenon is related to the local increase of pH at within the range of 8–15 wt % and zinc–nickel alloys
the cathode surface due to the hydrogen evolution with a nickel content of 13 wt % present the highest
which is the result of the type of absorbed zinc hydrox- corrosion protection [29, 73].
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 4. ZINC–NICKEL ALLOY
the final deposition. Zinc–nickel deposition is classi- COATING APPLICATIONS
fied as an anomalous codeposition through which
a less noble zinc metal (active) is deposited preferably In addition to zinc–nickel alloy coatings used in
and its percentage in the deposition is more than the steel car bodies [74, 75], they are considered for other
Poor
Automotive
Industry
Electronic Aerospace
Industry Industry
4 4
of corrosion resistance
Relative evaluation
Zn-Ni Alloy
Shipbuilding Fastener
coating
Industry Industry 3
Application 3 γ-phase
Pipe and
Transportation
profile
Industry
2 2
Industry
Other
Industry
1 1
Good
10 20 30 40 50
Concentration of alloying element
Fig. 3. Schematic of applications of zinc–nickel alloy coat- Ni in Zn coating layer, wt %
ings.
Fig. 4. Zinc–nickel alloy coated sheet design of different
corrosion tests in salt spray test (SST), external revealing
applications such as electrical catalysts [76–78], test, and corrosion simulation test (CST) [90].
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 sheet by electrodeposition process that does not
compared with the zinc coatings, zinc–nickel alloy change the mechanical properties of the base steel. In
coatings are investigated on electrical and building order to improve the anticorrosion performance of
products [83] and even for aluminum alloy coating typical electrogalvanized steel sheets, although it is
[84]. Also, zinc–nickel alloy coatings are suitable necessary to increase the zinc coating thickness, it
alternatives for cadmium coatings. Cadmium is highly reduces pressure weldability and ductility. The elec-
toxic and, considering the health and pollution risks, trodeposited metal coating should provide (1)
the environmental regulations are encouraging the use enhancing the corrosion resistance of zinc coating
of alternative protective systems [5]. In a study, zinc– layer [90] and (2) reducing the thickness of the coating
nickel alloys are sprayed in the ceramic coatings’ inter- and improving pressure ductility and weldability.
Designing the improved corrosion resistance in elec-
face on the steel substrate to improve the corrosion
trical deposition based on zinc protection in natural
and adhesion properties of plasma ceramic coating
environments is related to stabilizing Zn(OH)2 in nor-
[82]. Moreover, zinc–nickel alloy coatings are used for
chromate or other coatings [85–88]. Applications for mal natural atmospheres. The studies conducted on
zinc–nickel alloy coatings are summarized in Fig. 3. the stability of Zn(OH)2 synthesized with different
alloys indicate that the alloy elements such as Co, Ni,
Zinc protects mild steel from corrosion because of Mg, Al, and Mn slow down the conversion of
its sacrificial property. This alloy is used on one or Zn(OH)2 into ZnO. According to this concept, nickel
both side of the galvanized steel sheets with a relatively and cobalt are selected as alloying elements that can be
heavy coating, galvannealed steel sheets, electrogalva- electrodeposited [91]. When the real alloy coating
nized and steel plates coated with an organic powder composition stability is performed, the phase γ alloy is
that is commercially used for automobile body panels. chosen as a good balance of different corrosion tests
Although corrosion resistant steel sheets do not have that shown as Fig. 4 [90]. Electrodeposited zinc–
the application of high strength steel sheets to reduce nickel alloy steel plates have a good paintability similar
weight and the heavy painting steel plates, they have to cold rolled steel and effectively prevent scaling and
the decorative and hygienic, ductility, weldability and color bubbles. Furthermore, the excellent corrosion
other properties required for application of corrosion resistance of the electrodeposited steel plates is con-
resistant steel sheet to be used in cars [89]. Ductility firmed by real cars test in salt coated paths [92].
and weldability are important properties for making Currently, zinc is the most widely used corrosion
car body and producing a corrosion resistant steel protective coating investigated either by hot dipping or
0 10 20 30 40 50 60 70 80 90 100
1600
1455°C
1400 L
1200
1034°C 51.6
Temperature, °C
1000 37.9
β 876°C
815°C 57.5 70
800 (Ni) 35.3
652°C
56 71.5
600
491°C
β1 85.2
400 419.58°C
γ
361°C
Tc
200 δ
(Zn)
0
0 10 20 30 40 50 60 70 80 90 100
Ni Atomic Percent Zinc Zn
peritectic reactions at 1040 and 490°C produced β and zinc–nickel alloy coatings, according to the con-
δ phases, respectively. ducted surveys, it is possible to classify the deposition
baths into acidic [107, 108] and alkaline [109–111] two
In most cases, the pure zinc is the substrate for main categories. Each of these baths can be classified
materials coating on the steel. However, over the past in terms of the chemical composition of sulfate [112–
three decades, alloys are presented for a higher quality 114], chloride [115, 116] baths and other baths such as
of the end product and long lifetime. Major pressures acetate, ammonium [117], and citrate [118]. In order
from the automobile industry and in the aerospace to the comparison, zinc–nickel alloy coating proper-
field are investigated on the demand for faster and ties are evaluated in both acidic and alkaline baths. For
electrical equipment. Today, it is highly recommended example, the acid bath used has a chemical composi-
replacing cadmium due to its toxic nature. Electrode- tion with a concentration of NiSO4, ZnSO4, NiCl2,
position of zinc alloy will be discussed more in the
continuous electrodeposition. Zinc–nickel alloys can H3BO3 and trisodium citrate with pH = 3–4 and alka-
be deposit by acidic or non-cyanide alkaline solutions. line bath which has ZnO, NiSO4 and triethanolamine
The acid bath can have higher nickel content than an with the pH = 13–14. Figure 7 presents the effect of
alkaline bath. Corrosion protection of steel with is solution ratio in acidic and alkaline baths on zinc–
increased by raising the nickel content. Apart from this nickel alloy coatings. As the figure shows, the zinc–
amount, the deposition is nobler than the substrate nickel deposits have anomalous behavior because the
may lose its sacrificial properties. Finally, the deposi- nickel ratio is much lower than its ratio in solution. As
tion of the acid bath has a low thickness distribution the figure suggests, the nickel concentration in the
and alloy changes are observed in low to high-density deposition is lower than the electrodeposition in the
areas. Moreover, the speed of alkaline electrodeposi- alkaline bath due to the presence of alloying elements
tion bath is lower. Therefore, the column structure is as free ions in solution [119].
