Accepted Manuscript

Electrodeposition of Ni–Fe alloys, composites, and nano coatings- A review

V. Torabinejad, M. Aliofkhazraei, S. Assareh, M.H. Allahyarzadeh, A. Sabour

Rouhaghdam

PII: S0925-8388(16)32731-1
DOI: 10.1016/j.jallcom.2016.08.329
Reference: JALCOM 38831

To appear in: Journal of Alloys and Compounds

Received Date: 23 April 2016

Revised Date: 25 August 2016
Accepted Date: 30 August 2016

Please cite this article as: V. Torabinejad, M. Aliofkhazraei, S. Assareh, M.H. Allahyarzadeh, A.S.
Rouhaghdam, Electrodeposition of Ni–Fe alloys, composites, and nano coatings- A review, Journal of
Alloys and Compounds (2016), doi: 10.1016/j.jallcom.2016.08.329.

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 ACCEPTED MANUSCRIPT

Highlights
• Electrodeposition of Ni-Fe alloy is concisely reviewed
• Effect of different parameters and additives on the properties is summarized
• Main practical usages of Ni-Fe alloy in different aspects are reviewed
• Thermal treatment has a significant influence on the properties of Ni-Fe alloy

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Electrodeposition of Ni-Fe Alloys, Composites, and Nano Coatings- A review

V.Torabinejad, M. Aliofkhazraei1, S. Assareh, M.H. Allahyarzadeh, A. Sabour
Rouhaghdam
Department of Materials Engineering, Faculty of Engineering, Tarbiat Modares University, P.O. Box: 14115-143,
Tehran, Iran

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Abstract:

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Electrodeposition is considered as an easy and cost effective technique for preparation of alloy
coating. A wide variety of properties for coatings can be achieved by selecting different

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parameters of electrodeposition. The electrodeposited Ni-Fe coating is employed in many fields
such as corrosion, wear, magnetic and electrical applications, and electrocatalytic materials. In
this study, as the evaluation of previous researches will be valuable to guide future researches,

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electrodeposition of Ni-Fe coating was investigated from different aspects. The electrodeposition
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process, effective parameters, properties, and application of Ni-Fe were summarized considering
the previous studies.
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Keywords: Coating; Direct current; Electrodeposition; Ni-Fe; Pulsed current.

Contents
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1. Introduction .......................................................................................................................... 4
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1.1. Preface.................................................................................................................................. 4
1.2. Electroplating of Ni and Ni-Fe alloy ................................................................................... 5
2. Mechanism of Ni-Fe electrodeposition................................................................................ 7
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3. Baths used in electrodeposition process of Ni-Fe coating ................................................... 8

3.1. Sulfate and chloride baths .................................................................................................... 8
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3.2. Fluorborate bath ................................................................................................................... 9

3.3. Sulphamate bath ................................................................................................................. 10
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3.4. Nonaqueous baths .............................................................................................................. 10

4. Additives ............................................................................................................................ 11
4.1. Boric acid ........................................................................................................................... 11
4.2. Citric acid ........................................................................................................................... 11
4.3. L-ascorbic acid ................................................................................................................... 12

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Corresponding author: Tel.: +98-912-6905626, Fax: +98-21-66960664, E-mail address: maliofkh@gmail.com, khazraei@modares.ac.ir

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4.4. Glycolic acid ...................................................................................................................... 12

4.5. Saccharin ............................................................................................................................ 12
5. Electrodeposition methods ................................................................................................. 13
5.1. DC electrodeposition ......................................................................................................... 13
5.2. PC electrodeposition .......................................................................................................... 14

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5.3. PRC Electrodeposition ....................................................................................................... 16
6. Electrodeposition parameters of Ni-Fe alloy ..................................................................... 17

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6.1. Current density ................................................................................................................... 17
6.2. Electrolyte agitation ........................................................................................................... 18

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6.3. Electrolyte pH .................................................................................................................... 18
6.4. Pulse frequency .................................................................................................................. 19
6.5. Duty Cycle ......................................................................................................................... 20

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7. Properties of electrodeposited Ni-Fe ................................................................................. 21
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7.1. Microstructure .................................................................................................................... 21
7.2. Mechanical properties ........................................................................................................ 22
7.3. Magnetic properties ........................................................................................................... 24
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7.4. Electrocatalytic properties ................................................................................................. 27

7.5. Corrosion behavior............................................................................................................. 28
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7.6. Wear behavior .................................................................................................................... 30

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8. Thermal treatment of electrodeposited Ni-Fe .................................................................... 30

9. Ni-Fe Composite coating ................................................................................................... 33
9.1. Effect of Al2O3 particles .................................................................................................... 35
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9.2. Effect of SiC ...................................................................................................................... 35

9.3. Effect of ZrO2 particles ...................................................................................................... 35
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9.4. Effect of Si3N4 particles ..................................................................................................... 36

9.5. Effect of In2O3 nanoparticles ............................................................................................. 36
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10. Addition of other elements to Ni-Fe coating ..................................................................... 36

10.1. Ni-Fe-W ........................................................................................................................... 36
10.2. Ni-Fe-Cr ........................................................................................................................... 37
10.3. Ni-Fe-P ............................................................................................................................. 38
10.4. Ni-Fe-Mo ......................................................................................................................... 38
10.5. Ni-Fe-C ............................................................................................................................ 39

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11. Applications ....................................................................................................................... 39

12. Future scope and conclusion .............................................................................................. 41

1. Introduction

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1.1. Preface
The mechanical, thermal, chemical and electrochemical interaction of a material in a given
environment initiate from its surface. Therefore, the surface of a material is the most important

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engineering part. Among the standards which are developing continuously for production and
manufacturing process, the use of surface modification technologies in the manufacturing

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process is inevitable. Since the surface of materials is often under threat of wear and corrosion
[1], tribology and corrosion are the most essential and important fields in surface technology.

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The tribological and corrosion phenomena impose huge damages to economy and industry. The
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damages will be irrecoverable if wear and corrosion phenomena are not controlled correctly.
Therefore, the surface technology can be considered as a key technology in the production
engineering process. The use of appropriate surface technologies can prevent the damages or at
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least delay them. The selection of a proper method to create distinctive surface properties is a
complex process as it includes modifying the various characteristics and properties. Furthermore,
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the selection of suitable process usually requires the economic and environmental investigations
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[2].
Electrodeposition is an electrochemical process applied for surface structure modification. The
electrodeposition process is an old method in surface engineering processes which has a long
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history. The electrodeposition technique was firstly applied more than 2000 years ago in several
hypothesizes [3, 4]. The production of a galvanic cell with Volta in about 1800 and then progress
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in electrical motors from 1800 to1900 led to use electrodeposition technique as a cost effective
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process to produce a coating. In this process, a monolayer or multilayer coating is formed

because of the electrochemical reactions occurred at the electrode/electrolyte interface and
deposition of ions from the electroplating bath on the surface [5]. The coating may be deposited
on the surface to enhance the solderabilty, lubricant properties, electrical conductance, corrosion
resistance, and wear and thermal resistance of the substrate material. Electrodeposition process
can be performed with both types of direct (DC) and pulse current (PC) [6]. In the DC method
current is continuously applied to the system. However, in a PC electrodeposition process, the

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electrical current is alternated swiftly between two different values [7]. The properties of
deposited coatings can vary because of pulsating parameters in PC electrodeposition process.
The progress in electronics made it possible to control the properties of the coating by using the
PC instead of DC method. The better dispersion of elements in the coating, compact and
nonporous nanostructure coating, a decrease in absorption of gasses in coatings, a reduced need

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for organic additives and thus a decrease in environmental pollution are advantages of PC
electrodeposition process.

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1.2. Electroplating of Ni and Ni-Fe alloy
Because Ni and its alloys have a variety of merits such as good corrosion and wear resistance,

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they have been receiving a great attention in deposition applications. Almost 12% of Ni
consumption in the world is allocated to the electrodeposition of Ni coating [8]. The use of Ni

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coating for decorative purposes is the main application of electroplated Ni coating [9]. The Ni
deposits are used in the industry to improve wear and corrosion resistance, to repair eroded
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metals, to change the dimensions of small size pieces, to improve magnetic properties, to prepare
the substrate surface for glazing or producing the organic coating, and other purposes [10]. In
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addition to pure Ni coating, it is possible to produce a Ni-based alloy coating by an

electrodeposition process. The Ni-Fe alloy coating is used in order to decrease the cost
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production and also provide soft magnetic properties, good electrical conductivity, proper
corrosion resistance and special optical properties [11]. This type of coating is widely used in
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electronic, sensors, communication and optic industries. There are several processes used to
produce Ni-Fe coating as follows: sputtering, molecular beam epitaxy, evaporation and
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electrodeposition [12]. The special conditions of temperature and pressure, ultra-high vacuum
and consequently expensive process are disadvantages of former methods over electrodeposition.
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Also, the coating produced by electrodeposition process is more homogenous and has lower
defects in comparison to that of produced with other coating processes [13]. Furthermore,
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increasing the thickness of coatings is possible and cost effective in electrodeposition while other
methods prepare thin films of Ni-Fe.
Nickel-iron alloys containing from 40-90 wt.%Fe possess very interesting magnetic properties.
Particularly, the alloy containing 78.5 wt.% Ni, sometimes referred to as Permalloy, has a very
high permeability in small magnetic fields. The magnetic properties of this alloy can be varied to
a marked extent by heat treatment. In this connection, many attempts have been made to

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correlate the changes in magnetic properties with the changes in structure, internal strain, etc.,
which are normally associated with variations in heat treatment. In past years, extensive
researches has been done to draw the phase diagram and different versions have been proposed
based on experimental or theoretical work. The mostly accepted diagram in Fig. 1 represents the
possible phases and transformations in this system. The phase boundaries of the Fe-rich side of

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the phase diagram, were established experimentally by Romig and Goldstein [14] from 900 to
300ºC by using STEM. The nickel-rich FeNi3 ordered fcc phase, which has an L12

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superstructure, was first detected by Leech and Sykes [15] using XRD measurements. A
eutectoid reaction was predicted suggesting that α and Ni3Fe were in equilibrium at low

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temperatures [16]. The critical ordering temperature of FeNi3 (516 ºC at 73 at.% Ni) was
determined by Deen and Woude [17] using Mossbauer spectroscopy. It is claimed that FeNi and

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Fe3Ni phases also existed in this phase diagram below the eutectoid temperature in the two-phase
(α+γʹ) region [16]. Little information concerning the Fe-Ni system at low temperatures exist due
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to the slow diffusion of Ni in Fe-Ni. Therefore, the low-temperature part of the Fe-Ni phase
diagram was according to speculations. The existence of ordered phases in this diagram
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demonstrates the equilibrium state can be reached via annealing for very long periods. Some
evidences about the ordered phases have been reported for annealing at temperatures higher than
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the room temperature for long periods [15, 18]. Based on the experimental works, the
electrodeposited Ni1-xFex (0.1<x<0.9) alloys consist of α and/or γ phases since the deposition
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condition is a non-equilibrium process [19-22].

