Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Recent researches on Cu-Ni alloy matrix composites through

electrodeposition and powder metallurgy methods: A review
Ajay D. Pingale a,⇑, Ayush Owhal a, Anil S. Katarkar b, Sachin U. Belgamwar a, Jitendra S. Rathore a
a
Department of Mechanical Engineering, Birla Institute of Technology and Science, Pilani, Rajasthan 333031, India
b
Department of Mechanical Engineering, National Institute of Technology Agartala, 799046, India

a r t i c l e i n f o a b s t r a c t

Article history: Copper-nickel (Cu-Ni) alloy matrix composites have been extensively used in many industries due to
Available online xxxx their high mechanical strength, good wear and corrosion resistance, and exceptional electrocatalytic
properties. This review gives a comprehensive overview of the recent development in the synthesis of
Keywords: Cu-Ni alloy matrix composites by electrodeposition and powder metallurgy methods. The incorporation
Coatings of particles into the Cu-Ni alloy matrix produced improved properties in the fields of mechanical, chem-
Cu-Ni alloys ical, marine and electronics engineering. In the marine environment, an increase in demand for high cor-
Electrodeposition
rosion and wear resistance properties for boat hulls, marine hardware, condensers and heat exchangers
Alloy matrix composites
Nanoparticles
were observed. Cu-Ni alloy matrix composites prepared using the electrodeposition method suggest a
most simple and economical way to improve the overall properties.
Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 3rd International Con-
ference on Advances in Mechanical Engineering and Nanotechnology.

1. Introduction the material surface is very important. The degradation of material

As the frontier of modern technology and science spread out
into more complex and sophisticated fields, the operating system
tackles harsh working conditions. Therefore, modern technology
quests for systems with high performance in extreme and often
an adverse working environment. Polymer composites have
attracted significant research interest due to their low cost, low
weight, biodegradability and facile processing [1]. Nowadays, poly-
mer composites are employed in several applications such as ther-
mal flow control, defence systems, energy storage, aeronautics and
aerospace due to enhanced thermal, mechanical and wear proper-
ties [2,3]. In addition, industrial waste filled polymer composites
are being used in automobile, aircraft and mechanical industries
due to enhanced thermal and mechanical properties [4]. The mate-
rial surface is the most vulnerable site for different forms of
attacks, including mechanical, electrochemical, chemical and ther-
mal. As these attacks proceed, the degradation of material surfaces
is initiated and leads to damaging changes at the material surface.
The damages mainly due to the corrosion and wear attack at the
material surface are not recoverable. Therefore, the protection of
⇑ Corresponding author.
E-mail address: ajay9028@gmail.com (A.D. Pingale).
surfaces can be decreased by applying a surface coating or chang-
ing the entire material of the part that will lessen the effect of
given working conditions and surrounding environment and
extending the service life, not just the surface but the entire equip-
ment. However, the application of a protective coating is more fea-
sible and economical than changing the entire material of the part.
Thus, surface modification technologies have found a wide range of
applications in several engineering industries to protect material
surfaces from corrosion and wear. The selection of the suitable
coating technique depends upon many factors including, applica-
tion, economics, feasibility, etc. Cu-Ni alloy parts and Cu-Ni alloy
coatings have been widely used in most engineering applications
due to their unique physical and mechanical property. However,
to enhance their performance in harsh working conditions, rein-
forcing elements have been added to them.
1.1. Major challenges facing by various engineering sectors
Nowadays, deterioration of active metals such as Al, Mg and Fe
under the influence of wear and corrosion is a serious problem
faced by marine, automobile and chemical industries [5]. Among
these active metals, mild steel is extensively used due to its good
mechanical strength, low cost and durability. The rate of wear

https://doi.org/10.1016/j.matpr.2021.07.145
2214-7853/Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 3rd International Conference on Advances in Mechanical Engineering and Nanotechnology.

Please cite this article as: A.D. Pingale, A. Owhal, A.S. Katarkar et al., Recent researches on Cu-Ni alloy matrix composites through electrodeposition and
powder metallurgy methods: A review, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2021.07.145
A.D. Pingale, A. Owhal, A.S. Katarkar et al.
and corrosion can be controlled using some approaches such as
changing the surrounding environment, selecting materials, and
providing metallic coatings. Among these approaches use of metal-
lic coating is the most acceptable approach. The efficiency of
metallic components which are subjected to corrosion and wear
is possible to improve by providing pure and alloy coatings [6].