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 5.1. Electrodeposition from Acid Baths
barrel and rack electrodeposition bath is the dilution 5.1.1. Sulfate bath. Krisha et al. [71] used sulfate
of the barrel bath compared to the rack bath and also solution containing ZnSO4, NiSO4, H2SO4, Na2SO4,
its lower operating temperature [8]. and H3BO4 to deposit zinc nickel alloy. The alloys are
Different parameters affect the properties and used with galvanostatic deposition at the investigated
characteristics of the electrodeposition coatings. To current density of 10 mA/cm2 for the deposition on a
analyze these parameters on properties such as corro- mild steel rod. In this study, the effect of sulfuric acid
sion resistance, hardness [19, 106], and specifications and nickel sulfate concentration and deposition time
such as the components in the deposition and coating (from 1 to 20 min) was investigated. Zinc–nickel alloy
thickness can be mentioned. In deposition baths of phases varied with nickel concentrations and detected
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
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
Component of Ni, %
Zn
Component of Zn, %
–0.4
Current, mA cm–2
20 90
0 15 85
Eco 10 80
0.4 a Zn–Ni
Eη b Zn–Ni in presence of CP 5 75
c without metal
0.8 0 70
0 0.2 0.4 0.6 0.8 1.0
Magnetic field, T
–1.6 –1.2 –0.8 –0.4 0
Potential vs. SCE/V
Fig. 12. The effect of magnetic intensity on zinc–nickel
layers [128].
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, refinement in the deposits decreases to nanocrystal-
(b) 0.2 mM, V = 30 mV/s [101].
line size [82].
Interesting analyses are performed on the effect of
ZnCl2, NiCl2, and KCl. The cathode is a gold layer magnetic field on electrochemical deposition of zinc–
deposited on teflon. The results showed that zinc nickel alloy coatings [126, 127]. To study the effect of
hydroxide is electrodeposited because of an increase this field, the chloride bath including ZnCl2, NiCl2,
in pH [73]. KCl, NH4Cl2, and H3BO3 were used. The deposition
was done in the magnetic field parallel to the elec-
The chloride bath is used in the early studies con- trodes. Figure 12 indicates the effect of magnetic field
ducted on optimizing the electrolytic bath through cell on the concentration of elements in depositions. As
methods. NiCl2, NH4Cl, boric acid, nitric acid and the figure suggests, nickel concentrations in the
Thiamine hydrochloride are used to deposit electro- deposit are between 5–10 wt %. Besides, Ni2+ and
lyte containing ZnO. The killed steel plated active sur- Zn2+ ions have an equal positive charge but the mass of
face area of the cathode is used after preparation. By
Zn2+ is lower than Ni2+. Thus, at first, the ions are
adding small amounts of thiamine hydrochloride, a
significant improvement is seen on the gloss and accelerated under the same electrical power. Zn2+ ions
homogeneity of the deposition [125]. form the colloids cathode Zn(OH)2 along with zinc.
When a magnetic field is investigated, a force against
To improve the coating properties of the alloys, the the Zn(OH)2 colloids accelerates nickel deposition pro-
pulsed current density is investigated. In one of these cess [128]. In another study, the effect of magnetic field
studies, the chloride bath was used to investigating the on the deposition of alloy coating is analyzed in the chlo-
pulsed current density. Zinc–nickel alloy pulsed elec- ride bath with the composition ZnCl2, NiCl2, boric acid,
trodeposition was carried out on a mild steel plate or NH4Cl, gelatin, and glycerol and pure zinc anode and
on rotating disc electrodes of chloride bath ZnO, killed steel cathode. The polarization curve in Fig. 13
NiCl2, NH4Cl, and H3BO3. The results showed that presents the corrosion resistance of these coatings in a
the on-time did not affect the Ni content of deposits different magnetic field. The optimal mode is obtained
by the pulsed current [26]. in the field 0.6 T with 8.5 mm/y [129].
In another study, in order to investigating electro- The deposition of zinc–nickel alloy coating in the
deposition the chloride base, electrolyte was used by chloride bath was used from ZnCl2, NiCl2, H3BO3,
adding an appropriate amount of compounds ZnCl2, and hexylsulphate for the alloy deposition of nickel up
NiCl2, (Sodium lauryl sulfate) SL, and boric acid by to 20 wt %. Figure 14 indicates the alloy coating sur-
stirring in distilled. Sodium lauryl sulfate is used as the face with different nickel concentrations in zinc–
wetting agent to reduce the risk of cavities. This special nickel alloy coating. As shown in this figure, by
wetting agent is used for its wide application in the increasing nickel concentration the structure becomes
industry. Boric acid is used to maintain the pH of the fine-grained [130].
bath. The advantage of using a high amount of metal is An example of optimized chloride bath with acidic
that the high current densities can be used and pro- pH can refer to the bath with a chemical composition
duce thick deposits. The setting is performed by add- zinc chloride, nickel chloride, NH4Cl, KCl, glycine,
ing hydrochloric acid (to decrease pH) or ammonia and gelatin. The deposition was done by pure zinc
(to increase pH). By increasing nickel content, grain anode and the air was used for stirring. Optimization
–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
(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].
(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 optimized withvalues 25–150 g/L under the working
Zn/Ni 0.9 [138]. conditions 10 mA/cm2 and 25°C [9].