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Fig. 1 The Fe-Ni phase diagram [23].
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2. Mechanism of Ni-Fe electrodeposition
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Codeposition of Ni and Fe from an electrolyte is believed as an anomalous deposition, where the

content of the more active element in the deposit is higher, however, the ratio of ions in the
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electrolyte for noble element compared to active element is higher. The deposition rate of Fe,
which is a more active element than Ni, is higher than that of Ni in an electrodeposition bath of
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Ni-Fe. Fig. 2 indicates the content of Fe versus the ratio of Ni/Fe ions in the electrolyte.
According to this diagram the relationship between Fe content of alloy and Ni/Fe ion ratio of the
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bath is not linear. For instance, the work of Sanaty-Zadeh [24] shows that at Ni/Fe ion ratio of 1
the content of Fe in the deposit is 84wt.%. Hence, the deposition rate of Fe is greater than that of
Ni indicating the anomalous deposition. In early studies, the anomalous deposition was attributed
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to the deposition of Fe hydroxide on the surface of the electrode which prevents reduction of Ni
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ions [25]. According to this mechanism, the reduction of H+ ions on cathode surface and thus the
local increase of pH value on the surface facilitates the formation of metallic hydroxides. In this
case, the formation of Fe(OH)2 on the surface is more than that of Ni(OH)2 which in turn inhibits
the deposition of Ni ions. Nevertheless, there are several reports which indicate the anomalous
deposition occurred at very low pH values [26, 27]. Accordingly, this is not reasonable to justify
this behavior with above mentioned theory. In the next models, the anomalous deposition was

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attributed to the formation of NiOH+ and FeOH+. The formation of these intermediate
compounds may be due to hydrolysis of Ni2+ and Fe2+ and discharging on the cathode surface
[28]. Therefore, the high concentration of FeOH+ ions near the electrode and coverage of the
surface with these ions inhibit the formation of NiOH+ ions. In a newer model suggested by
Matlosz [29], the kinetic rather than the chemical reaction is emphasized. Hence, it is assumed

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that the reduction reaction of both Ni and Fe ions occurs in two steps as follows:

    →

 step (1)

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    →
step (2)
In the first step, the reduction of Fe2+ and Ni2+ ions to Fe+ and Ni+ occurs respectively, and these

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intermediate species are adsorbed on the electrode surface. The deposition rate of ions is
controlled by the second step in which the reduction process of intermediate ions is performed
[30, 31]. In this step, the reduction rate of Fe+ compared to Ni+ ions is higher and thus many

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areas of the surface are covered with Fe ions. The covering of electrode surface with Fe+ prohibit
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from the deposition of Ni ions. According to this model, the hydrogen evolution and increase in
pH values near the electrode is not essential in the anomalous deposition process. This model has
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been confirmed by electrochemical impedance spectroscopy measurements [32].

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Fig. 2 The content of Fe as a function of Ni/Fe ion ratio in the electrolyte [24, 33-35].

3. Baths used in electrodeposition process of Ni-Fe coating

3.1. Sulfate and chloride baths

Sulfate-based and chloride-based baths are most widely used baths in the industry and previous
investigations. From economic aspects, sulfate and chloride baths are the best choices for

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electrodeposition process. Beside the sulfate compounds, Ni chloride is used in a sulfate bath.
The presence of Cl- due to the addition of Ni chloride to the electrolyte causes dissolution of Ni
anodes and increases the conductivity of the solution [8, 36]. The Fe chloride and Ni chloride are
usually used in sulfate baths of Ni-Fe electroplating. The absence of chlorides in electrolyte can
lead to a decrease in the internal stresses of the coating. In electroplating bath in which the

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consumable anodes are not used, the absence of chlorides will be favorable. In comparison, in
the presence of consumable anodes, chlorides and other reactive agents are used in electroplating

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bath [37, 38]. Moreover, the chloride baths alone is also used in electrodeposition of Ni-Fe alloy.
The coatings produced in chloride baths compared to the one prepared in sulfate baths is harder

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and have more stresses in its structure. The reason for this effect is unclear in many studies
concerned the internal stress of electrodeposits [39-41]. Furthermore, the corrosion resistance of

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these coatings is low and some special plans should be proposed to protect from corrosion
attacks [42]. It has been found that in both chloride and sulfate baths, current efficiencies were
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independent of Fe2+ concentrations, although their values in chloride baths were higher by about
20%. The higher limiting current for H+ in the sulfate bath rather than chloride bath was the main
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reason of latter. Accordingly, significant decrease in the overpotential of Ni-Fe in chloride baths
attributed to the catalysis effect of chloride through the formation of a Cl- bridge between the
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electrode and the metal ions [39, 43]. The electrodeposits fabricated in sulfate baths have larger
grains and less internal stress than chloride bath; however, the anode passivates and causes the
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metal ion concentration and solution pH to change [43].

3.2. Fluorborate bath
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The use of some special additives such as saccharine in chloride, sulfate or sulphamate baths
allows deposition of some other products beside the metallic coating [20]. The presence of these
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products in the coating can affect the properties of the coating. For instance, the properties of
coating deposited from a bath containing citrate additives can be changed due to the presence of
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active carbon in the composition of electroplating bath [22]. If consumable anodes such as Ni or
Ni powder are used in above mentioned baths, the dissolution rate of the consumable anode
cannot compensate the decrement rate of Ni ions in the bath. Therefore, local changes in pH
value and composition of bath occur that could be effective on the properties of the coating. To
overcome these problems fluorborate baths can be used in the electrodeposition process. In this
case, the problems issued from the presence of additive agents such as saccharine and sulfur will

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be solved. Furthermore, the dissolution of Ni and Fe powders in the bath is easy and thus the
decrement of Ni ions in the composition of the bath can be compensated. In addition, the
deposition rate in this bath is also high [22]. This bath has some drawbacks such as high cost and
corrosivity.
3.3. Sulphamate bath

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The sulphamate baths have some advantages such as high throwing power, high deposition rate,
and low internal stress of deposited coating. The hydrolysis process and formation of

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azodisulfonate are the major defects of these baths. The high concentration of Ni sulphamate
leads to decreased hydrolysis, but the intensified formation of azodisulfonate impurities.

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Azodisulfonate, persulfate, sulfate and sulfite are some of the impurities which may be generated
in sulphamate baths. Among these impurities, the azodisulfonate is the main source of sulfur

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which decreases the ductility and compressive stresses [44, 45].
3.4. Nonaqueous baths
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The Ni-Fe alloys are usually deposited from aqueous baths. The discharging process of H+ ions
and formation of hydrogen during electrodeposition process is the most important drawback of
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aqueous bath. It has been observed that hydrogen discharging in the electrodeposition process
degrades some of the deposit properties. Therefore, the use of an appropriate solvent without
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active hydrogen or a solvent, in which the hydrogen bonds are stronger than that of water bonds,
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is preferred. For this purpose, the organic electrolytes are preferred over the aqueous ones.
Ethylen glycol solution was used for Ni-Fe electrodeposition process. This solution has a good
amphoteric and complexing properties. Because the boiling point of this solution is higher than
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that of water, it is possible to use at higher temperatures. In comparison to water, ethylene glycol
provides a lower adhesion, better wettability, appropriate surface charge, higher viscosity and
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density. These properties cause the increased stability of ethylene glycol in suspensions. In this
electrolyte, since the chance of hydrogen releasing decreases, a coating with low content of
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hydrogen can be obtained [46, 47]. N,N-dimethylformamide (DMF) is another solvent, which
has least or no active hydrogen, is employed for electrodeposition of Ni-Fe-Si3N4 coating [48].
There are no information concerning the comparison of deposition rate and properties of
deposited Ni-Fe coatings in nonaqueous electrolyte with the ones deposited in aqueous solutions.

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4. Additives

4.1. Boric acid

The boric acid is added to chloride and sulfate baths used in the electrodeposition process of Fe
group metals. In electrodeposition process of Fe group metals, a part of the electrical current is

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consumed to form hydrogen. This reaction decreases the current efficiency and leads to an
increase in the pH value of cathode surface and thus affects the kinetics of reduction reactions for
metallic ions. Boric acid improves the range of required current density for electrodeposition

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process. Furthermore, the presence of Boric acid in an electroplating bath improves the
appearance of the coating and decreases the coating brittleness [49, 50] Many researchers believe

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that boric acid acts as a buffering agent and prevents pH increment on cathode surface [51, 52].
Some researchers believe that boric acid can act as a catalyst for the reduction reaction of

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metallic ions by the formation of some complexes with Ni [53]. This mechanism has been
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proven for Fe in chloride baths [54]. Zech [55] evaluated the effect of boric acid in Ni-Fe
electroplating bath. This author found that boric acid act as a source to produce proton in the
solution in a potential range in which reduction reactions occur and reduction of water is also
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possible. Therefore, the increase in the pH value of the cathodic areas occurs in nobler potentials.
The presence of boric acid in an electroplating bath inhibits pH raise and also the required
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potential range for the electrodeposition process is extended without hydroxide deposition.
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4.2. Citric acid

Citric acid is used in Ni-Fe electroplating baths as a complexing agent. Citric acid is a complex
agent for Fe3+, Ni2+ and Fe2+ions. The stability of the produced complexes decreases in the order
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of Fe3+, Ni2+ and Fe2+. The addition of citric acid to the sulfate baths leads to deposition of the
high content of Fe on the cathode surface; however, the current efficiency decreases significantly
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[56]. The results indicate that the local increase in the pH value of the cathode surface leads to
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the formation of hydroxide layer. In this case, citric acid quickly decomposes and provides the
necessary protons. The proton reduction leads to a decrease in cathodic efficiency. In the cases
the formation of hydroxide layer is not desirable (such as chloride baths in pH=3), the content of
Fe in the coating is very low and a high quantity of Fe3+ ions is formed in the solution. Since the
stability of Fe3+ ions is higher than that of Fe2+, the Fe2+ ions exit from the complex mode and
thus the equilibrium chemical reaction occurs in a direction to form Fe3+ ions [57]. The
complexing effect of citrate ions shifts the reduction potential of Ni-Fe alloy to the more

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negative potential and increases the diffusion-limited current. The other effect is raising the
nucleation sites and nucleation rate [58].

4.3. L-ascorbic acid

L-ascorbic acid prevents the oxidation of Fe2+/Fe3+ during electrodeposition process. The

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presence of this acid in electroplating bath inhibits the formation of Fe hydroxide films. When
the condition for the formation of Fe hydroxide layer in cathodic sites is ready, Ascorbic acid

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causes Fe discharge from hydroxide films. This behavior is often seen in sulphamate baths and it
is not reported in the case of chloride medium [57]. The ascorbic acid is not effective on the

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chemical composition of the coating, although it prevents oxidation of Fe2+ ions and thus hinder
decrement in the concentration of these ions [25].

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4.4. Glycolic acid
Glycolic acid with sodium citrate is used in chloride baths. According to the results of previous
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works, the presence of glycolic acid in the bath shifted the reduction potential of Ni-Fe alloy
toward more negative values. Furthermore, the nucleation rate increased with the presence of this
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acid in the electroplating bath. These behaviors can be explained by this fact that glycolic acid
acts as a buffer and a complexing agent. In the presence of glycolic acid, some spherical nuclei
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are formed on the surface which they continue to grow with the same growth rate. Furthermore,
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the addition of this acid decreased grain size and the surface roughness [56, 58, 59].
4.5. Saccharin
Saccharin is used as an additive agent in electrodeposition baths of many metals and alloys. This
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material can act as a grain refiner and stress reliever in electroplating solutions [60]. Effect of
saccharin addition on the internal stress of coating is presented in Fig. 3. Based on the plot, it is
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found that internal stress of Ni-Fe coating is reduced with saccharin concentration. Different
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mechanisms are reported for the effect of this additive on the coating properties. One of the most
important mechanisms is the formation of complex compounds on the surface of the cathode and
decrease in the diffusion rate of adsorbed Ni ions and thus the increase in the frequency of
nucleation sites [61]. The addition of additive agents such as saccharine affects the cathodic
polarization behavior. According to some investigations, the reduction potential of Ni ions shifts
toward more positive values due to the addition of saccharin to the electrolyte solution. This
behavior can be attributed to the barrier properties of the generated complexes against diffusion

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of Ni ions. High overpotential values re in a good compatibility with the increase in nucleation
rate and a decrease in grain size [62]. The stress relieving in the structure can be attributed to the
grain refinement. The grain refinement and increase in the volume of grain boundaries releases
the energy produced due to internal stresses [59]. The study on the concentration of saccharin in
the bath revealed that at low concentrations (<3g/l ) shiny surface with nano-size grains,

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probably induced by stress relaxation and grain refinement, is formed. Increasing the saccharin
concentration to higher values caused a rough surface with bimodal size distribution [63]. The

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effect of saccharin concentration on the chemical composition of deposits is a controversial
issue. Jin-Ku et al. [64] reported partial changes of chemical composition (from 4.60 to 4.45

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wt.%) with increasing saccharin from 0 to 8 g/l. On the other hand, Tabakovic et al. reported the
partial change of chemical composition at concentrations greater than 0.8 g/l while the lower

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values had a noticeable effect on the chemical composition of deposit and increased the Fe
content [22].
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Fig. 3 The effect of saccharin addition on the internal stresses of Ni-Fe alloy [42]
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5. Electrodeposition methods
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5.1. DC electrodeposition
Electrodeposition process can be carried out through DC, PC, and PRC methods. Fig. 4
represents different modes of electrodeposition process. So far, above three different modes have
been used in electroplating of Ni-Fe coating. In DC electrodeposition process, the electrical
current is continuously exerted to the system in an uninterruptible manner. This method is the
conventional and old method that have used for electrodeposition of metals and alloys. The main

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advantages of DC over PC and PRC method are: (i) simple and economically affordable process
and (ii) the sufficient technological knowledge.