1.2. Cu-Ni alloy: characteristics and applications
The copper alloy has played an important role in electrotechnol-
ogy, building and construction, chemistry, offshore applications,
mechanical engineering, automotive, marine engineering, medical
purposes and many others [7]. Cu is alloyed with several metals.
Cupronickel alloys have outstanding anti-fouling and anticorrosion
properties in seawater and thus have been extensively used in
marine applications such as heat exchanger tubes, ship pipes, boi-
ler parts, pump impellers, conduits, pump bodies and components,
boat hulls, valve bodies, seawater condensers, pipe fittings, oil rigs
and platforms, seawater intake screens, fish farming cages and
other ship hardware [8]. Some of the most used cupronickel alloys
consist of copper with 30% nickel and copper with 10% nickel. In
the year 1920 s, a 70–30 copper-nickel alloy was fabricated for
application in naval condensers. A 90–10 copper-nickel alloy was
first fabricated in the year 1950 s. In the beginning, it was used
for seawater piping and is now the more widely used alloy [9].
The addition of nickel to copper enhances its tensile strength, duc-
tility, thermal conductivity and thermal expansion as well as
improves its resistance to corrosion, cavitation and erosion in all
kinds of water. The alloy also shows excellent corrosion resistance
to fatigue and stress corrosion cracking [10]. The chemical industry
uses cast products, tubes and sheets made of copper-nickel alloys
in oil refineries industries for fittings, impeller wheels, valves and
pump bodies and piping for the salt environment and other highly
corrosive solutions in heat exchangers, agitators and mixers, pres-
sure and other vessels, cooling devices, autoclaves and many other
types of equipment. The food processing industry uses copper
nickel alloys for agitators, multistage evaporators, feed water boil-
ers, sugar refineries, piping and apparatus for fruit sieves, mixers
and presses, food packaging [11].
2. Environmental and health concerns
Several methods were adopted to fabricate particle reinforced
metal matrix composites coatings such as electrodeposition,
plasma spraying, laser cladding, CVD and high-velocity oxygen fuel
flame spraying [12,13]. However, electrodeposition and powder
metallurgy methods are most widely employed for the synthesis
of Cu-Ni alloy composites. The electrodeposition method has been
used to synthesize Cu-Ni alloy and Cu-Ni alloy composite coatings
to protect the base material from harsh working conditions. Also,
powder metallurgy has been used for the synthesis of Cu-Ni alloy
and Cu-Ni alloy composites. Electrodeposition is an economical
and simplest process to fabricate metal composites coatings. This
is an ancient method with numerous features that make it best sui-
ted for nano and macro technologies. The electrodeposition pro-
cess can be carried out on different substrates. It can be scaled
up. It can be performed at room temperature, and it has a high pro-
duction rate with pore-free coatings. The characteristics of depos-
ited coatings can be controlled by optimizing the process
parameters such as magnetic stirring rate, pH, temperature, rein-
forcement concentration, current density, and bath composition
[14]. However, electroplating process of Cu and Ni (Cu and Ni
cause’s selective skin irritations) produces extremely hazardous
substances such as various nonmetallic and metallic ions, which
are very harmful to human health and the environment. The
2
Materials Today: Proceedings xxx (xxxx) xxx
alternative of some harmful bath materials is considered the most
appropriate way to decrease the risk.
3. Synthesis Cu-Ni alloy matrix composite coatings through
electrodeposition method
Pure Cu and Cu alloys are widely used in electrical, automobile,
chemical, electrical, mechanical and marine applications due to
various merits such as high strength and good corrosion and wear
resistance. Cu coating has a widespread application in the manu-
facturing of electronic devices because of its high electromigration
resistance, superior electric and thermal conductivity, and excel-
lent mechanical and chemical characteristics. Also, Cu is used in
some medical applications owing to its excellent anti-bacterial
properties [15–17]. To increase the utilization of pure Cu, it is
strengthened by work hardening or by the addition of alloying ele-
ments. Copper is alloyed with different metals and is mainly clas-
sified into Cu-Zn [18], Cu-Sn [19], and Cu-Ni [20]. Nowadays, Cu-Ni
alloy coatings are extensively used in automobile, chemical, mar-
ine, and mechanical applications because of their superior resis-
tance against corrosion in seawater, durability and good strength.
Also, Cu-Ni alloy coatings are preferred in the condenser, heat
exchangers, microelectronics, and pipeline in marine environ-
ments [11]. The 70–30 Cu-Ni alloy has high strength and excellent
corrosion resistance in many oxidizing and reducing gas environ-
ments, seawater, and alkaline and acidic media than the 90–10
Cu-Ni alloy coating, hence more widely used [21]. Also, 70–30
Cu-Ni alloy coating has a higher hardness than 90–10 Cu-Ni alloy
coating due to the high weight percentage of nickel.