5.2.2. Chloride bath. Chloride baths that are ana- 5.2.3. Commercial alkaline baths. An example of
lyzed in the alkaline range are scarce. To study the fac- alkali baths containing NaOH, the base solution , pol-
tors affecting the zinc–nickel alloy coating properties isher, Ni and Zn ions were used in the research con-
such as temperature, pH, the ratio of components, and ducted by Hajjami et al. [47] zinc–nickel alloy deposi-
tion was carried on plain carbon steel using commer-
the effect of additives the chloride solution within the cial alkaline electrolyte solution with the dissolution of
range of pH = 7–8 was used. This bath included the the reagent ZnO, NiSO4, NH2CH2CH2NH2 and
materials with the concentration of NiCl2, ZnCl2, NaOH. Copper and platinum sheets were used as the
KCl, and HEDP (coordinating agent), and other cathode and anode, respectively. Figure 22 illustrates
additives with working conditions and current density the SEM images of zinc–nickel alloy deposition in 50
8.5–20 mA/cm2 where the zinc is the anode. Effects of and 100 mA/cm2. The nickel concentration in the
parameters based on nickel content in the bath are 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].
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)
Fe
Fe
400 nm 20 30 40 50 60 70 80 90
(c) (d)
Fig. 23. X-ray diffraction patterns of zinc–nickel codepos-
Fig. 22. SEM images of zinc–nickel alloys of zinc solu- ited coating [41].
tions containing ethylenediamine and triethanolamine
[83].
sition of zinc oxide, nickel sulfate, sodium hydroxide,
complexing agent (amine), and suitable additives.
ylenediamine solutions is 9.8 and 13.8 wt % while the Under these circumstances, the coating with nickel
deposits are at 50 and 100 mA/cm2 of triethanolamine content between 14–17 wt % is obtained. The corro-
solution as 8.4 and 79.2 wt %, respectively. The depo- sion resistance of the coating is 1000 h in the natural
sition obtained at 50 mA/cm2 of ethylenediamine salt spray without red rust [139].
solution presents the smooth surface of the trigonal-
pyramid (Fig. 22a) while at 100 mA/cm2 the dark edge In the electrodeposition of zinc–nickel composite,
of the trigonal pyramid is observed (Fig. 22b). In addi- alloy with alumina particles and alkaline bath with
tion, in the deposition of 100 mA/cm2, small crystals chemical composition NaOH, zincate75 (including
in the form of the crystalline core are seen above the zinc and NaOH), Ni-CPL were used. Deposition cur-
inner surface. Furthermore, the deposit at 50 mA/m2 rent density of composite is kept constant at
of the solution triethanolamine shown in Fig. 22c has 20 mA/cm2 by potentiostat-galvanostat. Figure 24
a smooth surface consisting of fine grains while the presents the X-ray diffraction of composite coatings.
deposit presented in Fig. 22d could be observed as As seen in this figure, the amount of Al2O3 and the
plane blocks. Surface morphology dependence with a phase γ value increases and the preferential orientation
current density in triethanolamine creates alloy com- appears at (330) and (600) [140]. Table 2 presents the
position. The nickel concentration in depositions of properties of Zn–Ni alloy coating of electrodeposited
ethylenediamine solutions is almost similar to that of from the alkaline bath.
triethanolamine solution and the surface morphology
of both deposits is compared. In the deposits in eth-
ylenediamine solution, the crystal plate surfaces are Cr Kα
Zn–Ni (a) λ = 2.2897 nm
smoother and few cracks are observed between the Zn–Ni–Al2O3 5 g/L (b)
γNi5Zn21(600)
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]
i, A cm–2
among the electrochemical deposition bath parame-
ters that have a major effect on properties and chemi-
cal composition of the surface [143–145]. Optimiza- 0
tion of these parameters is studied in several studies 0.10 M
[146–149]. In addition to the chemical composition, 0.20 M
thickness and surface morphology, hardness and cor- –0.005 0.30 M
rosion resistance are among determining factors in the 0.40 M
optimal state [150]. In the following, some of these 0.50 M
studies are discussed. –0.010
–1100 –1000 –900 –800 –700 –600 –500
E vs. Ag/AgCl mV
6.1. Compositions and Additives
In an electrodeposition bath, optimizing the vari- Fig. 25. Cyclic voltammetry curves for steel in different
ous concentrations of metal ions in the electrodeposi- concentrations of nickel sulfate at the scan rate 5 mV/s at
tion solution is important especially when industrial 30°C [71].
electrodeposition process of zinc–nickel alloy is
developed [151]. The effect of bath compositions on
characteristics of coatings such as brightness [152] is the cell patterns present burned deposits. The burned
considered as a means of a change in its concentrations areas without coatings are reduced when the nickel
[82, 153]. sulfate concentration exceeds 80 g/L. When the con-
centration of sodium sulfate reaches 100 g/L, the
6.1.1. Zinc sulfate. In a conducted survey to under- bright deposit provides. Thus, increasing the concen-
stand the zinc ion effect, the sulfate concentration was tration of sodium sulfate had no effect on the nature of
altered while the sodium sulfate, boric acid, and the deposition. Based on these observations, sodium
CTAB being kept. At lower zinc sulfate concentra- sulfate concentration is fixed at 100 g/L as the opti-
tions, the bright deposit was observed. At a lower cur- mum [46].