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Fig. 4 The various modes of current density for electrodeposition; (a) DC, (b) PC and (c) PRC.

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5.2. PC electrodeposition
In the PC electrodeposition the current in a periodic manner reaches zero (Fig. 4). In this case,
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negatively charged layer is formed on the cathode surface. The thickness of this layer increases
to a particular extent and then remains constant. This layer hinders diffusion of ions. The
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discharging of this layer during off-time in PC electrodeposition permits diffusion of ions toward
the cathode surface [7]. In addition to electroplating bath variables (temperature, composition,
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and pH) which are effective in any type of electrodeposition process, peak current density (Ipeak),
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pulse On-time (ton) and off-time (toff ) are the other effective parameters in PC electrodeposition
process. These parameters are shown in Fig. 4. The pulse frequency and duty cycle are used for
better evaluation of pulse variables in electrodeposition process. Pulse frequency and duty cycle
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are calculated according to equations (1) and (2), respectively:

1
f = (1)
+ t on
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t off

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%   100 (2)
 

Where, f is the pulse frequency and d% is pulse duty cycle in each pulse. The average current
density can be defined as follows:

       %    (3)
 

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Where Ipeak is the pulse peak current density and Iave is the average current density in each pulse.
Each of these variables can be changed independently in a wide range and thus a wide variety of
coating properties can be obtained by changing any of these parameters [65].
In general, the advantages of pulse current in comparison to direct current is summarized as
follows:

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(1) Yielding a more compact structure: Pulse off-time in PC electrodeposition inhibits the
grain growth and increases n the possibility of nucleation on the cathode surface. When a

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pulse is fully completed, the next pulse will start immediately[66]. This condition leads to
an increase in the nucleation rate and a decrease in growth rate, which in turn cause the

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formation of a more compact structure [67].
(2) The ability to control the chemical composition and microstructure: The change in pulse

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parameters such as Ipeak, duty cycle and frequency make it possible to control the
adsorption and desorption of various species in the electrolyte [68, 69]. Therefore, the
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microstructure, chemical composition and properties of coatings can be controlled in PC
electrodeposition [70].
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(3) The decrease in frequency of generated pores and cracks because of reduced oxygen and
hydrogen gases on the cathode surface: The decrease of pores in coating can be attributed
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to two factors; (i) during electrodeposition process, the released gases on the cathodic
such as oxygen and hydrogen have enough time to leave the surface of the cathode and
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thus the possibility of their entrapment in the coating is low. (ii) The volume of gasses
released from the water electrolysis during pulse on-time compared to DC
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electrodeposition is very low [67]. The micrometer and nanometer sized bubbles are
formed during pulse on-time in PC electrodeposition in which the joining of bubbles to
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form a larger bubble is impossible. Nevertheless, the possibility of joining these bubbles
and formation of porosity in DC electrodeposition process is high.
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(4) Increasing the content of ceramic particles in nanocomposite electrodeposition [71-73]:

Once the electrodeposition process starts, a negative charge layer is formed on the
cathode in the presence of ceramic particles suspended in an electrolyte. This layer acts
as a barrier between ceramic charged nanoparticles and surface of the electrode. Within
PC electrodeposition, this negatively charged layer is discharged during pulse off-time in

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pulse current electrodeposition process. In this case, diffusion of ceramic particles into
the adjacent layer and finally reaching the electrode surface become easier [74].
5.3. PRC Electrodeposition
The current required for reduction of ions reaches to zero by a change in polarity in the PRC
electrodeposition process and thus the oxidation reaction occurs on the cathode surface. In this

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case, at the anodic potential of electrode dissolution rate of Ni is very low while the dissolution
rate of Fe from the cathode is higher than that of Ni [75, 76]. Therefore, the pulse

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electrodeposition process is a useful method to reduce the anomalous deposition of Fe. The
higher dissolution rate of Fe in comparison to Ni during exerting anodic current can be attributed

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to the oxidation of absorbed H2 on the surface of the substrate [77]. When cathodic current is
applied to the cathode, hydrogen gas is released. Such high fraction of released hydrogen does

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not have enough time to leave the surface. The presence and oxidation of hydrogen gas on the
surface of coating prevents the increment of pH value which in turn leads to a decrease in the
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extent of anomalous deposition [30]. Another effect of PRC is lowering the internal stresses in
the deposits. Fig. 5 shows the internal stress of PRC electrodeposited Ni-Fe coating in
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comparison to DC deposited one. Clearly, the internal stress increases with current density due to
more hydrogen evolution in the cathode surface; however, the internal stress is lower in the PRC
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[78].
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Fig. 5 The effect of current mode on the internal stress of Ni-Fe coating [78].

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6. Electrodeposition parameters of Ni-Fe alloy

6.1. Current density

The current density is one of the most important parameters in electrodeposition of alloys
because it can affect the cost, chemical composition and properties of coatings. Fig. 6 shows the

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effect of current density on the Fe content of Ni-Fe coatings. It can be seen that the Fe content in
the coating decreases with an increase in current density. The Fe content in coating also
decreases with an increase in average current density in PC electrodeposition process [19, 79,

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80]. This behavior has been reported in various electroplating baths and discussed repeatedly in
the literature [81-84]. This behavior can be explained by Fe deposition mechanism. Deposition

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of Ni is activation controlled, while the deposition of Fe is controlled by diffusion in an
anomalous deposition [85]. Horkan [39] proved the reduction of Fe content in electrolyte around

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the cathode surface. This author also suggested that the decrease in Fe content in the electrolyte
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is controlled by a diffusion process. An increase in current density leads to the increase in
cathodic overpotential thereby the activation of reactions on the electrode surface increases,
which in turn cause an increase in Ni content and a decrease in Fe content. According to previous
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studies, regarding the increase in current density and assuming the increase in pH values of
cathode surface, the decrease in Fe content in electrolyte around the cathode by an increase in
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current density is attributed to the formation of metallic hydroxides [25, 57]. Nevertheless, some
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works revealed that the diffusion process has a dominant role on the Fe content at higher current
densities. The main effect of high current density is depletion of cathode’s surface from Fe ions.
Thus, the diffusion of ions from the bulk of the solution toward the cathode surface is an
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effective parameter [84].

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Fig. 6 Effect of current density on the chemical composition of Ni-Fe coatings electrodeposited from
baths with different metallic ion ratios [42].
6.2. Electrolyte agitation

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The stirring of the solution has a significant effect on the chemical composition of alloys
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deposited with anomalous deposition. Fig. 7 illustrates the effect of stirring rate on the Fe content
in fluorborate bath. The figure shows that an increase in the stirring rate increased Fe content in
the coating. In this case, the role of mass transfer is more important than the kinetics of reactions.
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The stirring rate leads to an increase the transfer rate of Fe ions in the electrolyte and thus their
facilitated diffusion from the bulk of solution toward the cathode surface [86]. It should be noted
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that the raising the agitation rate to a certain value leads to increase in Fe content, while more
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increase has a slight effect on the chemical composition of the coating. Furthermore, the current
efficiency decreases with rising the stirring rate as shown in Fig. 7. This behavior can be
attributed to the mass transfer process and its effect on the hydrogen evolution rate. The
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significant decrease in current efficiency can be described with the decrease in deposition rate of
metals on the cathode surface. In this process, the hydrogen evolution is the dominant reaction in
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cathode [82, 84].

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6.3. Electrolyte pH
The electroplating baths with pH values in the range of 2-3.5 are used in the electrodeposition
process of Ni-Fe. The formation of hydroxides, particularly iron hydroxide, is possible at higher
pH values [82]. The results of previous investigations indicate that a decrease in pH value
reduces both current efficiency and Fe content in the coating. Fig. 7 shows an instance for effect
of pH on the chemical composition. The increase in Fe content in the coating can be attributed to
the increase in pH value on the cathode surface, which consequently leads to the accelerated
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formation of FeOH+. According to Matlosz [29] mechanism, the covering of the surface with
FeOH+ increases the possibility of an increase in Fe content in the coating. The content of
protons at low pH values is very high and a high fraction of current is consumed through the
reduction process of these protons which in turn decreases the current efficiency.

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(a) (b)

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Fig. 7 The effect of pH and stirring rate on the chemical composition and current efficiency of
electrodeposited Ni-Fe alloy from a fluorborate bath [86].
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6.4. Pulse frequency

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The adsorption and desorption of various ions in the electrolyte can be controlled by changing
the PC variables such as Ipeak, duty cycle, and frequency [5, 87, 88]. Therefore, the control of
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microstructure, chemical composition and properties of coatings in PC electrodeposition is

possible [89]. There are several reports about the effect of frequency on the chemical
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composition of electrodeposited alloys. Yin et al. [79] indicated that the frequency variation has
not been effective on the content of Fe. Sanaty-zadeh et al. [24] reported that the increase in
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frequency from 0.5 to 1000 Hz has a negligible effect on the Fe content in the coating, but
further increase in frequency from 1000 to 16000 Hz increased the Fe content from 61 to 71
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wt.%. This behavior is explained by the increase in local concentrations of Fe ions near the
cathode surface during pulse off-time. The recent research of Torabinejad et al. [19] is also
showed that frequency variation is not effective on the chemical composition of the Ni-Fe
coating. The change in grain size is a known influence of frequency variation on the coating
microstructure [70]. The pulse duration is very short in high frequencies. Therefore, the time of
charging and discharging process in pulse on-time and off-time is very short. Under such a

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condition, the nucleation rate increases and growth rate decreases which in turn results in the
formation of a compact structure [66, 90]. This behavior was also observed in the previous
reports [24]. In fact, when the nuclei are formed on the surface the grain growth is limited due to
the repeated interruption of current (high frequencies) and thus, so many nuclei are formed on
the surface which eventually leads to a decrease in grain size [5]. The influence of pulse

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frequency on the microstructure of Ni-Fe has received less attention in the literature. The
possible effect of this parameter on the resultant properties of the coatings may be attractive for

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many field of science and technology.
6.5. Duty Cycle

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The chemical composition, grain size and texture of the coating can be affected by variation of
the duty cycle. In PC electrodeposition of Ni-Fe alloy, the decrease in duty cycle increases Fe

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deposition. This phenomenon was confirmed in several recent studies [19, 91]. The mechanism
of Fe deposition in Ni-Fe coating is an anomalous process and thus the events observed can be
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explained accordingly. In an anomalous deposition, the deposition of Ni is an activation
controlled process, while the deposition of Fe is controlled by diffusion. Since the concentration
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of Fe ions in the electrolyte is lower than that of Ni ions, the chemical composition of the coating
is more dominated by diffusion of ions to reach the cathode surface. The presence of pulse off-
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time helps eliminate the concentration gradients near the cathode surface and thus the Fe ions
have enough time to move toward the cathode surface [92]. The mass transfer is a continuous
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process in PC electrodeposition because of stirring the electrolyte, while the charge transfer
occurs just at pulse on-times. At short duty cycles in the PC electrodeposition, the off-time of a
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cycle is much longer than that of on-time. In this case, the depletion of Fe ions adjacent the
cathode surface is compensated with diffusion of Fe ions from bulk. In the presence of ions on
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the cathode surface, the reduction continues without restrictions and thus the content of Fe in Ni-
Fe coating increases [93]. The above discussion is a summary of speculations in the literature.
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Thus, there is a serious need for research in this area to explore the exact mechanism of
deposition at different duty cycles by taking the electrochemical aspects into consideration.

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7. Properties of electrodeposited Ni-Fe

7.1. Microstructure
The XRD patterns of Ni-Fe coatings with different Fe content is depicted in Fig. 8. As shown,
the characteristic peaks of FCC phase are clear and increasing Fe to 43 wt% affects the intensity

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of (1 1 1) and (2 0 0). In comparison, increasing the Fe to 58wt% in the deposited coating leads
to the appearance of a new peak at (1 1 0) which is the characteristic peak of BCC phase. This
observation determined the approximate range of phase stability in electrodeposited Ni-Fe

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coatings. This patterns illustrates that Ni1-xFex alloy at x<58% is FCC phase, while at
58%<x<65% mixed state of FCC and BCC is observed. Finally, at x>65% the only phase is BCC

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[86].