3.1. Mechanism of Cu-Ni electrodeposition
The mechanisms of Cu-Ni alloy electrodeposition are presented
in Fig. 1. Fig. 1 gives an idea of the different aspects involved in the
selection of operational conditions and bath composition. The stan-
dard reduction potentials of Cu and Ni are + 0.34 V and
0.25 V,
respectively, which considerably differ from each other [5]. Hence,
in the electrolyte bath, the concentration of Ni2+ is usually kept
higher than that of Cu2+ and a complexing agent is also added, thus
allowing the co-deposition of Cu and Ni on the cathode surface. For
instance, the work of Pellicer et al., [22] shows that the nickel con-
tent in the Cu-Ni alloy coating is augmented with an increase in
current density. Also, at a low current density deposition rate of
copper is higher than the deposition rate of nickel; hence, Cu-Ni
alloy coating is rich in copper color. However, at a higher current
density, the deposition rate of Ni is higher than the deposition rate
of Cu; hence Cu-Ni alloy coating is rich with nickel color [7]. Usu-
ally, Cu and Ni anode plates are used in Cu-Ni alloy coating depo-
sition to maintain the concentration of Cu and Ni ions in the
electrolyte bath during the electrodeposition process.
The electrodeposition reactions of Cu-Ni alloy coating have
been modeled as follows:
In case of a soluble anode, Cu and Ni ions are formed at the
anode surface (Eq. (1) & Eq. (2))
Cu þ 2e
¼ Cu2þ ð1Þ
2þ
Ni þ 2e
¼ Ni ð2Þ
In the case of an insoluble anode such as Pt/Ti, oxygen is
evolved at the anode (Eq. (3))
2H2 O þ 4e
¼ O2 þ 4Hþ ð3Þ
At the cathode, Cu and Ni ions are discharged simultaneously to
form Cu-Ni alloy coating (Eq. (4) & Eq. (5)):
A.D. Pingale, A. Owhal, A.S. Katarkar et al.
Fig. 1. Electrodeposition of Cu-Ni alloy coating and different aspects involved in the selection of operational conditions and bath composition.
Cu2þ þ 2e
¼ Cu
2þ
Ni þ 2e
¼ Ni
2Hþ þ 2e
¼ H2
Eq. (6) shows the hydrogen evaluation reaction that occurs dur-
ing the electrodeposition process at the cathode surface, which
results in a decrease in local pH and current efficiency and an
increase in the porosity of the coating. This is due to the increased
H2 bubbles on the coating surface, in case surfactant is not used or
cathode movement is fixed.
3.2. Electrolytes used in electrodeposition of Cu-Ni alloy and composite
coatings
For electrodeposition of Cu-Ni alloy and composite coatings,
different baths have been used, such as chloride, acetate, sulfate
(Watt- type), sulfamate, lactate and glycine. A survey of the litera-
ture for the bath composition for electrodeposition of Cu-Ni alloy
and composite coatings is shown in Table 1.
3.3. Chloride bath
The basic composition of a chloride bath consists of copper
chloride and nickel chloride. Boric acid, sodium citrate, sodium
dodecyl sulfate, and saccharin are commonly used as supporting
agents. The chloride-based bath is not favorable for non-
consumable electrodes. The coatings prepared in chloride-based
baths are rough and loose surfaces with several defects and cracks,
which would result in low corrosion resistance. A chloride bath can
be used to increase the ductility of nanocrystalline materials for
several industrial applications. However, its deposits have high
internal stress [31]. Deng et al., [39] have described the electrode-
position of Cu-Ni alloy in 1-ethyl-3-methylimidazolium dicyana-
mide ionic liquid (EMI-DCA IL) containing anhydrous nickel
Materials Today: Proceedings xxx (xxxx) xxx
ð4Þ chloride and copper chloride. It was found that the metal ions con-
centration in the electrolyte bath and the deposition potential had
an impact on the compositions of the Cu-Ni alloy coating. Also,
ð5Þ
EMI-DCA IL is difficult to synthesize, costly, and can have an
adverse effect on human health and the environment. Recently,
ð6Þ Wang et al., [40] fabricated the Cu-Ni alloy coating by electrodepo-
sition method from a eutectic-based ionic liquid containing nickel
chloride hexahydrate and copper chloride dihydrate and investi-
gated the electrodeposition effect on the compositions, microstruc-
tures and corrosion resistances of Cu-Ni alloy coatings. The results
showed that the deposition current density significantly influenced
the compositions, microstructures, and corrosion resistance of Cu-
Ni alloy coatings.