rent density range, a thin deposit was observed. It is
noticeable that the cell pattern has no burned deposits 6.1.4. ZnCl2. In an electrodeposition chloride
when the zinc sulfate concentration is 200 g/L. At bath, ZnCl2 concentrations were studied by keeping
higher concentrations, there is no change in nature of other additives constant. The variations of the ZnCl2
the deposit. Zinc concentration at 200 g/L is proven concentration change nickel concentration in the
optimal [46]. deposit in the range of 12.2–14 wt %. As expected, the
6.1.2. Nickel sulfate. To find out the impact of higher ZnCl2 concentrations in the bath first give
nickel metal ion, the nickel sulfate was varied by higher zinc amount (lower nickel). However, as Bren-
polynitroaniline, zinc sulfate, sodium sulfite, boric ner [50] suggested, the alloy composition has an
acid, and CTAB. At lower concentrations of nickel approximate dependence to increasing the amount of
sulfate, the bright deposition was observed. With the ZnCl2 in the bath. The results show that the electrode-
increase in the concentration of nickel sulfate, the position under these conditions is anomalous at the
bright deposition was developed [46]. The effect of area above the concentration of ZnCl2. The concen-
nickel concentrations in solution on the cyclic voltam- tration of nobler metal (nickel) is much lower than its
metry cathodic polarization is presented in Fig. 25. value in the bath. The changes in nickel percentage
Deposition potentials are shifted to positive values ions in the bath between 26.5 and 68% calculated by
with increased nickel concentrations. In addition, the the ratio of Ni/(Zn + Ni) in the bath are presented by
cathode current peak is associated with the release of changing the zinc content of the bath (adding ZnCl2)
hydrogen which consequently is reduced by increasing while nickel concentration in the bath is kept constant.
Ni2+ concentration. The phenomenon is caused by Using different electrolytes and direct electrodeposi-
adsorption competition between Ni2+ and H+ to tion conditions, similar results were observed in some
occupy the active sites by which the preferential studies. The electrodeposit surface morphology is not
adsorption of nickel is increased by increasing Ni2+ significantly affected by the changes in the concentra-
concentration [71]. tion of ZnCl2 in the tested range. As a typical example,
6.1.3. Sodium Sulfate. Sodium sulfate is commonly the SEM image for zinc–nickel alloy produced in
added to bath solution for increasing the conductivity concentrations of ZnCl2 is shown in Fig. 26. The
[46, 71, 114]. At lower sodium sulfate concentrations, deposits have a fine grain structure with average of
Current efficiency, % 100 6.1.6. Boric acid. The effect of boric acid on the
electrochemical deposition of zinc–nickel alloy layers
95 is highly complicated [71]. The purpose of adding
boric acid in electrodeposition bath is to control the
90
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-
85 centrations of boric acid, the deposit is bright in a
higher current range. The bright area is developed by
80 boric acid. Since the higher concentration of boric
0 0.1 0.2 0.3 0.4 0.5 0.6 acid has no effect on the pattern of cell pattern [46].
Concentration of formic acid, mol/L Experiments show that in most cases boric acid shifts
nickel concentration in the alloy toward the nickel-
Fig. 26. SEM image of zinc–nickel alloy pulsed electrical rich phases to prevent the deposition (by alloying).
deposition at a concentration of 300 g/dm3 ZnCl2 [82]. Boric acid also blocks the release of hydrogen. It is
expected that neutral molecules are boric acid are
grain size of about 0.5–2 μm. This result is expected replaced by the adsorbed anions (sulfates and chlo-
because the chemical composition had no specific rides) in the negative electrode in an electrochemical
changes. Moreover, it was also observed that nickel deposition due to more negative electrostatic force.
concentration in the deposition is an important When boric acid exists electrode surface, it is expected
parameter in controlling the morphology of the pulse to affect all the intermediate processes (release of
plated zinc–nickel alloys. All deposits had single hydrogen, zinc, and nickel deposits) [154]. Boric acid
phase γ caused by the XRD experiments. Based on the either forms a complex with Ni2+ and is used as a
above results, it is concluded that the resulting chemi- homogeneous catalyst or absorbed on the electrode
cal composition (12–14 wt % Ni) for corrosion pro- surface. This acid has a special role in the morphology
tection is obtained with the input ZnCl2 range. How- and composite characteristics. The presence of boric
ever, the high levels of ZnCl2 are selected to increase acid increases the efficiency of the deposition process,
the electrical conductivity of the bath [82]. the amount of zinc in the deposited alloy and nucle-
ation density. These effects are attributed to the
6.1.5. NiCl2. A series of tests are done in the chlo- absorption reactions at the electrode surface. More-
ride electrodeposition bath to determine the individ- over, boric acid is a buffer to hold electrolyte pH. Sim-
ual effects of NiCl2 concentration in the bath on the ilar effects of boric acid are observed during zinc–
chemical composition, morphology, and phase struc- nickel alloy deposition in sulfate baths [155]. It also
ture distribution in the deposit. The amount of depos- indicated that the impact of boric acid at different
ited nickel is increased up to 12.5 wt % by increasing ratios of Ni/Zn is due to the discharge reaction of H+
NiCl2 in the electrolyte. These results are consistent [156]. Boric acid at different concentrations is used in
with other studies indicating that by increasing the a chloride bath for galvanostatic coating of zinc–
nickel ions in the bath the nickel concentration of the nickel alloy with different concentrations of H3BO3.
deposition also increases. It is proposed that the linear Figure 27 presents the corrosion rate of zinc–nickel
relationship observed in the low range of NiCl2 is in coatings obtained by measuring the weight loss in
accordance with the theory that the reduction of NaCl solution. As shown in this figure, by increasing
nickel ions is controlled by the influence. The mor- the formic acid in solution, the corrosion rate is and
phology of deposition produced show that for deposits does not change thereafter. This behavior is attributed
generated at low concentration of NiCl2, the smooth to the reduction of nickel content in the deposition
surface morphology is obtained and the structure [157]. Figure 28 presents summary of effect of compo-
includes both fine-grained γ and coarse η crystals sitions Zn–Ni alloy coating bath.