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Fig. 8 The XRD results of electrodeposited Ni-Fe alloys with different Fe content [86].
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The deposition of Ni-Fe alloys results in a solid solution alloy. The lattice strains are generated
in the coating structure due to the difference in atomic radius of Fe and Ni atoms. An increase in
Fe content causes lattice distortion and thus lattice defects such as vacancies and dislocations are
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developed in the coating structure. When the number of dislocations reaches to a certain value,
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the low angle boundaries are formed which leads to grain refinement of coating structure. The
effect of Fe content on the grain size of the coating is shown in Fig. 9. When Fe content in Ni-Fe
coating is lower than 25 wt.%, the grain size decreases with a decrease in the Fe content of the
coating. However, the variation of grain size with Fe content is negligible in Fe contents of 25-40
wt.% . This is in a good agreement with those of the previous works, which they reported a
similar behavior for variation of grain size with Fe content [35, 94-96]. Furthermore, the grain

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size of Ni-Fe alloy usually is in the nanoregime although grain size may be varied by variation of
electrodeposition parameters.

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Fig. 9 The effect of Fe content on the grain size of Ni-Fe deposit [24, 33-35].
7.2. Mechanical properties
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Ebrahimi et al. [97] evaluated the microhardness and flow stress of electroplated Ni-Fe coating.
They reported that the optimum mechanical properties obtained in Fe contents of 20 wt. %. The
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results indicated that the increase in Fe content to 20 wt.% leads to the enhanced hardness and
flow stress, but the presence of more amounts of Fe leads to a decrease in hardness and flow
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stress values. In contrast, Sanaty-Zadeh et al. [24] observed that the variation of microhardness is
negligible when the Fe content is in the range of 20 to 40 wt.%, while more contents of Fe and
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thus formation of a metallic phase with BCC structure leads to a significant increase in
microhardness. Fig. 10 presents the engineering stress-strain curves of Ni-Fe alloys with
different grain sizes determined by TEM observations. The first point indicates a significant
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increase of strength in the nanostructured alloy in comparison to the microcrystalline alloy [98].
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There is a more accessed fact in the mechanical behavior of alloys and demonstrated by Hall-
Petch relationship [99]. The second point shown in Fig. 10 indicates the enhanced strength of Ni-
6%Fe in comparison with pure electrodeposited Ni. This increment is the result of the hardening
effect of the substitutional solid solution. The other point of tensile plots is the higher strength of
Ni-15%Fe than the Ni-15%Fe alloy that is attributed to the grain size of former alloy and its
stronger strain hardening [98]. When strain hardening in the above alloys exhausted, the plastic

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instability occurs as a consequent. Instability of plastic deformation can be attributed to various

mechanisms such as necking, microcracks, and shear bands. These researches claimed as there
are no signs of microcracks and shear bands in the microstructure of deformed specimens, the
possible mechanism of instability is necking [100], which is also confirmed by other research
works [21]. Fig. 11 displays a series of multiple load-unload tensions of electrodeposited Ni–Fe

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samples. The specimen was unloaded when the stress was close to the maximum during the
transient regime. This figure shows that during each reloading, higher stresses are observed,

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clearly exceeding the stresses obtained for the continuous tensile test. This phenomenon is
named as yield point phenomenon [101]. Yield points are often ascribed to a lack of mobile

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dislocations [102]; however, the main reason for this observation is unclear in literature for Ni-
Fe alloy.

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Fig. 10 Engineering stress-strain curves of tensile tests for electrodeposited Ni-Fe alloys and Ni at
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a strain rate of 10-41/s [98].

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Fig. 11 Stress–strain curves of Ni–Fe during load–unload tensile test. The black dashed line
represents the continuous tensile experiment [101].

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7.3. Magnetic properties
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The chemical composition of the alloy, electroplating bath, applied potential, and the addition of
additive agents are the parameters which can control the magnetic properties of an electroplated
Ni-Fe coating [103, 104]. The effect of these parameters on the magnetic properties of the
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coating was investigated in the previous studies. The coercivity, magnetic flux density, saturation
magnetization, magnetic remanence, permeability, anisotropy, and squareness are the magnetic
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properties which have been investigated [105-107]. The coercivity and magnetic flux density are
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the most attractive properties investigated by researchers. A decrease in coercivity and an

increase in magnetic flux density and also saturation magnetization causes to promote the
magnetic properties of the coating [108-111]. Therefore, many investigations have been done to
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decrease the coercivity and increase the magnetic flux density and saturation magnetization. The
concentration of Fe in Ni-Fe coating is an effective parameter on the magnetic properties of
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coatings, so that the alloy coating provides better magnetic properties when the Fe content of the
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coating is almost 19-24 wt.% [112]. In this regard, Permalloy is the most important alloy which
is widely used in the electrodeposition process of Ni-Fe coatings [113]. It is stated that an
increase in cathode potential for Ni-Fe coatings with the same thickness leads to a decrease in the
percentage of Fe and an increase in the percentage of Ni in the coating; thus, the coercivity
increases and magnetization decreases [114]. A similar behavior with an increase in thickness
was observed in the case of coatings with the same cathodic potential of deposition [115]. It has
been suggested that the type of applied current is effective on the grain size and subsequently the

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magnetic properties. The coercivity reduction in coating electroplated with PRC is almost 37 %
more than that of electroplated with DC. This behavior is explained with the smaller grain size of
coatings electroplated with PRC [77]. As shown in Fig. 12, an increase in Fe content causes an
increase in magnetic saturation and a decrease in coercivity. This is ascribed to the grain size of
deposit that is decreased with increasing Fe content [112]

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Fig. 12 Effect of Fe content on the magnetic saturation and coercivity of Ni-Fe alloy [77].
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The presence of sodium saccharin which as a strain reducer agent in electrolyte leads to a
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decrease in the grain size, which in turn decreases the coercivity and subsequently enhances the
magnetic properties of the coating [22](see Fig. 13).
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Fig. 13 The effect of saccharine on Fe concentration and saturated magnetization [22].

The annealing process is also effective on the magnetic properties so that the lattice strain and
defects decrease with increase in temperature, which in turn decreases the coercivity since
coercivity is highly controlled by the number of dislocations and grain boundaries [46, 116].

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Therefore, an increase in annealing temperature increases saturation magnetization and magnetic
flux density.

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The use of a magnetic field in electrodeposition process is effective on magnetic permeability
[117, 118]. The presence of a magnetic field parallel or perpendicular to the substrate surface in

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an electrodeposition system leads to the increased permeability. In this case, the permeability
reaches a maximum value when a magnetic field is parallel to the substrate surface. Fig. 14

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indicates the effect of magnetic field on the coercivity. As shown in Fig. 14, the coercivity can
be affected by a magnetic field, while it is independent of the direction of the magnetic field
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[118]. The presence of a magnetic field is also effective on the composition of the coating. An
increase in magnetic flux density leads to a subsequent increase in Fe content. The magnetic
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properties of a coating can be influenced by the increase in Fe content, which results in saturated
magnetization state [119].
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Fig. 14 The Effect of magnetic field on the coercivity [118].

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7.4. Electrocatalytic properties

Finding an appropriate, cost effective, and eco-friendly replacement for fossil fuels is necessary.
The electrical energies generated by fuel cells are proposed as a popular source of energies. It
seems that the use of fuel cells is a good choice to solve the problem of energy and environment
pollutions because it provides a high efficiency without contamination and also uses hydrogen as

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a fuel (hydrogen gas can be achieved from renewable and nonrenewable resources) [120, 121].
Many studies are conducted in order to produce the hydrogen in acidic and alkaline solutions.

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Different materials are used as a catalyzer to produce hydrogen. For instance, water electrolysis
reaction in alkaline solutions occurs within two stages as follows: Hydrogen evolution reaction

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(HER) and oxygen evolution reaction (OER). In order to increase efficiency of the electrolysis
cell, these reactions should occur at lower values of overpotential. The overpotential of oxygen

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evolution reaction is considered as the main factor for energy loss in water electrolysis reaction
[122, 123]. Ni is a good choice to use in electrolysis reaction, because of its appropriate chemical
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stability. Furthermore, Ni can be used as a catalyzer for anodic and cathodic reactions.
Preparation of an alloy coating with Ni and Fe elements improves the electrocatalytic behavior of
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Ni [124-126]. The results show that activity of Ni-Fe anodes for oxygen evolution reaction is
controlled by the chemical composition of electrodes and the morphology of coating [125]. The
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entrance of Fe into the electrodes ( as Fe oxide or Fe hydroxide) changes the electrical properties
of electrodes so that these variations enhances the activity of OER [127]. Ullal and coworkers
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[128] investigated various Ni-Fe coatings deposited with different current densities. They
reported that coating with 35 wt.% Ni provides a high efficiency for OER and HER. According
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to this report, the surface conditions which improve the HER have a negative effect on the OER.
Ni-Fe alloy has been also used as an electrocatalyst in an air-hydrazine fuel cell. The main
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problem with an air-hydrazine fuel cell is the use of expensive noble metals as a catalyzer;
though having many benefits [129]. Multiwall carbon nanotube (MWCNT) filled with Ni-Fe
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alloy are used for oxidation of hydrazine [130]. This alloy is embedded in nanotubes using the
electrodeposition process in the presence of methylbenzene. Fig. 15 displays the cyclic
voltammograms of MWCNT based alloys with in comparison to graphene based alloys. As
observed the catalytic activity of MWCNT-based Ni–Fe is higher than the graphene-based one,
and the reason of this phenomenon is not clear up to now. Thorough dispersion of Ni-Fe alloy on
the carbon cathodes led to the high catalytic activity of MWCNT- and graphene-based Ni–Fe

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alloy. The significant result of this graph is that Ni is the active catalyst, while iron has a
synergistic role in the oxidation of hydrazine hydrate [131].

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Fig. 15 Cyclic voltammetric measurements of MWCNT- and graphene-based alloys in 0.1 M
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hydrazine hydrate–0.015 M KOH–1 M NaCl solution, 60 °C, 20 mV s-1 [131].

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7.5. Corrosion behavior

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A widely used method for measuring the corrosion resistance is polarization curve of alloys.
Addition of Fe as an active element rather than Ni reduces the corrosion resistance. According to
Starosta et al. [132], the corrosion rate has a proportional relation while the corrosion potential is
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inversely proportional to iron content. For instance, the difference between corrosion potentials
for nickel and Ni–19% Fe coatings were small but it rose to over 330mV for Ni–29% Fe and Ni–
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41% Fe. Torabinejad et al. [133], taking this fact into consideration, deposited functionally
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graded coating. By using the continuous alteration of duty cycle and Ipeak in eight steps from 88%
duty cycle to 11% duty cycle, the content of Fe from 37 wt% in the interface of coating-substrate
was reduced to 15 wt% in the outer layer of coating. This variation in chemical composition is
displayed in Fig. 16 that is ascribed to Ipeak. Therefore, content of active element in the top layer
of coating is lower than that of the beneath layers, leading to the improved corrosion resistance.
To improve the corrosion resistance of Ni-Fe alloys, the addition of neutral ceramic particles to
the matrix is proposed. In this respect, Starosta [132] added the micrometric particles of Al2O3
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into the Ni-Fe matrix, which deteriorated the corrosion resistance of coatings. Such a behavior
may be attributed to the large size of particles embedded in the matrix. Fig. 17 shows the
influence of SiC nanoparticles on the corrosion behavior of Ni-Fe alloy. It is obvious that the
corrosion potential shifted to the positive value and the corrosion current reduced to a lower
value indicating the better corrosion resistance of Ni-Fe-SiC coating [134]. The main

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mechanisms effective in improving the corrosion resistance will be explained in the next
sections.