3.4. Watts-type (sulfate) bath
The watts type baths are one of the most popular baths in elec-
trodeposition methods. The watts type bath was invented by O. P.
watts about 100 years ago. The Cu-Ni coatings prepared from
watts-type baths are explored in earlier studies. Sulfate-based
baths are extensively used baths in the industry due to their eco-
nomic aspects. This bath consists of copper sulfate, nickel sulfate,
and supporting agents. Sodium citrate is used as a complexing
agent to stabilize the electrolyte system, and boric acid is
employed to adjust the pH of the electrolyte solution. To avoid
an insoluble citrate complex forming and precipitating out of the
solution, the pH value of the citrate bath is restricted [41]. Citrate
type bath has several advantages such as less maintenance, easy to
use, low cost, low corrosion of equipment and its deposits have low
internal stress compared to other baths. However, deposits from
this bath have high tensile strength and hardness. Ghosh et al.,
[21] synthesized the Cu-Ni alloy coating by pulse electrodeposition
method from citrate bath containing copper sulfate, nickel sulfate,
and supporting agents. It was found that the pulse parameters and
operating conditions had a significant effect on the composition,
current efficiency, and quality of the Cu-Ni alloy coatings.
3
A.D. Pingale, A. Owhal, A.S. Katarkar et al. Materials Today: Proceedings xxx (xxxx) xxx

Table 1
Bath composition and operating conditions employed for preparing Cu-Ni alloy and Cu-Ni alloy matrix composite coatings by the electrodeposition process.

Coating Bath composition pH Temp. Current density Goal Ref.

(°C)
Cu-Ni 0.475–0.5 M NiSO47H2O, 9 40 20 A.dm
2 (PC) Improving corrosion resistance and microhardness [21]
0.10–0.125 M CuSO45H2O,
0.2–0.3 M Na3C6H5O7
Cu-Ni 0.02 M NiSO47H2O, 5 55 ± 1 2.5, 5, 7.5, 10, 15 & Investigating the effect of duty cycle and current density [7]
0.002 M CuSO45H2O, 20 A.dm
2 (PC) on lattice constant and magnetic properties
0.2 M Na3C6H5O7
Cu-Ni 184 g/L NiSO47H2O, 4.5 30 0.210 V Improving corrosion resistance in a chloride medium [22]
6.24 g/L CuSO45H2O,
87 g/L Na3C6H5O7,
0.5 g/L C7H5NO3S,
0.2 g/L NaC12H25SO4
Cu-Ni 2.0 M Ni(SO3NH2)24H2O 2, 2.6 & 23
1.7 V Investigating the effect of electrolyte pH and Cu [23]
0.01–0.04 M CuSO45H2O, 3.3 concentration on the microstructure of Cu-Ni alloy films
0.5 M H3BO3
Cu-Ni 0.07 M NiSO47H2O, 3.5 ± 1 25
1.2,
1.4,
1.6 & Investigating the effect of deposition potential on [24]
0.0014 M CuSO45H2O,
1.8 V morphological and structural properties of Cu-Ni alloy
0.04 M H3BO3 films
Cu-Ni 0–0.5 M Ni(H2NSO3)24H2O 3, 4, 5 & 25
1.5–0.5 V Developing plating baths to produce reflective Cu-Ni [25]
0–0.025 M (CH3COO)2CuH2O 6 films
0–0.25 M Na3C6H5O72H2O
Cu-Ni 174 g/L NiSO47H2O, 16 g/L CuSO45H2O, 4.5 30 0.25 V Improving corrosion resistance and hardness [26]
87 g/L Na3C6H5O7,
0.5 g/L C7H5NO3S,
0.2 g/L NaC12H25SO4
Cu-Ni 0.07 M NiSO47H2O, 4.4 ± 0.2 25, 40,
9 mA.cm
2 (DC) Investigating the effect of electrolyte temperature on [27]
0.0014 M CuSO45H2O, 55 & morphological and structural properties
0.04 M H3BO3 70
Cu-Ni 0.2 M NiSO47H2O, 2, 2.5, 3 25 100 mA.cm
2 (PC) Synthesis of Cu-Ni alloy nanoparticles using pulsed [28]
0.04 M CuSO45H2O, & 3.5 sonoelectrochemistry
0–0.2 M Na3C6H5O7
Cu-Ni 0.2–0.8 M NiSO47H2O, 9 20 1 & 2 A.dm
2 (DC) Investigating the effect of current density and bath [29]
0.05–0.2 M CuSO45H2O, composition on elemental composition and structure of
0.2 M Na3C6H5O7 coatings
Cu-Ni 0.02 M NiSO47H2O, 5 23 5, 10, 50, 100, 150 Improving electrocatalytic performance of the Cu-Ni [30]
0.002 M CuSO45H2O, and 300 mA.cm
2 alloy electrodes.