phase. With increasing NiCl2 concentrations, the
deposit is very smooth and includes the phase γ with 6.1.7. Polynitroaniline. The effect of polynitroani-
fine grain nodded morphology with a grain size of line deposition was investigated in Hall Cell bath with
about 0.5–2 μm. Besides, there is an additional bene- the basic components of zinc sulfate, sodium sulfate,
fit of using high NiCl2 concentration to produce a CTAB and rough dark boric acid deposition. To
fixed concentration of deposit that even more fluctu- improve the deposition nature, polynitroaniline was
ations of NiCl2 concentration in the bath do not dissolved in ethyl alcohol and a certain amount of this
change the chemical composition of the deposit. Sim- solution was added to the bath. The bright deposition
ilar effects of fluctuations in the concentration of in is developed between the current density of 10 and
the bath at the lower range result in higher relative 30 mA/cm2. The deposit is dark at a lower density,
changes in the chemical composition and the phase while it is burned at high current densities. With
presence in the closer control of bath chemistry [82]. increasing the concentration of polynitroaniline has
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-
10 μm tion indicates that the black deposit is formed with
higher zinc ratio at a lower temperature and the bright
Fig. 27. Corrosion rate obtained by measuring the weight
deposit is formed with higher nickel ratio at a higher
loss of electrodeposited zinc–nickel weight [157]. 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
no effect on the deposition nature exceeding which a higher nickel content in the deposit [125].
darker deposit is achieved [46]. Temperature is one of the important factors the
changes of which affecting the zinc–nickel alloy coat-
6.1.8. CTAB. In a study conducted in the single ing properties. The effect of temperature on coating is
sulfate bath, at low CTAB concentrations, the nature studied while keeping constant the other electrodepo-
of deposit is semi-bright. The burned deposit is sition variables. Bath temperature changes the chemi-
observed at the high concentration. By increasing the cal composition (nickel content) of the deposits. It has
ZnSO4
NH4Cl H3BO3
Fig. 28. The schematic of effect of compositions on Zn–Ni alloy coating electrodeposited.
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- amorphous produced is similar to chemical compo-
ning, is increased by raising the temperature and then sition using direct current electrodeposition. The
increases much faster with the high temperature. This morphological changes observed in this study are due
behavior is attributed to a decrease in cathodic polar- to the changes in nickel concentration. The bath
ization and increased the kinetic parameters related to temperature in direct current electrodeposition had
temperature. Moreover, similar behaviors were no effect on both the crystal structure and on zinc–
observed in the studies on zinc–nickel coatings for nickel deposit texture. Similar results have been
electrical deposition and for pulsed and direct current reported by Fellion et al. [130] for direct current elec-
electrodeposition. The effect of temperature on sur- trodeposition of zinc–nickel alloys with comparable
face morphology revealed that for the deposits pro-
nickel values [82].
duced the smooth surface morphology is obtained and
the structure containing the γ-phase fine grain and Figure 30 presents the effect of temperature on the
coarse crystals of η phase are confirmed. At high tem- nickel content of the coating. It can be observed that
peratures, the deposition included α phase with mir- the nickel amount of coating increases by 5–10 wt %
rored morphology. In addition, the structure includes by increasing the temperature. The higher nickel con-
a relatively high number of micro-cracks that are a sign tent with increasing temperature can be attributed to
of the highly bright deposit. XRD pattern line width
cathodic polarization and temperature dependence of
analysis for this deposit indicates that the structure is
either the nanocrystalline (almost 2 nm according to kinetic parameters. The observations presented some
Scherrer formula) or amorphous. It should be noted small holes on the surface of the electrodeposition at
that the transfer from nanocrystalline to amorphous in high temperatures due to the release of hydrogen gas
electrodeposited alloys is not understandable now and that is not eliminated. Making holes could be due to
X-ray diffraction and electron tests are not suitable to the fact that higher temperatures activate hydrogen
determine the structure from peak widths diffraction release at low polarizations. Therefore, more nickel is
with crystal size lower than 3 nm. However, the results presented compared to the lower temperature and a
are in agreement with recent studies of Fratesi et al. better surface quality is achieved compared to the
[159] who reported that the electrodeposition of higher temperature [160].
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
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].
120 20 20 96
Deposition rate, mg h–1 Deposition Rate 18
110 18.9
Ni component, %
Ni Component 16 93.3 wt % Nickel
100 14 wt % Zinc
91.6
16 92
90 12 15.4
10 88.9
80
wt % Nickel
wt % Zinc
8
6 12 88
70
4 11.1
60 84.6
293 303 313 323 333
Temperature, K 8 8.4 84
wt % Nickel
6.7 wt % Zinc
Fig. 33. The effect of temperature on composition and 81.1
deposition rate of zinc–nickel film in bath chloride with
pH 6, the current density of 20 mA/cm2 deposition time of 4 80
the 1800 s [162]. 5 10 15 20 25 30 35
Deposition current density, mA cm–2
6.4. Current Density
Hall cell tests were investigated for 5 min by opti- Fig. 34. Nickel concentration and zinc in coatings based
on deposition current density [165].
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 ode current density on the coating thickness is linear.
that the optimized bath produces bright deposit within Linear dependence of thickness on the current density
the current density of 3–40 mA/cm2 [46]. might be due to metal hydroxide absorbed in the cath-
To optimize zinc nickel alloy bath for better corro- ode (induced by the constant increase in pH due to the
sion resistance, the effect of current density is evalu- release of hydrogen gas). Zinc–nickel alloy coatings
ated. Zinc–nickel alloys (with a different composi- adhesion was also investigated at different current
tion) formed on the Hall cell panel showed that the densities and found that all coating, except those at
cathode current density plays an important role in sed- high current density, have high adhesion to the
iment properties. The deposit range was from semi- smooth cut edges and no part of the deposit is isolated
bright to bright and then porous bright within the cur- from the substrate, implying that the coatings have
rent density range of 20–80 mA/cm2. Zinc–nickel excellent adhesion [163, 164].
alloy coatings were investigated at different current Figure 34 presents the effect of current densities on
densities and in different physical tests. The effect of the electrodeposition of zinc–nickel in sulfate bath.
current density on nickel wt %, hardness, thickness This figure presents atomic absorption spectroscopy as
and resistance to corrosion are were investigated. Cor- weight percentage. With increasing current density, the
rosion data show that the corrosion current density weight percentage of nickel concentration increases up to
decreases with the increased corrosion protection 7–19 wt %. The average grain size decreases with
[125]. It is observed that nickel wt % increases in the increasing current density. Dislocation density and
current density. Since at high current density zinc microstrain increased by reducing the grain size. By
metal deposition occurs more easily on the surface of
increasing the current density to 30 mA/cm2 corrosion
the cathode, an anomalous behavior of electrodeposi- resistance improved [165].