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Fig. 16 Variation of Fe content across the functionally graded Ni-Fe-Al2O3 coating at different
frequencies [133].
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Fig. 17 The effect of SiC nanoparticles on the corrosion behavior of permalloy [134].
7.6. Wear behavior
Limited studies have been performed on wear properties of Ni-Fe. These studies found that Fe
addition reduces the wear resistance in comparison to Ni coating. Also, the wear resistance of the

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composite Ni-Fe-Al2O3 coating is higher than the Ni-Fe coating. To improve the wear resistance
of Ni-Fe, several methods have been applied in the recent years; the addition of hard ceramic
particles such as Al2O3 and employing the PC electrodeposition parameters is one of these
methods. The low duty cycle leads to the high fraction of embedded ceramic particles. Hence,
the deposited Ni-Fe composite coatings at low duty cycle may have a higher wear resistance.

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This fact has used also to deposit functionally graded and multilayer coatings for wear-resistant
applications [91, 133]. Continuous variation of duty cycle during the PC electrodeposition can

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result in the high fraction of ceramic particles in the top layers rather than the layers adjacent to
the substrate. Fig. 18 shows the variation of hardness across the functionally graded composite

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coating. It is obvious that the hardness of the surface layer is greater than the beneath layers,
leading to improved wear resistance of the functionally graded coating. Although there are few

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studies on the wear behavior of Ni-Fe coatings, researchers have claimed that using multilayer
coatings can improve their wear resistance [19, 135]. These studies are still in progress.
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Fig. 18 Variation of microhardness across the functionally graded Ni-Fe-Al2O3 coating. Retrieved
from [133].
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8. Thermal treatment of electrodeposited Ni-Fe

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The applications of Ni-Fe coatings are greatly influenced due to the presence of internal stresses
in the coating structure. An increase in Fe content in electrodeposited Ni-Fe alloys causes a
consequent increase in internal stresses. The presence of stress in Ni-Fe coating decreases the
fatigue life time and stimulates the stress corrosion cracking [136]. The results of previous
studies indicate that an increase in current density and a resulted decrease in Fe content results in
a decrease in internal stresses in Ni-Fe coating. The increase in Fe content and distortion in the

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coating structure leads to the development of some defects such as vacancies, dislocations, voids,
and twins. This fact together with a nonhomogeneous dispersion of Fe in different areas of the
coating can lead to an increase in internal stresses. In order to decrease internal stresses in the
coating, two different ways are available: (1) the use of stress relieving additives such as
saccharine and/or (2) annealing treatment of coating. The effect of saccharin additive has been

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investigated in several studies, and a ductility reduction was observed after annealing process in
the view of the mechanical behavior of Ni-Fe coating. Mechanical properties of the electroplated

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coatings were investigated by several researchers using tension and compression tests and the
obtained results compared with coatings annealed at different temperatures. Fig. 19 is an instance

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which indicates the mechanical properties of electroplated Ni-20%Fe coating after annealing
treatment. The mechanical properties of coatings show the annealed coatings were embrittled. In

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order to decrease the internal stresses of coating, saccharin is used in the electroplating bath. The
microstructure studies by Buchheit [92] indicate that high quantity of sulfur is added to the
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coating in the presence of saccharin in an electroplating bath, which diffuses into grain
boundaries by annealing treatment. The solubility of sulfur in Ni is very low and thus sulfur
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diffuses toward grain boundaries with an increase in temperature. In this case, precipitation of
thin layer of sulfur in grain boundaries leads to an increase in the coating brittleness. According
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to Fig. 19(a), an increase at temperature enhanced the coating brittleness. The increase in
annealing temperature to 300 °C promotes the mechanical properties. The grain size and also
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precipitation of sulfur in grain boundaries are increased with temperature at temperatures above
300°C; thus, Fe sulfides and Ni sulfides are formed. The effect of annealing treatment on the
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mechanical properties of Ni-23%Fe coating which was investigated by Li et al. [137], is shown
in Fig. 19(b). As seen in this figure, an annealing treatment at 250 °C leads to a decrease in
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ductility and an increase in coating strength. It is known that the plastic deformation of metals is
controlled with activities of dislocations and grain boundaries [138]. In the case of large grain
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size metals, the movement of dislocations plays a dominant role in plastic deformation. The
production and dispersion of dislocation initiate from grain boundaries and then intergranular
glide occurs. The grain growth of coatings annealed at 250 °C is negligible while relaxation of
grain boundaries in this temperature leads to the ordering of grain boundaries. Therefore, the
dislocation dispersion from grain boundaries hindered and strength increases. The presence of
dislocation and dividing them into the partial dislocations facilitates generation of the Lomer-

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Cottrell locks which act as a barrier against the other dislocations, leading to the enhanced strain
hardening. The decrease in dislocation density in the grain boundaries of the annealed coating
indicates the reduced Lomer-Cottrell locks. This behavior leads to a decrease in the rate of strain
hardening which can be another reason for the reducing ductility [34, 98, 100, 138].

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(a)

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(b)
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Fig. 19 (a) The typical Tensile test stress–strain curves of Ni-20%Fe [92], (b) Compressive stress–
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strain curves of the as-deposited (AD) and annealed (AN) at 250 °C Ni–23%Fe [137].
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The changes in the microstructure of Ni-Fe coating after annealing process depend on the
chemical composition of the coating and electroplating bath additives. The addition of Fe
element into the Ni nanocrystalline coating enhances thermal stability of the coating. Fig. 20
represents the effect of heat treatment on the grain size of Ni-Fe coatings. According to previous
studies, the lattice strain and hardness of Ni-21%Fe coating decrease significantly through heat
treatment at 100 °C; although the heat treatment process is not effective on the grain size. The

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relaxation of grain boundaries is the most common event at 100 °C. The grain size increases in
the temperature range of 100-264 °C and accelerates at 264 °C. The mechanism of grain growth
at a temperature lower than 264 °C is grain boundary diffusion and above this temperature, the
grain growth is controlled by lattice diffusion mechanism [138]. According to Fig. 20, the effect
of temperature on the grain size can be divided into two distinct stages. The grain size variations

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with temperature are negligible at temperature below 327 °C, while above that a fast grain
growth occurs. According to previous investigations [98, 139] , the grain growth in this range of

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temperature is abnormal. In this case, some of the grains with a better orientation than the
neighbors are grown and surround the other grains. Therefore, the difference in grain sizes

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increases in this region and thus a bimodal structure is formed [139].

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Fig. 20 The effect of annealing temperature on the grain size of Ni-Fe alloys [139-141].
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9. Ni-Fe Composite coating

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The Ni-Fe composite coating produced by electrodeposition process has been rarely investigated.
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The presence of second phase particles in the composite coating can affect the corrosion and
tribological properties of the coating. The hard (rigid) particles improve the tribological
properties and hardness of composite layer by dispersion hardening mechanism. The presence of
a hard ceramic phase in a metallic matrix leads to the increased hardness of composite because of
the Orowan and Hall-Petch effects. The rigid particles can act as a barrier against grain boundary
mobility and thus prevent grain growth (Hall-Petch effect). The increase in the number of rigid

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particles leads to a subsequent rise in the number of locked dislocations and thus, according to
Orowan effect, the required stress for movement of dislocations will be increased [142].
However, the interfacial intersections in the presence of particles with smaller grain size lead to
the decreased mobility of grain boundaries due to the increase in surface area of particles [143].
The ceramic particles can improve the corrosion resistance of coating with various mechanisms.

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These particles can act as a barrier against the corrosive agents and prevent diffusion of them
into the coating and subsequently leads to the reduced number of defects potentially created by

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corrosion attacks in the coating [144]. However, the embedding of nanoparticles in the coating
decreases the defects and intergranular discontinuity and thus a high quality smooth coating can

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be created [145]. It was also stated with Praveen et al. [146] that the embedded particles on the
surface decrease the exposed area against corrosion attacks and accordingly, the corrosion

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resistance of the coating can be increased.
In the case of composite coating with Ni-Fe matrix, the effect of Al2O3, SiC, Si3N4, ZrO2, and
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In2O on properties of the coating was investigated. Table 1 indicates the condition of
electroplating used in these studies. The effect of these particles on the properties of coating can
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be described as follows:

Table 1. The bath condition for different Ni-Fe composite coatings

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Particle
Temperature Particle
TE

Coating Bath composition pH concentration Ref.

(⁰C) size (µm)
(g/L)
250g/l NiSO4·7H2O, 40g/l H3BO3, 0-50g/l FeCl2· 4H2O,
Ni-Fe- Al2O3 special chemicals 0.6g/l IM-PEX NF and 0.1g/l IMPEX 3 55 50-250 0.5-5 [132]
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NZ
112g/l NiSO4·6H2O, 5g/l FeSO4·7H2O, 2g/l H3BO3, 0.5
Ni-Fe-SiC 4 50 0-25 0.05 [134]
g/lsodiumdodecylsulfate, 1g/l L-ascorbic acid
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100g/l H4N2NiO6S2.4H2O, 4g/l FeSO4·7H2O, 30g/l H3BO3

Ni-Fe-ZrO2 3 34 5 <0.1 [47]
(Ethylene glycol solution)
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Ni-Fe- Si3N4 NiSO4·7H2O, FeSO4·7H2O, NiCl2.6H2O H3BO3, Saccharin* 3 55 50 0.086 [20]

Ni-Fe- In2O 100g/l H4N2NiO6S2.4H2O, 4g/l FeSO4·7H2O, 30g/l H3BO3 3 34 2 <0.1 [46]

* The quantity of chemical compounds didn’t mentioned in the reference.

9.1. Effect of Al2O3 particles

Starosta et al. [132] reported that a fine grain composite coating with good coherency can be
achieved with the addition of Al2O3 micro particles. The amount of ceramic particles embedded

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in coating increases with the increase in the content of Fe. Also, it is found a decrease in content
of ceramic particles from 50 to 250 g/dm3 in the electrodeposition bath led to a decrease in
contents of ceramic particles embedded in the coating. The embedded ceramic particles increases
the roughness of coating. The hardness of the coating increases with Fe contents while the size
and content of ceramic particles have a slight effect on hardness. An increase in Fe content of the

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coating causes an increase in corrosion current; thus, the maximum corrosion attacks occur in
Fe-reached areas. This behavior may be due to the formation of a Ni-Fe Galvanic cells. The

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functionally graded coatings have been produced in recent studies [91]. The constant variation in
duty cycle results in a gradual increase in alumina content from interface toward the surface. The

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maximum content of particles is in the outer layer at the minimum duty cycle.
9.2. Effect of SiC

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The presence of SiC nanoparticles in Ni-Fe matrix leads to an improvement in hardness and
corrosion resistance. The texture of the coating can be affected by the presence of second phase
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particles. In this regard, the addition of nanoparticles prevents the formation of preferential
texture and thus a structure with a more random texture is achieved. A major part of the
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composite coating structure are composed of (200) fiber texture. Some (111) and (311) fiber
streaks are created by the addition of particles which increase the possibility of forming a
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random microstructure [78].

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9.3. Effect of ZrO2 particles

Ni-Fe-ZrO2 nanocomposite has been produced using sulphamate bath in ethylene glycol solution.
According to obtained results, the content of particles in the composite is not the only effective
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parameter on the composite hardness; however, the maximum contents of particles embedded in
the composite coating reached 36%. The hardness value for Ni-Fe coating was between 570 and
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750 HV while the hardness value obtained for nanocomposite coating was between 590 and 842
HV. The microstructure, nature, and dispersion of reinforcing particles and electrodeposition
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parameters such as the current and chemical composition of electroplating bath are some other
parameters effective on hardness value. The grain size for this nanocomposite was between 50
and 60 nm [47].
9.4. Effect of Si3N4 particles
The effect of the ratio of Si3N4 particles to saccharine in the electroplating bath has been
investigated. In general, the presence of saccharin in Ni-Fe coating can lead to grain refinement.