0.2 M Na3C6H5O7 (DC or PC)
Cu-Ni 300 g/L Ni(O3SNH2)2 4.5 50 2 A/dm2 (PC) Improving tensile ultimate and tensile strength of Cu-Ni [31]
2.5–15 g/L CuSO45H2O, alloys
20 g/L NiCl2, 20 g/L H3BO3,
80 g/L Na3C6H5O7,
2 g/L C7H5NO3S,
0.1 g/L NaC12H25SO4
Cu-Ni/MMT 0.32 M Ni(NH4)2(SO4)26H2O 6 25
1.0 V Improving mechanical and corrosion properties of [32]
0.06 M CuSO45H2O, 70:10 Cu-Ni alloy
0.25 M Na3C6H5O7,
MMT (0.05, 0.1, 0.2%)
2.0 M NaOH
Cu-Ni/Al2O3 105 g/L NiSO47H2O, 4 35 2 A/dm2 (DC) Improving microhardness, wear resistance and [33]
25 g/L CuSO45H2O, corrosion resistance
59 g/LNa3C6H5O7
Al2O3 (0–30 g/L)
Cu-Ni/MMT 0.24 M Ni(NH4)2(SO4)26H2O 0.06 M 6 25
1.0 V Improving hardness, shear strength and corrosion [9]
CuSO45H2O, 0.25 M Na3C6H5O7, MMT resistance properties of 90:10 Cu-Ni alloy
(0–0.15%), 2.0 M NaOH
Ni-Cu/TiN 160 g/L NiSO47H2O, 4.3 ± 0.2 50 2 and 4 A/dm2 (PC) Improving corrosion resistance by ultrasonic agitation [34]
15 g/L CuSO4.5H2O,
20 g/L H3BO3, 8 g/L TiN,
1 g/L C7H5NO3S, 0.05 g/L NaC12H25SO4
Ni-Cu-ZrO2 70.96 g/L NiSO47H2O, 8–9 30 6–20 mA/cm2 (DC) Improving microhardness and corrosion resistance [35]
15 g/L CuSO4, properties
42.6 g/L Na2SO4,
63 g/L Lactic acid
(0–16 g/L) ZrO2
Ni-Cu/TiN- 160 g/L NiSO47H2O, 4.2 ± 0.1 50 ± 1 3–6 A/dm2 (PC) Investigating the effect of pulse parameters on surface [36]
ZrO2 15 g/L CuSO45H2O, morphology and microstructure of coatings and
20 g/L H3BO3, improving corrosion resistance
1 g/L C7H5NO3S, 0.05 g/L NaC12H25SO4,
6 g/L ZrO2, 4 g/L TiN
Cu–Ni–Cr 100 g/L NiSO47H2O, 7 35 1 A/dm2 (DC) Improving oxidation resistance [37]
5–20 g/L CuSO45H2O,
12 g/L NiCl7H2O,
25 g/L H3BO3,
120 g/L Na3C6H5O7,

4
A.D. Pingale, A. Owhal, A.S. Katarkar et al.
Table 1 (continued)
Coating Bath composition pH Temp.
(°C)
(0, 15, and 20 wt%.) Cr
Cu–Ni–Gr 21 g/L CuSO45H2O, 4 40
105 g/L NiSO47H2O,
59 g/L Na3C6H5O7,
(0, 100, 200 or 400 mg/L) Gr
Ni–Cu-Y2O3 150 g/L NiSO47H2O, 4–5 60
30 g/L CuSO45H2O,
50 g/L Na3C6H5O7,
30 g/L H3BO3, 1 g/L C7H5NO3S, 0.4 g/L
NaC12H25SO4
0–5 g/L Y2O3
3.5. Sulfamate bath
The basic composition of the sulfamate bath consists of nickel
sulfamate, copper acetate and sodium citrate. Sulfamate, citrate
and acetate are selected as being less hazardous substances to
the environment [42]. In most of the studies to accomplish simul-
taneous deposition of Cu and Ni ions, sodium citrate was used as a
complexing agent [27]; also it acts as a buffering, brightening and
leveling agent, thus eliminating the need of bath additives [43].