tion is noticed in Zn–M (the Fe and M = Ni, Co)
alloys. However, the nickel wt % increases at low cur- The effect of electrodeposition of current density in
rent density probably due to less hydrogen which pre- an acid-sulfate bath on nickel content at 40°C is pre-
vents the effects of high alkaline (hydroxide saturated sented in Fig. 35. As shown in the figure, the nickel
mechanisms). The hardness of zinc–nickel coatings content is almost doubled by increasing the current
changes within different current densities. It is con- density range. Increasing nickel concentration in the
cluded that the hardness of the coatings is reduced by coating is associated with the hydrogen prevention in
increasing the cathodic current. The reduced hardness the anomalous deposition mechanism of zinc–nickel
is related to the metal hydroxide obstacle in the crystal coatings. Based on this mechanism, the activity of
lattice due to the excessive release of hydrogen during nickel (less noble ion) in the bath is reduced by the for-
electrodeposition. Thus, through thick deposit formed mation of a stable complex [160]. The effect of depo-
at high current density, porosities with less hardness sition current density on the topography of the depos-
are reported. Thus, the coatings at a high current den- ited coatings obtained in Kelvin probe alkaline sulfate
sity become bright shiny deposits. The effect of cath- bath is presented in Fig. 36. It is observed that the
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
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
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].
80
25 Ni/Zn = 0.5 Ton/ms
70
Ni/Zn = 1.5 100
60 10
50 1
j, mA cm–2
20
Ni, %
40 0.1
DC
15 30
20
10
10 0
–10
0 10 20 30 40 –0.9–0.8–0.7–0.6–0.5–0.4–0.3–0.2–0.1 0 0.1
i, mA/cm2 E/V vs. SCE
Fig. 37. Nickel percentage in the deposit as a function of Fig. 38. The linear sweep voltammetry curves in Na2SO4 +
current density at different concentrations [166]. EDTA solution, dissolution of zinc–nickel alloys in direct
current, and pulsed current with Toff : Ton = 1 at different
values of Ton [26].
complex agents. Anodic linear sweep voltammetry is a
convenient electrochemical method for detecting the
alloy phase structure. Two dissolution peaks are In a study, chloride bath is used to deposit the
observed in the anodic linear sweep voltammetry that zinc–nickel alloy, using pulsed current and square
shows the presence of two different phase structure. In wave cathode pulses. Pulsed deposition time as the
all tested cases the current peak related to less noble alloy chemical composition resulting in constant cur-
potential peak is more than other current peaks and rent density is presented in Fig. 38, where the nickel
charging from this peak to another one is higher. The content is analyzed within the time, Ton. The increased
increased stop to pulse ratio shift the potential to less ratio of stop to pulse results in reduced amount of
noble amounts. Compared with direct current electro- nickel in the alloy; however, all zinc–nickel alloys
deposition, pulse electrodeposition can improve the require nickel concentration of 10–15 wt % to have a
deposition process and some properties such as poros- good corrosion protection [26].
ity, ductility, hardness and surface roughness. For 6.5.2. Toff. Similar to Ton, Toff has little impact on
alloy codeposition, the pulse electrodeposition can nickel concentration deposition. The surface mor-
produce the structures that are not possible to be pro- phology resulting from Toff values did not present a
duced by direct current electrodeposition [26]. For considerable difference; however, grain refinement is
most systems, electrodeposition speed that is deter- slightly increased when Toff is increased. Possibility,
mined by current density and current efficiency in the Ton is increased as a result of a small increase in
pulsed electrodeposition is usually higher than direct
nickel concentration. X-ray diffraction patterns indi-
current electrodeposition. Although a large number of
cate a change in the context based on Toff. The results
works has investigated zinc–nickel alloys electrodepo-
sition, less attention has been paid to pulse electrode- show that all the deposition produced at different Toff
position of these materials [82]. values have various γ structures. At the relatively low
Toff, the deposit had a strong preferred orientation
6.5.1. Ton. The effect of on time on microstructural (330), (411). With increased levels of Toff, peak inten-
characteristics of deposition is studied. This tempera- sities (600) and (422) were increased [82].
ture is set for the best alloy compound with the best 6.5.3. Toff/Ton ratio. The Toff/Ton ratios were ana-
corrosion resistance (12–14 wt % Ni) obtained a this lyzed over similar cathodes for all deposits. A potential
temperature. It is observed that Ton in the tested range shift to less noble values is consistent with the observa-
has a slight effect on the composition and nickel con- tion on the nickel content dependency of Toff/Ton ratio
tent is around 12–14 wt %. Also, the previous studies which indicates that by increasing the amount of
conducted by Knodler et al. [169] on the effect of Ton Toff/Ton nickel content is reduced in the alloy. Since it
on the chemical composition of the Zn-Ni alloy deposi- is assumed that the higher values of nobler nickel in
tion indicate that nickel content is highly dependent on the deposit presents nobler dissolution potential, it is
Ton. The present results suggest that Ton has a special concluded that by increasing Toff/Ton the nickel con-
effect on the surface morphology of the deposits such tent is reduced and the current peaks in anode linear
that all deposits had fine grain. The deposit produced at sweep voltammetry curves shift to more negative val-
Ton 75 ms indicates the normal morphology of deposits ues. The corrosion results show that the nickel content
for the range of Ton. X-ray diffraction patterns only indi- of the alloy is not the only factor responsible for corro-
cate the presence of γ phase for all deposits with preferred sion protection since nickel concentration in deposits
orientation (330) and (411) [82]. in this analysis is mostly the result of direct current
–Im Z (Ω cm2)
cluded that among all explored deposits in this study, 80
the deposit obtained by Ton = 1 ms and Toff/Ton of b
70
1 presents the best result [26].