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An increase in Si3N4 to saccharine ratio leads to a decrease in grain size and an increase in
hardness of the coating. The use of Si3N4 ceramic particles can help grain refinement so that the
presence of these particles prevents grain growth [20]. Furthermore, the presence of Si3N4
particles can increase the surface roughness of the coating [147, 148]. Increasing the current
density enhanced the embedment of Si3N4 particles into the Ni-Fe matrix as well as the

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microhardness. Presence of Si3N4 particles shifted the reduction potential of Ni-Fe to the less
negative potential by 287 mV. This ascribed to the availability of more active sites on the surface

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offered by conducting Si3N4 particles [48].
9.5. Effect of In2O3 nanoparticles

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Indium oxide particles have a good electrical conductance, because of their small band gap
energy and a high number of carriers in comparison to other ceramic particles. In addition, these

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particles are widely used considering their high chemical stability at high temperatures, excellent
transparency, and luminescence. The use of indium oxide promotes the corrosion resistance,
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hardness, magnetic properties, and electrical conductance. The current density is not effective on
the content of embedded nanoparticles in this coating [46].
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10. Addition of other elements to Ni-Fe coating

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10.1. Ni-Fe-W
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The W metal cannot deposit alone with electrodeposition technique and requires a metal from Fe
group for this purpose [149, 150]. The presence of an oxide layer as an intermediate phase for
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deposition of alloy has been introduced as the main mechanism to produce an alloy coating of W
and Fe group metals. The W ions are adsorbed on the hydroxyl species of Ni. Therefore, the
occurrence of parallel reactions leads to the formation of a heteropoly-tungstate film on the
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surface. Some microcrack can be generated on the surface due to the presence of high stresses in
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the presence of W alone in Ni-W coating. Despite the fact that Fe-W coatings have a good
adhesion to the substrate, their appearance and surface roughness is not favorable. To overcome
this problem, Fe, Ni, and W alloys are used with together [151]. Incorporation of W in the
composition of Ni-Fe alloy leads to the increased hardness of the coating. However, the presence
of Fe and a decrease in stresses can lead to a significant decrease in the number of microcracks.
An increase in W content improves the strength and hardness, since W in the lattice which acts

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as a barrier against dislocations movement [152, 153]. The temperature rise has a significant
effect on the structure and mechanical properties of the coating. The temperature increase to 500
°C during heat treatment can lead to an increase in hardness while by exceeding this temperature
the hardness value is decreased [150].
10.2. Ni-Fe-Cr

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Various efforts have been made to enhance the corrosion resistance of Ni-Fe coating. The
addition of alloy elements such as chromium is one of the methods to increase the corrosion

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resistance. To apply trivalent chromium, Cr(III), which has fewer risks compared to Cr(VI), the
chloride bath is used in the electrodeposition process. FeCl2, NiCl2, and CrCl3 as well as some

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other additives, are used in chloride electroplating baths [154]. The effect of current density and
PC electrodeposition parameters on the deposition of alloying elements in Ni-Fe-Cr system has

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been investigated [154, 155]. The content of Cr in these coatings often is in the range of 2-
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14wt% and depends on the electrodeposition condition. The increase in current density led to a
decrease in the deposition of Fe and Ni, while the deposition of Cr increased. This behavior is
attributed to the fact that the potential of Cr element is lower (more negative) than that of Ni and
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Fe. The lower potential (more overpotential) for Cr can stimulate the reduction of Cr at more
negative potentials. Therefore, the increased current density, which leads to higher overpotential,
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provides the condition for deposition of Cr on the substrate [154]. The increase in pulse
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frequency leads to a decrease in the deposition of Cr and an increase in deposition of Ni in PC

electrodeposition process. In comparison, the Fe content does not change significantly with a
variation of frequency. A decrease in duty cycle leads to an increase in the Cr content in the
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chemical composition of the coating. The reduction reaction of trivalent Cr occurs in two steps.
At the initial step, the reduction of Cr3+ to Cr2+ occurs and then next reduction reaction converts
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Cr2+ to Cr. At lower duty cycles, which the pulse toff is long, Cr2+ ions have sufficient time to exit
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from cathode surface which, in turn, leads to a decrease in Cr content in the chemical
composition of the coating. The results of studies indicated that the corrosion resistance of three
component coatings produced by PC is higher than that produced by DC [155]. Furthermore, the
use of heat treatment process immediately after coating resulted in a significant decrease in
microcracks [154]. In the more recent work, using the pulse duty cycle in an alternative manner
between two values of 20% and 90% resulted in a multilayer Ni-Fe-Cr coating. This work

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showed that at high duty cycles the content of deposited Cr in the coating is higher than the one
deposited at a low duty cycle of 20% [156].
10.3. Ni-Fe-P
The control of Fe in Ni-Fe coating produced by electrodeposition process is difficult due to
anomalous deposition. In addition, the properties of Ni-P coating is weakened because of the fast

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grain growth at temperatures above 350 ºC [44]. Some studies indicate that the control of Fe
content in the coating is possible by use of phosphorus element in the electroplating bath. The

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use of phosphorus and the presence of Fe in the chemical composition of the coating facilitates
the control of grain growth [45]. Furthermore, the presence of phosphorus in the composition of

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the coating can lead to the formation of an amorphous structure. The use of phosphorus leads to
the enhanced ductility, corrosion resistance, and magnetic properties of the coating, although it

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increases the stresses of coating structure. To reduce the residual stresses in the coating the
sulphamate baths can be used. One of the most important limitations to applying this type of bath
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is the formation of impurities in coating structure [157].
10.4. Ni-Fe-Mo
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The incorporation of Mo into the chemical composition of Ni-Fe was carried out by the addition
of molybdate into sulphamate and/or chloride baths. This ternary alloy is used for electrocatalytic
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applications and HER [158]. The results show that this alloy provides a good stability and
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catalytic activity in KOH 30%.

Zn and Mo were also used simultaneously in the chemical composition of Ni-Fe coating. Zn
element can be dissolved by the use of leaching treatment. In this case, a structure with a high
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surface area is created. The high activity of produced structure provides a favorable HER
condition [159].
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Permalloy is widely used for applications that need soft magnetic properties. The electrical
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resistance is also one of the most important physical features for magnetic applications. The
oxidation resistance and special resistance of this alloy can be promoted by addition of Mo and
Cr elements [94]. The electrical resistance is also an important characteristic of soft magnetic
films which can increase the performance of these films. The electrical resistance of Permalloy
can be built up from 180 to 240 Ωμcm by the adding small amounts of Mo. The presence of Mo
and Cr in the chemical composition of coating leads to a decrease in magnetoresistance of
Permalloy. This behavior can be attributed to the structural variations such as a change in grain

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size and chemical composition. The addition of above-mentioned elements can cause a decrease
in grain size, which in turn leads to a decrease in magnetoresistance [160].
10.5. Ni-Fe-C

Electroplated Ni-Fe-C coating is used for hydrogen evolution reaction because of its high

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catalytic activity and a good stability [161]. The appropriate activity of this coating is attributed
to the natural activity of carbon, which is entered into Ni-Fe coating. The Lysine is used in
sulfate based solution for embedding carbon in Ni-Fe coating. Song et al. [162]reported that the

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maximum content of carbon in the coating can reach 1.59 %. The overpotential value for a
coating with a carbon content of 1.59% is very low and thus this coating is very convenient for

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HER. The catalytic behavior of the coating can be influenced by the content of carbon and grain
size. A decrease in grain size causes an increase in density of grain boundaries which act as

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preferred places for HER, leading to the reduced values of overpotential.
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11. Applications

Nowadays, the main use of Ni-Fe is related to its magnetic properties. The magnetic properties of
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the coating can be improved by a decrease in coercivity and an increase in saturated current
density and saturated magnetization. Some of the industrial applications of Ni-Fe deposits are
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shown in Fig. 21. The Ni–Fe alloy deposits are used in the electronic industry for memory,
recording and storage devices in computers, Null-balance transformer for residual current
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devices with medium response sensitivity, measurement transducers, pulse transformers,

thyristor protective chokes, transducer cores, relay parts, stator laminations for stepping motors
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in quartz watches, shielding for low temperature applications (e.g. liquid helium or nitrogen),
storage chokes, flux conductors and pole pieces in magnetic valves, printer, electro valves,
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magnetic heads for tape recorders [51, 52, 58, 160, 163-167]. The above mentioned applications
have used extensively in practical applications, however there are some ongoing applications that
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is expected to be expanded in near future. These cases are briefly demonstrated in the following.
Ni-Fe powders are widely used as functional filler for electromagnetic wave absorbent
composites. Presently, Ni-Fe powder with a disk-shaped morphology is produced using
mechanical alloying [168]. The high density of Ni-Fe powders is a drawback for fabrication of
light-weight magnetic absorbent composites. To overcome this drawback, the core-shell particles
are used as a substrate in the electrodeposition of Ni-Fe alloy. For this purpose, Diatomite

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particle, which is a kind of silica stone, is used in the electrodeposition process. At first, a copper
coating is applied on the surface of these particles using the electroless technique to increase
their electrical conductivity and subsequently a Ni-Fe coating is produced by an
electrodeposition process. Therefore, a particle with low density is produced which provide good
magnetic properties and can be used as a magnetic absorbent functional filler [169].

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NiFe2O4 spinel is used in microwave devices, storage of large volumes of data in the magnetic
form, solid oxide fuel cell, and neutral anodes for the electrolysis process of aluminum. Ni-Fe

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coatings produced by electrodeposition process have been considered recently for fabrication of
NiFe2O4 spinel [35]. Electrodeposition process is a cost effective process which is ideal for

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coating the components with complex geometry. In order to produce the NiFe2O4 spinel, the
thermal oxidation process for Ni-Fe coatings is performed at high temperatures. The heat

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treatment process in the presence of oxygen or air can lead to a change in microstructure which
is dependent on the properties of the coating produced by an electrodeposition process.
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D
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C EP
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Fig. 21 Examples of different Ni-Fe based coatings applied on components in various industries
[167].

12. Future scope and conclusion

This article summarized different aspects of Ni-Fe electrodeposition and its properties. The

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process, effective parameters and related properties were reviewed. The effects of alloying
elements to Ni-Fe electrodeposits and reinforcements are briefly discussed and eventually
applications of Ni-Fe alloy were mentioned.

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Based on the mentioned assessments in previous sections, although the magnetic and electrical
properties of electrodeposited Ni-Fe alloy has attracted attentions, corrosion and wear resistance

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of the Ni-Fe coating is not still appropriate. It is obvious that using the coating in various
industries need an improvement of corrosion and wear resistance. For instance, this alloy has

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used in electro-valves, relay parts and printers as a coating or electroformed material. In these
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situations, resistance to wear and corrosion is critical for this coating. In the case of wear and
corrosion behavior of Ni-Fe coating in various conditions, not only few studies have been
considered but also for improvement of these properties little efforts have dedicated. Increasing
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the wear and corrosion resistance can be done by different methods such as addition of other
alloying elements, addition of ceramic particles, and manipulation of electrodeposition
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parameters. Addition of other elements and ceramic particles to the Ni-Fe matrix have
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considered in previous studies, however a deep understanding of subject is not yet achieved.
These studies are not enough for judgment about the performance of above methods.
Accordingly, it is expected that more attentions will devote to these subjects in future studies.
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Moreover, the effect of alloying elements and embedding particles on the magnetic properties of
Ni-Fe coatings, as a main character of this kind of alloys, are neglected in previous reports.
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Superior resistance to wear and corrosion may also be achieved by manipulation of pulsed
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current parameters. In this regard, multilayer and graded metallic Ni-Fe coatings have been the
subject of investigations in recent years due to their proper electrical, magnetic, optical and
mechanical properties and appropriate corrosion resistance [170-172]. The developed multilayer
coatings fabricated through capability of PC electrodeposition parameters. It seems that
development of multilayer and graded Ni-Fe coatings in the future as well as investigation of
their magnetic and electrocatalytic properties of these coatings become the popular issues for
researchers. In addition, electrochemical aspects of PC electrodeposition is more important in

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future. Incorporation of alloying elements into the Ni-Fe deposits may be interesting as they may
improve the corrosion or wear resistance. Maintenance of magnetic properties is the most
important subject in this field and the dedicated works seem not to be sufficient up to now.
Electrodeposited Ni-Fe coatings could have bright future for electrocatalytic applications.
Combination of electrodeposition and other methods for production of a system with more

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exposed area for HER or OER may be useful. In this regard, electrodeposits of Ni-Fe on CNT
and MWCNT and hierarchically structured coatings [173] were fabricated and probably will be

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used in future.