Sulfamate bath has several advantages, such as excellent stability
for temperatures by up to 60 °C and for pH range from 2 to 4
[44]. The sulphamate baths can operate at high concentration
and high current effectively. The properties of sulfamate deposits
such as hardness, thermal conductivity, ductility, mechanical
strength, internal stress, microstructure, porosity, roughness, den-
sity, specific heat can be affected by operating conditions and
impurities [45]. The sulphamate baths are used for many engineer-
ing applications due to the high deposition rate, low residual
stress, excellent dimensional corrections and high throwing power.
3.6. Lactate bath
The Ni–Cu alloy thin films prepared from an environmentally
friendly lactate bath have been studied [46]. This bath is composed
of nickel sulfate, copper sulfate, lactic acid and supporting agents.
Lactic acid has been used as a complexing agent. Lactic acid is
cheap, easily available and non-toxic in nature. Bright, compact
and smooth Ni–Cu alloy thin films have been successfully obtained
using a lactic acid-based electrolyte bath. Cathodic polarization
measurements revealed that the amount of Ni in the coating is less
than its amount in the electrolyte bath, demonstrating that the
deposition of Ni–Cu alloy is of a regular type [47]. It is also reported
that the cathodic efficiency is high and mainly depends on temper-
ature, pH and the applied current density. The deposited Ni-Cu
alloy films consist of a single solid solution phase with f.c.c. struc-
ture. The obtained crystallite sizes for deposited Ni-Cu alloy films
range from 12 to 25 nm. Also, it is observed that the increase in
the temperature of the electrolyte bath leads to an increase in
the crystallite size of the Ni-Cu alloy film.
3.7. Glycine bath
The glycine bath is employed as a complexing agent in the elec-
trodeposition of alloy coatings including Zn-Co-Cu, Co-Ni-Mo, Cu-
Co, Zn-Co, and Zn-Ni to achieve high-quality deposits [48]. Also,
it acts as a buffering agent and stabilizes the pH of electrolyte dur-
ing the deposition process of metals and alloys. Cu-Ni alloy coat-
ings have been synthesized using a glycine bath by varying pH of
electrolyte and bath composition to investigate the mechanism
that controls the elemental composition of Cu-Ni alloy coatings.
This bath is composed of nickel sulfate, copper sulfate, glycine acid
Materials Today: Proceedings xxx (xxxx) xxx
Current density Goal Ref.
6 A/dm2 (DC) Improving microhardness, wear and corrosion [20]
resistance properties
3 A/dm2 (DC) Improving corrosion resistance properties [38]
and NaOH. NaOH was used to adjust the pH of the electrolyte bath.
The elemental composition study of deposited Cu-Ni alloy coatings
showed that the electrolyte pH significantly affected the elemental
composition of coatings. Ni content of deposited coating is higher
at pH values of 5 and 6, mainly due to the similar reduction poten-
tial of Ni2+ and Cu2+. At pH value 8, Ni content in the deposited
coating is low due to the decrease in the formation of Ni2+-
glycine complex as compared to Cu2+-glycine complex. TEM anal-
ysis along with EDS confirmed the uniform composition of coating
at all positions.
3.8. Properties of Cu-Ni alloy and Cu-Ni alloy composite coatings
Cu and Ni belong to f.c.c. structure with a molar mass of 63.54
and 58.9 u and density of 8.96 and 8.9 g.cm
3. Some important
properties of Cu and Ni are listed in Table 2. The addition of Ni
to Cu can develop their utilization in different engineering sectors
due to improvement in characteristics such as corrosion resistance,
electrical, tribological, electrochemical magnetic and mechanical
properties [12,49,50]. In addition to Ni as alloying elements, rein-
forcement of particles into the Cu-Ni matrix can improve tribolog-
ical, mechanical and electrochemical properties. A few researchers
have prepared Cu-Ni alloy matrix composite coatings based on
Al2O3 [33], Gr [20,51], TiN [34], ZrO2 [35], Y2O3 [38], Cr [37] and
layered silicate (MMT) [32]using the electrodeposition method.