6.5.4. Pulse current density. In another study, to 60
examine the characteristics of pulsed electrodeposi- 50 d
tion, the chloride bath was used and the pulse param- a
40
eters were studied. To study the effect of peak current
30 c
density (iP) on the deposit microstructure, the current
density was changed within the range of 10 to 30 mA/cm2 20
by setting the current average density and keeping Ton 10
and Toff constant. The increase in ip changes the Ni 0
between 12 and 14 wt %. Based on the results of 20 40 60 80 100 120
Knodler et al. [169] the nickel content of deposits has Re Z (Ω cm2)
higher or lower dependence on the current density
peak versus the higher zinc content in the bath. How- Fig. 39. Nyquist curve of zinc–nickel alloy coating soaked
ever, they proved that in the bath with 2 and 5 g/dm3 in NaCl solution of 3.5% for 24 h [170].
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 their good corrosion resistance [173]. Manufacturing
observed. This behavior is confirmed by the report of multilayer coating of zinc to protect the iron substrates
other deposited metals. Grain size reduction is the against corrosion is progressed significantly. In multi-
result of higher additional potential and the establish- layer coatings, each layer has its own role and the type
ment of nucleation. Also, the higher ip increases the and form of the layers are designed based on a number
electric strength of deposit of nickel-molybdenum of goals. Multiple coating systems including zinc and
alloy. X-ray diffraction patterns of zinc–nickel alloy other elements such as Zn–Co, Zn–Mn, Zn–Fe, and
deposition obtained indicate that the crystalline struc- Zn–Ni are recently developed to protect against cor-
ture of all deposits is the single γ phase. The XRD rosion of metal substrates [174].
results show that the preferred orientation is (330) and In zinc multilayer coatings such as the multilayer
(411). It should be noted that the copper peak in a zinc–nickel coatings, the noble layer of nickel has a
spectrum (in ip 10 mA/cm2) appears in the copper sub- protection against the aggressive ions and the zinc
strate partially in scanning X-ray diffraction [82]. layer protects the substrate against the corrosion the
The effect of pulsed reverse current density on the damaged areas in the coating [174]. Kalantary et al.
zinc–nickel alloy coating is analyzed by marking the [175, 176] and Chawa et al. [177], have deposited mul-
specimens as A, B, C, D, and E with respectively tilayer zinc–nickel coatings from pure zinc, sulfate,
pulsed reverse current densities of 0–100 mA/cm2 in a and nickel sulfamate electrolytes and measured their
chloride bath. The substrate is made of copper. corrosion resistance. The improvement in the corro-
Impedance spectroscopy curves of Fig. 39 presents the sion properties of multilayered coatings appears versus
corrosion behavior of the coating. As shown in this fig- pure zinc coatings [171, 173, 178, 179]. In addition, ini-
ure, the specimen A has weaker corrosion resistance tial electrochemical evaluation by salt spray indicates a
compared to other specimens [170]. The effect of var- good improvement by multilayered zinc–nickel coat-
ious parameters for electrodeposition of Zn–Ni alloy ings compared to the single-layer zinc–nickel coating
coating presents in Fig. 40. with the same thickness [172, 180].
The decrease in
The weight percentage the pH results in
Compact morphology, single The nickel content increases slowly of nickel in the deposit increased corrosion
phase and no-crack could until the temperature reaches 50°C increases with increasing resistance
be obtained at 30–40°C pH at values up to 5.5
sary to powerful vacuum system and its related costs, trolled by the amount of charge transferred, it has the
formation of nanoscale multilayer systems by electro- ability of deposition of layers with complicated forms,
deposition method to be more interesting than PVD the combination, and chemical defect is controlled by
and CVD procedures. Through this method, it is pos- controlling the over potential. Although unstable
sible to deposit smoother layers as every other one; phases can be also deposited, using one bath it is pos-
deposition of layer occurs at room temperature, there- sible to deposit several alloys and crystalline layers are
created with minimal defects. The disadvantages of
fore the possibility of diffusion between the layers is
this method are that the substrate and film should be
severely reduced. The layer thickness can be con- 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
10 μm coating with 11 substrates where the final layer is
nickel. The sample of cracks between the layers is
Fig. 41. Cross-section image of zinc–nickel multi-layer associated with the preparation of the cross-section
coating with 12 layers [184]. using mechanical methods [171].
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].
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
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 –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
10 000 due to the small size of the particle and the relatively low
Zn–NI amount that is under the X-ray fluorescence detection.
Background
Background
Zn–Ni–Al2O3 Figure 48 presents the Laser Ablation Inductively Cou-
Al intensity/counts per sec
(a) (b)
(a) 10 μm (b) 10 μm
1 μm ×5000 1 μm ×5000
(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)
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 cles to the deposit affects the microhardness. In fact,
capacity ring at higher frequency and conductor rings crystals with a smaller size produce greater grain
at a lower frequency. Nyquist curve values indicate boundaries that prevent the dislocation movement
that the amounts of electrochemical parameters are and increase the material’s hardness. Electrochemical
lower for the composite coating. Thus, by adding alu- impedance spectroscopy (EIS) for pure and compos-
mina no certain impact is seen on the double layer ite zinc–nickel coatings after 24 h of immersion to
capacity at the interface between the electrode and the measure polarization resistance indicates that polar-
electrolyte. Charge transfer resistance in the codepo- ization resistance (Rp) for zinc–nickel alloy coating is
sition of alumina was 50% lower than pure electrode- lower than composite zinc–nickel alloy coating. As it
position of pure zinc–nickel coating. In addition, hav- can be observed, the polarization resistance of the
ing a smaller ring diameter of the composite coating composite coating is better than pure alloy. The
indicated a higher corrosion resistance compared to reduced corrosion severity is related to structural and
pure alloy coating [188]. electronic properties of passive oxide [198].