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References

[1] S. Mahdavi, S.R. Allahkaram, Composition, characteristics and tribological behavior of Cr,

U
Co–Cr and Co–Cr/TiO2 nano-composite coatings electrodeposited from trivalent chromium
AN
based baths, J. Alloys Compd., 635 (2015) 150-157.
[2] J.T. De Hosson, A. Cavaleiro, Galileo comes to the surface!, in: Nanostructured coatings,
M

Springer, 2006, pp. 1-26.

[3] S.S. Djokic, Electrodeposition: Theory and Practice, Springer Science & Business Media,
D

2010.
[4] B. Hong, C.-h. Jiang, X.-j. Wang, Texture of electroplated copper film under biaxial stress,
TE

Materials transactions, 47 (2006) 2299-2301.

[5] K. Asa Deepthi, R. Balachandran, B.H. Ong, K.B. Tan, H.Y. Wong, H.K. Yow, S. Srimala,
EP

Physical and electrical characteristics of NiFe thin films using ultrasonic assisted pulse
electrodeposition, Appl. Surf. Sci., 360 (2016) 519-524.
[6] M.S. Chandrasekar, M. Pushpavanam, Pulse and pulse reverse plating—Conceptual,
C

advantages and applications, Electrochim. Acta, 53 (2008) 3313-3322.

AC

[7] M. Sajjadnejad, A. Mozafari, H. Omidvar, M. Javanbakht, Preparation and corrosion

resistance of pulse electrodeposited Zn and Zn–SiC nanocomposite coatings, Appl. Surf. Sci.,
300 (2014) 1-7.
[8] G.A. Di Bari, Electrodeposition of nickel, Modern Electroplating, 5 (2000) 79-114.
[9] M. Schlesinger, M. Paunovic, Modern electroplating, John Wiley & Sons, 2011.
[10] J.R. Davis, Nickel, cobalt, and their alloys, ASM international, 2000.

42
 ACCEPTED MANUSCRIPT

[11] Y. Liu, Y.-X. Yu, W.-D. Zhang, Photoelectrochemical properties of Ni-doped Fe2O3 thin
films prepared by electrodeposition, Electrochim. Acta, 59 (2012) 121-127.
[12] Y. Motomura, T. Tatsumi, H. Urai, M. Aoyama, Soft magnetic properties and heat stability
for Fe/NiFe superlattices, IEEE Trans. Magn., 26 (1990) 2327-2331.
[13] H. Kuru, H. Kockar, M. Alper, O. Karaagac, Growth of binary Ni–Fe films:

PT
Characterisations at low and high potential levels, J. Magn. Magn. Mater., 377 (2015) 59-64.
[14] A.D. Romig, J. Goldstein, Determination of the Fe-Ni and Fe-Ni-P phase diagrams at low

RI
temperatures (700 to 300 C), Metall. Trans. A, 11 (1980) 1151-1159.
[15] P. Leech, C. Sykes, LXIX. The evidence for a superlattice in the nickel-iron alloy Ni3Fe,

SC
The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, 27 (1939)
742-753.

U
[16] C.-W. Yang, D. Williams, J. Goldstein, A revision of the Fe-Ni phase diagram at low
temperatures (< 400 C), Journal of Phase Equilibria, 17 (1996) 522-531.
AN
[17] F. Van Der Woude, Phase diagram of the order-disorder transition in Ni 3 Fe, Acta Metall.,
29 (1981) 1255-1262.
M

[18] C. Wei-Su, W. Yang, G. Jun-Ming, H. Feng-Jiao, Thermal Stability of Ni-Fe Alloy Foils
Continuously Electrodeposited in a Fluorborate Bath, Open Journal of Metal, 2012 (2012).
D

[19] V. Torabinejad, A.S. Rouhaghdam, M. Aliofkhazraei, M. Allahyarzadeh, Electrodeposition

of Ni–Fe and Ni–Fe-(nano Al 2 O 3) multilayer coatings, J. Alloys Compd., 657 (2016) 526-536.
TE

[20] M. Yusrini, Y.I. Idris, Dispersion of Strengthening Particles on the Nickel-Iron-Silicon

Nitride Nanocomposite Coating, Advanced Materials Research, 647 (2013) 705-710.
EP

[21] S. Van Petegem, J. Zimmermann, H. Van Swygenhoven, Microstructure and deformation

mechanisms in nanocrystalline Ni–Fe. Part II. In situ testing during X-ray diffraction, Acta
C

Mater., 61 (2013) 5846-5856.

[22] I. Tabakovic, V. Inturi, J. Thurn, M. Kief, Properties of Ni1−xFex (0.1<x<0.9) and Invar
AC

(x=0.64) alloys obtained by electrodeposition, Electrochim. Acta, 55 (2010) 6749-6754.

[23] I. Vernyhora, V. Tatarenko, S. Bokoch, Thermodynamics of fcc-Ni–Fe Alloys in a Static
Applied Magnetic Field, ISRN Thermodynamics, 2012 (2012).
[24] A. Sanaty-Zadeh, K. Raeissi, A. Saidi, Properties of nanocrystalline iron–nickel alloys
fabricated by galvano-static electrodeposition, J. Alloys Compd., 485 (2009) 402-407.

43
 ACCEPTED MANUSCRIPT

[25] H. Dahms, I. Croll, The Anomalous Codeposition of Iron‐Nickel Alloys, J. Electrochem.

Soc., 112 (1965) 771-775.
[26] S. Hessami, C.W. Tobias, A Mathematical Model for Anomalous Codeposition of Nickel‐
Iron on a Rotating Disk Electrode, J. Electrochem. Soc., 136 (1989) 3611-3616.
[27] P. Andricacos, C. Arana, J. Tabib, J. Dukovic, L. Romankiw, Electrodeposition of Nickel‐

PT
Iron Alloys I. Effect of Agitation, J. Electrochem. Soc., 136 (1989) 1336-1340.
[28] W.C. Grande, J. Talbot, Electrodeposition of Thin Films of Nickel--Iron, Metal Deposition

RI
and Dissolution, (1992) 62-73.
[29] M. Matlosz, Competitive Adsorption Effects in the Electrodeposition of Iron‐Nickel Alloys,

SC
J. Electrochem. Soc., 140 (1993) 2272-2279.
[30] C.-C. Hu, A. Bai, The inhibition of anomalous codeposition of iron-group alloys using

U
cyclic voltammetry, J. Electrochem. Soc., 149 (2002) C615-C622.
[31] Á. Llavona, L. Pérez, M.C. Sánchez, V. de Manuel, Enhancement of anomalous
AN
codeposition in the synthesis of Fe–Ni alloys in nanopores, Electrochim. Acta, 106 (2013) 392-
397.
M

[32] B.C. Baker, A.C. West, Electrochemical Impedance Spectroscopy Study of Nickel‐Iron
Deposition I. Experimental Results, J. Electrochem. Soc., 144 (1997) 164-169.
D

[33] C. Cheung, F. Djuanda, U. Erb, G. Palumbo, Electrodeposition of nanocrystalline Ni-Fe

alloys, Nanostruct. Mater., 5 (1995) 513-523.
TE

[34] H. Li, F. Ebrahimi, Synthesis and characterization of electrodeposited nanocrystalline

nickel–iron alloys, Materials Science and Engineering: A, 347 (2003) 93-101.
EP

[35] L. Ma, L. Zhang, X.-b. Li, Z.-y. Li, K.-c. Zhou, Fabrication and characterization of
electrodeposited nanocrystalline Ni–Fe alloys for NiFe2O4 spinel coatings, Transactions of
C

Nonferrous Metals Society of China, 25 (2015) 146-153.

[36] A.O. Gezerman, B.D. Corbacioglu, Analysis of the Characteristics of Nickel-Plating Baths,
AC

International Journal of Chemistry, 2 (2010) 124.

[37] A. Ispas, H. Matsushima, A. Bund, B. Bozzini, A study of external magnetic-field effects on
nickel–iron alloy electrodeposition, based on linear and non-linear differential AC
electrochemical response measurements, J. Electroanal. Chem., 651 (2011) 197-203.

44
 ACCEPTED MANUSCRIPT

[38] A. Ramazani, V. Asgari, A.H. Montazer, M. Almasi Kashi, Tuning magnetic fingerprints of
FeNi nanowire arrays by varying length and diameter, Current Applied Physics, 15 (2015) 819-
828.
[39] J. Horkans, Effect of plating parameters on electrodeposited NiFe, J. Electrochem. Soc., 128
(1981) 45-49.

PT
[40] I. Tabakovic, J. Gong, S. Riemer, V. Venkatasamy, M. Kief, Stress evolution in Co x Fe 1−
x (x= 0.33–0.87) electrodeposited films, Electrochim. Acta, 55 (2010) 9035-9041.

RI
[41] A. Vicenzo, Structure and Mechanical Properties of Electrodeposited Nanocrystalline Ni-Fe
Alloys, J. Electrochem. Soc., 160 (2013) D570-D577.

SC
[42] Y.-h. Zhang, G.-f. Ding, Y.-l. Cai, H. Wang, B. Cai, Electroplating of low stress permalloy
for MEMS, Mater. Charact., 57 (2006) 121-126.

U
[43] N.V. Myung, K. Nobe, Electrodeposited iron group thin-film alloys: structure-property
relationships, J. Electrochem. Soc., 148 (2001) C136-C144.
AN
[44] M.H. Seo, D.J. Kim, J.S. Kim, The effects of pH and temperature on Ni–Fe–P alloy
electrodeposition from a sulfamate bath and the material properties of the deposits, Thin Solid
M

Films, 489 (2005) 122-129.

[45] D.J. Kim, Y.M. Roh, M.H. Seo, J.S. Kim, Effects of the peak current density and duty cycle
D

on material properties of pulse-plated Ni–P–Fe electrodeposits, Surf. Coat. Technol., 192 (2005)
88-93.
TE

[46] A.K. Chaudhari, V.B. Singh, Studies on Electrodeposition, Microstructure and Physical
Properties of Ni-Fe/In2O3 Nanocomposite, J. Electrochem. Soc., 162 (2015) D341-D349.
EP

[47] A.K. Chaudhari, V. Singh, Structure and Properties of Electro Co-Deposited Ni-Fe/ZrO2
Nanocomposites from Ethylene Glycol Bath, Int. J. Electrochem. Sci, 9 (2014) 7021-7037.
C

[48] M.K. Tripathi, D.K. Singh, V. Singh, Microstructure and properties of electrochemically
deposited Ni-Fe/Si3N4 nanocomposites from a DMF bath, J. Electrochem. Soc., 162 (2015)
AC

D87-D95.
[49] Y. Tsuru, M. Nomura, F.R. Foulkes, Effects of boric acid on hydrogen evolution and
internal stress in films deposited from a nickel sulfamate bath, J. Appl. Electrochem., 32 (2002)
629-634.
[50] Y. Wu, D. Chang, D. Kim, S.-C. Kwon, Influence of boric acid on the electrodepositing
process and structures of Ni–W alloy coating, Surf. Coat. Technol., 173 (2003) 259-264.

45
 ACCEPTED MANUSCRIPT

[51] A. Dolati, M. Ghorbani, A. Afshar, The electrodeposition of quaternary Fe–Cr–Ni–Mo

alloys from the chloride-complexing agents electrolyte. Part I. Processing, Surf. Coat. Technol.,
166 (2003) 105-110.
[52] A. Saedi, M. Ghorbani, Electrodeposition of Ni–Fe–Co alloy nanowire in modified AAO
template, Mater. Chem. Phys., 91 (2005) 417-423.

PT
[53] R. Oriňáková, A. Turoňová, D. Kladeková, M. Gálová, R.M. Smith, Recent developments
in the electrodeposition of nickel and some nickel-based alloys, J. Appl. Electrochem., 36 (2006)

RI
957-972.
[54] S. Gadad, T.M. Harris, Oxygen Incorporation during the Electrodeposition of Ni, Fe, and

SC
Ni‐Fe Alloys, J. Electrochem. Soc., 145 (1998) 3699-3703.
[55] N. Zech, D. Landolt, The influence of boric acid and sulfate ions on the hydrogen formation

U
in Ni Fe plating electrolytes, Electrochim. Acta, 45 (2000) 3461-3471.
[56] M. Ghorbani, A. Dolati, A. Afshar, Electrodeposition of Ni–Fe Alloys in the Presence of
AN
Complexing Agents, Russ. J. Electrochem., 38 (2002) 1173-1177.
[57] V.C. Kieling, Parameters influencing the electrodeposition of Ni-Fe alloys, Surf. Coat.
M

Technol., 96 (1997) 135-139.