The addition of the reinforcing element in the Cu-Ni matrix can
affect the tribo-mechanical properties of the coating. Ceramic par-
ticles such as Al2O3, TiN, and ZrO2 have been used to synthesize
composite coatings due to their excellent mechanical properties
such as hardness and wear resistance. The addition of ceramic par-
ticles in the composite coatings resulted in improved tribo-
mechanical and anticorrosion properties. During the deposition
process, the presence of ceramic particles inhibits the crystal
growth and reduces the crystallite size (Hall-Petch effect). Also,
the rise in the concentration of ceramic particles in the electrolyte
bath results in an increase in the incorporation of ceramic particles
in composite coatings up to a certain limit. The increase in ceramic
particle content in the composite coating results in a subsequent
increase in the required stress for the movement of dislocations,
and hence, according to the Orowan mechanism, microhardness
is improved [33]. The ceramic particles can enhance the wear prop-
erties of composite coatings owing to their excellent lubricant
properties. The corrosion resistance of the ceramic particle rein-
forced composite coatings has been enhanced by providing a more
tortuous mean free path of corrosion and a decrease in intergran-
ular discontinuity by filling microholes, gaps, and cracks. The addi-
tion of ceramic particles can alter the texture of the composite
coating and covers the matrix’s metallic surface, thus, corrosion
resistance is increased.
5
A.D. Pingale, A. Owhal, A.S. Katarkar et al. Materials Today: Proceedings xxx (xxxx) xxx

Table 2 However, organic solvents (acetone, ethanol, etc.) are used in the
Important properties of pure Cu and Ni. ball milling process to prevent agglomeration of reinforcing ele-
Properties Copper Nickel ments such as graphene, CNT, etc. Before the consolidation process,
Atomic number 29 28 vacuum rotary air-drying, vacuum infiltration, freeze-drying and
Molar mass (u) 63.54 58.69 evaporation drying are generally employed to remove organic sol-
Electron configuration [Ar] 3d10 [Ar] 3d8 4 s2 or [Ar] 3d9 vent from the mixture. Bakhshaei et al., [60] have fabricated Cu50-
4 s1 4 s1 Ni50/CNT nanocomposite by the mechanical alloying method. First,
Density (g.cm
3) 8.96 8.9
Crystal structure f.c.c. f.c.c.
Cu and Ni powders are mixed with equal quantity and then CNTs
Vickers-Hardness (MPa) 369 638 are added to them. Then multi-walled carbon nanotubes were
Young’s modulus (GPa) 128 200 reinforced with Cu-Ni alloy using a ball mill. The XRD analysis con-
Boiling point (°C) 2562 4946 firmed that the formation of Cu50-Ni50 alloy in 10 h milled sample.
Melting point (°C) 1085 1455
The presence of CNT significantly affected the elemental composi-
Electrical resistivity (nX.m) 63.54 69.3
Magnetic ordering Paramagnetic Ferromagnetic tion and microstructure of Cu50-Ni50/CNT nanocomposite. Also, it
Thermal conductivity (W m
1 398 90.9 was observed that decrease in crystalline size of Cu50-Ni50/CNT
K
1) nanocomposites with an increase in milling time. The addition of
CNTs to Cu-Ni powder enhances the work hardening and decreases
the cold-welding rate of the powder particles during the ball
4. Synthesis Cu-Ni alloy matrix composites through powder milling which resulted in reduction in the particle size of
metallurgy method nanocomposite. The addition of CNT in Cu-Ni alloy decreases satu-
ration magnetization and increase coercivity than that of the Cu50-
4.1. Introduction of powder metallurgy method Ni50 powder. Hence ball milling parameters needs to be appropri-
ate to obtain uniform dispersion of CNT in Cu-Ni alloy matrix while
Powder metallurgy is ideal for producing metallic components decreasing CNT structural damage.
from metallic powders because of its several advantages, such as
fine-grained microstructure and enhanced homogeneity in terms 4.3. Consolidation
of the distribution of alloying elements, phase distribution and
grain size. Nowadays, powder metallurgy is extensively used in The sintering method has been widely used to consolidate the
the fabrication of MMCs because of its near-shape capability, sim- metal, alloy and composite powders. In some research studies,
plicity and flexibility. The powder metallurgy method involves four green compacts were formed using a hydraulic press and sintered
different steps for completion of the process. The first step involves using a conventional or microwave furnace [61–63]. Microwave
the preparation or production of powder. The second step involves sintering is highly preferred compared to conventional sintering
mixing reinforcement with metal matrix powder, which is gener- because it produces composites with much finer grain sizes due
ally carried out using a ball, planetary, high enemy mill, etc. The to quick heating. Several researchers have reported hot pressing
third step involves the compaction of powder, which is generally consolidation of metal, alloy and composite powders [64,65]. Ini-
done using a hydraulic press. And the final step involves the sinter- tially, the composite powder is filled in a graphite die, and then
ing of compacts, which is carried out using a muffle furnace or simultaneous application of uniaxial pressure and heat is provided
induction furnace. Powders under 200 lm are generally used to to obtain the consolidation of composite powder.