The effect of composite particles on the micro- In the study conducted by Praveen et al. [192], the
hardness of the zinc–nickel composite coating with corrosion resistance properties of Zn–Ni–carbon
SiO2 particles presents the increased hardness from nanotube coatings were analyzed. The presence of
140 HV for the pure zinc–nickel alloy to 360 HV for carbon nanotube provides a higher corrosion resis-
the specimens prepared by SiO2 particles. It can be tance for Zn–Ni–carbon nanotube coatings. The
concluded with the addition of this type of nanoparti- 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
1.5 shifted to more positive values in all current densities.
Zn–Ni Rs Rct
Zn–Ni–Al2O3 CPE The shifting indicates that Zn–Ni–carbon nanotube
Fit results L1 R1 composite has more satisfactory reducing power.
1.0
Thus, the corrosion behavior is improved. The results
Zim, Ω cm2
Polarization potentiodynamic test was performed zinc–nickel alloy coating compared to other chemical
on zinc–nickel coated steel obtained by the bath con- compositions of the alloy and increases the life length
taining additives and TiO2 nanoparticles at different of the specimens. The more satisfactory corrosion
concentrations. TiO2 nanoparticles (21 nm) were resistance mechanism of zinc–nickel coating com-
added to the electrodeposition bath to obtain a com- pared to zinc and cadmium can be divided into two
posite coating with different concentrations. As it can stages. In the first stage of immersion better corrosion
be observed, adding polyethyleneglicol (PEG) and resistance is because of desenfication speed. Dezenfi-
vanillin to the electrodeposition bath has reduced cor- cation is related to surface morphology and wettability
rosion current density compared to the zinc–nickel of zinc–nickel alloy. After the passage of immersion
coating without the additive. Furthermore, the addi- time, the corrosion performance of zinc–nickel alloy
tion of TiO2 reduces corrosion current density com- is related to the combination of corrosion products.
pared with pure zinc–nickel coating [199]. 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-
8.3. Zinc–nickel Composite Coating Applications pared to zinc and cadmium coatings. Zinc–nickel
In order to develop the application of coatings, alloy coating has lower internal stress at the concentra-
metal matrix composite coatings are recently devel- tions below 10 wt %. An important property of this
oped to improve the chemical and mechanical proper- alloy is the anomalous behavior that increases the
ties. Composite coatings have various properties such fractional zinc content in coating compared to its
as uniform hardness, self-lubricating, high-tempera- amount in deposition bath. Electrodeposition of
ture oxidation resistance, excellent coverage, and cor- zinc–nickel alloy coating is done in a variety of acidic
rosion resistance [187]. Generally, oxide and carbide and alkaline baths. The chemical composition of these
components such as Al2O3, TiO2, ZrO2, SiO2, Fe2O3, baths is often as sulfates, chlorides, and other materials
SiC, and WC or even diamond and carbon nanotube and additives. The selected bath and the presence and
are used as the second phase. Coelectrodeposition is type of additives have a great effect on the zinc–nickel
widely used to prepare metal matrix compounds alloy coating deposition properties that have been
because of the low cost and versatility. Usually, the studied with a variety of analyses. The reports indicate
solid micro/nanoparticles are added to the electrode- the presence of γ-phase of one of zinc–nickel alloy
position bath under severe agitation, air injection, or phases in most phases appeared in the XRD analysis.
ultrasonic vibration [200]. Table 4 presents a summary In zinc–nickel alloy coating, deposition parameters
of the properties and various types of Zn–Ni compos- such as materials and additives, bath pH, temperature,
ite alloy coatings. deposition current, and pulsed and direct deposition
are effective on the quality and coating properties.
Reports of resistance to corrosion, composition and
9. SUMMARY AND FUTURE TREND grain size of the coating and surface morphology
Because of its low price, favorable properties, and influenced by the parameters in the report reflect the
abundance, steel has found widespread applications in improved properties by forming the phase γ in the
industry. One of the major problems of this alloy is its coating.
low corrosion resistance in corrosive environments, Zinc–nickel alloy coating as composite and multi-
especially in the atmospheric environment. One of the layered are also being investigated. These coatings
methods of improving corrosion resistance is a surface incorporated a variety of oxide and non-oxide parti-
improvement by coating through electrodeposition cles are reported to improve corrosion and wear resis-
and cadmium coating. Toxicity of cadmium coatings tance. Different types of particles like Al2O3, TiO2,
has inspired an international attention toward an alter- ZrO2, SiO2, and WC or even diamond and carbon
native for this coating. Zinc based coating with sacrifi- nanotubes have been used in this method. Zinc–
cial properties and low electrode potential is considered nickel multilayer coating is another coating that is
as a suitable alternative coating for toxic cadmium. Elec- widely studied in these analyses. The studies con-
trodeposition of zinc coating is investigated in industries ducted on these coatings indicate their importance
such as automotive, aerospace, electronics, etc. To and the future applications. It is predicted that these
achieve corrosion resistance and increase long life coatings are suitable alternatives to zinc–nickel coat-
these coatings are investigated with a higher thickness ings to improve the properties and corrosion resistance
which reduces ductility and weldability. more importantly. It is reported that the corrosion
Zinc-based alloy coating with an iron group (iron, resistance of the coatings is 35 times more than the
cobalt, and nickel) is an example of a zinc alloy coat- corrosion resistance of single layer coatings with simi-
ing that improves ductility, weldability, and paintabil- lar thickness. Multilayered zinc–nickel coatings are
ity of the specimen. Among these coatings, zinc– both as periodic pure zinc–nickel coating and in the
nickel alloy has higher corrosion resistance and better form of alloy layers. With the increase in the number
properties than other alloys groups. This coating with of layers in the coatings, the corrosion resistance of the
8–15 wt % nickels has better corrosion resistance in coatings is increased. Another parameter affecting the
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]
ZnSO4–NiSO4–Na2SO4 SiO2 20, 2000 1–12 N.R. –550 to –1050 N.R. N.R. [193]
Other
sion resistance in the environment with high-tempera-
4% ture conditions. Thus, these coatings might have good
Defense
industries
results in hydrogen embrittlement (ASTM F519)
8% [201], fatigue, and SO2 corrosion tests as well.
Aerospace industries
8%
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