produce metallic components. During the sintering of metallic
components, the sintering temperature is kept below the melting
5. Social significance of the present work
temperature of metallic powder. Also, an inert atmosphere is nec-
essary to avoid the oxidation of the metallic components during
Natural resources play an important role in the economic devel-
the sintering process.
opment of any country. The durability of infrastructures and effi-
ciency of industries can be affected by corrosion caused due to
pollution. The deterioration of active metals through corrosion
4.2. Mixing
and wear attacks is a key challenge faced by the marine, automo-
bile, chemical, aircraft and aerospace industries [66]. Industrial
The composites powders have been synthesized by several mix-
plant shutdowns can occur as a result of corrosion. The risk of cor-
ing methods such as vortex mixing, sonication, magnetic stirring,
rosion failure can be reduced by material selection, application of
mechanical alloying, ball milling and mechanical stirring [52–59].
composite coatings, use of inhibitor, proper design of parts and
However, mechanical alloying is commonly used for powder pro-
cathodic protection. Each metal has inherent and unique corrosion
cessing to prepare alloy and composite materials. In this process,
performance. Applying Cu-Ni alloy composite coating on active
initially, reinforcement and metallic powders are added in the
metals provides high resistance to corrosion. In addition, the use
desired proportion. After this, grinding of metallic powders and
of Cu-Ni alloy composite coatings can enhance the service life of
reinforcement is carried out using an attritor, planetary mill or sha-
base material and reduce the cost associated with corrosion main-
ker mill. An inert atmosphere is required to protect the metallic
tenance and repair.
powder mixture from oxidation in the grinding mill. The energy
milling process depends on several process parameters such as
the operating temperature, milling speed, milling time, milling 6. Summary
atmosphere, ball mill design, and charge ratio. The intimate mixing
of metallic powders and reinforcement occurs at the atomic level This review has considered Cu-Ni alloy matrix composites pre-
due to the welding processes, deformation and repeating fracture pared by electrodeposition method and powder metallurgy
during the milling process. Several process control agents (petro- method and their utilization in different engineering sectors. Most
leum ether, stearic acid, etc.) have been used to avoid the agglom- of the research work has been done on the Cu-Ni alloy matrix com-
eration and sticking of metallic powder during the milling process. posite coatings using electrodeposition method. The electrodeposi-
Process control agent is absorbed on the metallic powder surface tion method limits the thickness of the composite up to 200 mm. No
and decreases cold welding between impacted metallic particles. study has been there that reports a method for economical as well
6
A.D. Pingale, A. Owhal, A.S. Katarkar et al.
as scale-up and gives a huge amount of production for Cu-Ni alloy
matrix composites. The mechanism of electrodeposition and pro-
cess parameters affecting microstructure, elemental composition,
tribological, mechanical and corrosion properties coatings have
been discussed. Uniform dispersion of particles in the Cu-Ni matrix
can be easily achieved using electrodeposition method and powder
metallurgy method. Reinforcement of particles during electrode-
position method has been affected on the crystallite size of the
Cu-Ni alloy coatings. Properties of Cu-Ni alloy composite coatings
have been increased up to a certain concentration of particles in
the electrolyte bath and then start decreasing with a further rise
in particle concentration in the electrolyte bath due to the agglom-
eration of particles. The exceptional properties of Cu-Ni alloys and
composite coatings reveal that these coatings are more suitable in
wear, mechanical and corrosion applications.
CRediT authorship contribution statement
Ajay D. Pingale: Conceptualization, Data curation, Formal anal-
ysis, Visualization, Writing - original draft, Writing - review & edit-
ing. Ayush Owhal: Conceptualization, Data curation, Formal
analysis, Visualization, Writing - original draft, Writing - review
& editing. Anil S. Katarkar: Conceptualization, Data curation, For-
mal analysis, Visualization, Writing - original draft, Writing -
review & editing. Sachin U. Belgamwar: Conceptualization, Data
curation, Formal analysis, Supervision, Validation, Visualization,
Writing - original draft, Writing - review & editing. Jitendra S.
Rathore: Conceptualization, Data curation, Formal analysis, Super-
vision, Validation, Visualization, Writing - original draft, Writing -
review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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