[58] A. Afshar, A. Dolati, M. Ghorbani, Electrochemical characterization of the Ni–Fe alloy
D

electrodeposition from chloride–citrate–glycolic acid solutions, Mater. Chem. Phys., 77 (2003)

352-358.
TE

[59] C.-J. Chen, K.-L. Lin, Internal stress and adhesion of amorphous Ni–Cu–P alloy on
aluminum, Thin Solid Films, 370 (2000) 106-113.
EP

[60] A. Bhandari, S.J. Hearne, B.W. Sheldon, S.K. Soni, Microstructural origins of saccharin-
induced stress reduction in electrodeposited Ni, J. Electrochem. Soc., 156 (2009) D279-D282.
C

[61] D. Mockute, G. Bernotiene, The interaction of additives with the cathode in a mixture of
saccharin, 2-butyne-1,4-diol and phthalimide during nickel electrodeposition in a Watts-type
AC

electrolyte, Surf. Coat. Technol., 135 (2000) 42-47.

[62] F.R. Bento, L.H. Mascaro, Electrocrystallisation of Fe–Ni alloys from chloride electrolytes,
Surf. Coat. Technol., 201 (2006) 1752-1756.
[63] S.H. Kim, H.J. Sohn, Y.C. Joo, Y.W. Kim, T.H. Yim, H.Y. Lee, T. Kang, Effect of
saccharin addition on the microstructure of electrodeposited Fe–36 wt.% Ni alloy, Surf. Coat.
Technol., 199 (2005) 43-48.

46
 ACCEPTED MANUSCRIPT

[64] J.-k. Yu, M.-z. Wang, Q. Li, J. Yang, L. Liu, Effects of saccharin on microstructure and
property of electro-deposited Ni-Fe alloys, Transactions of Nonferrous Metals Society of China,
19 (2009) 805-809.
[65] S. Mohajeri, A. Dolati, S. Rezagholibeiki, Electrodeposition of Ni/WC nano composite in
sulfate solution, Mater. Chem. Phys., 129 (2011) 746-750.

PT
[66] A. Sharma, S. Bhattacharya, S. Das, K. Das, Fabrication of Sn nanostructures by template
assisted pulse electrodeposition, Surf. Eng., (2015) 1743294415Y.0000000091.

RI
[67] A. Sharma, S. Bhattacharya, S. Das, K. Das, A Study on the Effect of Pulse
Electrodeposition Parameters on the Morphology of Pure Tin Coatings, Metallurgical and

SC
Materials Transactions A, 45 (2014) 4610-4622.
[68] A. Sohrabi, A. Dolati, M. Ghorbani, A. Monfared, P. Stroeve, Nanomechanical properties of

U
functionally graded composite coatings: Electrodeposited nickel dispersions containing silicon
micro- and nanoparticles, Mater. Chem. Phys., 121 (2010) 497-505.
AN
[69] S. Sanjabi, A. Shirani, The morphology and corrosion resistance of electrodeposited Co-
TiO2 nanocomposite coatings, Mater. Corros., 63 (2011) 695-702.
M

[70] S. Spanou, E.A. Pavlatou, Pulse electrodeposition of Ni/nano-TiO2 composites: effect of

pulse frequency on deposits properties, J. Appl. Electrochem., 40 (2010) 1325-1336.
D

[71] M.H. Allahyarzadeh, M. Aliofkhazraei, A.R.S. Rouhaghdam, V. Torabinejad, Gradient

electrodeposition of Ni-Cu-W(alumina) nanocomposite coating, Materials & Design, 107 (2016)
TE

74-81.
[72] M.H. Allahyarzadeh, M. Aliofkhazraei, A.R.S. Rouhaghdam, V. Torabinejad,
EP

Electrodeposition of Ni–W–Al2O3 nanocomposite coating with functionally graded

microstructure, J. Alloys Compd., 666 (2016) 217-226.
C

[73] M. Allahyarzadeh, M. Aliofkhazraei, A. Sabour Rouhaghdam, V. Torabinejad, Functionally

graded nickel–tungsten coating: electrodeposition, corrosion and wear behaviour, Can. Metall.
AC

Q., 55 (2016) 303-311.

[74] M.E. Bahrololoom, R. Sani, The influence of pulse plating parameters on the hardness and
wear resistance of nickel–alumina composite coatings, Surf. Coat. Technol., 192 (2005) 154-163.
[75] H. Schultz, M. Pritzker, Modeling the Galvanostatic Pulse and Pulse Reverse Plating of
Nickel‐Iron Alloys on a Rotating Disk Electrode, J. Electrochem. Soc., 145 (1998) 2033-2042.

47
 ACCEPTED MANUSCRIPT

[76] F. Giro, K. Bedner, C. Dhum, J. Hoffmann, S. Heussler, L. Jian, U. Kirsch, H. Moser, M.

Saumer, Pulsed electrodeposition of high aspect-ratio NiFe assemblies and its influence on
spatial alloy composition, Microsystem technologies, 14 (2008) 1111-1115.
[77] D. Flynn, M.P. Desmulliez, Influence of pulse reverse plating on the properties of Ni-Fe
thin films, Magnetics, IEEE Transactions on, 46 (2010) 979-985.

PT
[78] Y.-M. Yeh, C.-S. Chen, M.-H. Tsai, Y.-C. Shyng, S.-Y. Lee, K.-L. Ou, Effect of Pulse-
Reverse Current on Microstructure and Properties of Electroformed Nickel–Iron Mold Insert,

RI
Jpn. J. Appl. Phys., 44 (2005) 1086-1090.
[79] K.-M. Yin, S.-L. Jan, Current pulse plating of nickel-iron alloys on rotating disk electrodes,

SC
Surf. Coat. Technol., 79 (1996) 252-262.
[80] A. Tokarz, P. Wieczorek, A. Lis, J. Morgiel, Microstructure of electrodeposited NiFe/Cu

U
multilayers, Journal of microscopy, 237 (2010) 456-460.
[81] N. Zech, E. Podlaha, D. Landolt, Anomalous Codeposition of Iron Group Metals: II.
AN
Mathematical Model, J. Electrochem. Soc., 146 (1999) 2892-2900.
[82] J. Vaes, J. Fransaer, J.P. Celis, The role of metal hydroxides in NiFe deposition, J.
M

Electrochem. Soc., 147 (2000) 3718-3724.

[83] J. Vaes, J. Fransaer, J.-P. Celis, Cathodic Inhibition Effects during NiFe and ZnNi Alloy
D

Deposition, J. Electrochem. Soc., 149 (2002) C567.

[84] S.D. Leith, S. Ramli, D.T. Schwartz, Characterization of Ni x Fe1− x (0.10< x< 0.95)
TE

Electrodeposition from a Family of Sulfamate‐Chloride Electrolytes, J. Electrochem. Soc., 146

(1999) 1431-1435.
EP

[85] S.M. Lari Baghal, M. Heydarzadeh Sohi, A. Amadeh, A functionally gradient nano-Ni–
Co/SiC composite coating on aluminum and its tribological properties, Surf. Coat. Technol., 206
C

(2012) 4032-4039.
[86] C.-W. Su, E.-L. Wang, Y.-B. Zhang, F.-J. He, Ni1−xFex (0.1 &lt; x &lt; 0.75) alloy foils
AC

prepared from a fluorborate bath using electrochemical deposition, J. Alloys Compd., 474 (2009)
190-194.
[87] S. Singh, M. Sribalaji, N.P. Wasekar, S. Joshi, G. Sundararajan, R. Singh, A.K. Keshri,
Microstructural, phase evolution and corrosion properties of silicon carbide reinforced pulse
electrodeposited nickel–tungsten composite coatings, Appl. Surf. Sci., 364 (2016) 264-272.

48
 ACCEPTED MANUSCRIPT

[88] S. Sangeetha, G.P. Kalaignan, J.T. Anthuvan, Pulse electrodeposition of self-lubricating Ni–
W/PTFE nanocomposite coatings on mild steel surface, Appl. Surf. Sci., 359 (2015) 412-419.
[89] R.S. Bhat, A.C. Hegde, Production of layer by layer Zn–Fe compositional multilayer alloy
coatings using triangular current pulses for better corrosion protection, Transactions of the IMF,
93 (2015) 157-163.

PT
[90] Y. Yang, Y.F. Cheng, Fabrication of Ni–Co–SiC composite coatings by pulse
electrodeposition — Effects of duty cycle and pulse frequency, Surf. Coat. Technol., 216 (2013)

RI
282-288.
[91] V. Torabinejad, M. Aliofkhazraei, A. Rouhaghdam, M. Allahyarzadeh, Electrodeposition of

SC
Ni–Fe–Mn/Al2O3 functionally graded nanocomposite coatings, Surf. Eng., (2016) Inpress doi:
10.1080/02670844.2016.1151577.

U
[92] T.E. Buchheit, S.H. Goods, P.G. Kotula, P.F. Hlava, Electrodeposited 80Ni–20Fe
(Permalloy) as a structural material for high aspect ratio microfabrication, Materials Science and
AN
Engineering: A, 432 (2006) 149-157.
[93] K.-M. Yin, S.-L. Jan, C.-C. Lee, Current pulse with reverse plating of nickel-iron alloys in a
M

sulphate bath, Surf. Coat. Technol., 88 (1997) 219-225.

[94] K. Nakamura, M. Umetani, T. Hayashi, Electrodeposition of iron-rich Ni-Fe alloys from
D

sulphate and chloride baths, Surface technology, 25 (1985) 111-119.

[95] R. Balachandran, H. Yow, B. Ong, K.B. Tan, K. Anuar, H. Wong, Surface morphology and
TE

electrical properties of pulse electrodeposition of NiFe films on copper substrates in ultrasonic

field, Int. J. Electrochem. Sci, 6 (2011) 3564-3579.
EP

[96] R. Abdel-Karim, Y. Reda, M. Muhammed, S. El-Raghy, M. Shoeib, H. Ahmed,

Electrodeposition and characterization of nanocrystalline Ni-Fe alloys, Journal of Nanomaterials,
C

2011 (2011) 7.
[97] F. Ebrahimi, H. Li, Structure And Properties Of Electrodeposited Nanocrystalline FCC Ni-
AC

Fe Alloys, Reviews on Advanced Materials Science, 5 (2003) 134-138.

[98] H. Li, F. Ebrahimi, H. Choo, P.K. Liaw, Grain size dependence of tensile behavior in
nanocrystalline Ni–Fe alloys, Journal of materials science, 41 (2006) 7636-7642.
[99] N.P. Wasekar, P. Haridoss, S.K. Seshadri, G. Sundararajan, Sliding wear behavior of
nanocrystalline nickel coatings: Influence of grain size, Wear, 296 (2012) 536-546.

49
 ACCEPTED MANUSCRIPT

[100] H. Li, F. Ebrahimi, Tensile behavior of a nanocrystalline Ni–Fe alloy, Acta Mater., 54
(2006) 2877-2886.
[101] S. Van Petegem, J. Zimmermann, H. Van Swygenhoven, Yield point phenomenon during
strain rate change in nanocrystalline Ni–Fe, Scripta Mater., 65 (2011) 217-220.
[102] T. Kruml, C. Dupas, J. Martin, A critical assessment of dislocation multiplication laws in

PT
germanium, Acta Mater., 54 (2006) 4721-4729.
[103] D. Liang, J. Liu, K. Reuter, B. Baker-O’Neal, Q. Huang, Electroplating of Fe-Rich NiFe

RI
Alloys in Sub-50 nm Lines, J. Electrochem. Soc., 161 (2014) D301-D308.
[104] Y. Cao, G. Wei, H. Ge, X. Meng, Study on preparation of NiFe films by galvanostatic

SC
electrodeposition, Surf. Eng., 30 (2014) 97-101.
[105] J. Gong, S. Riemer, M. Kautzky, I. Tabakovic, Composition gradient, structure, stress,

U
roughness and magnetic properties of 5–500nm thin NiFe films obtained by electrodeposition, J.
Magn. Magn. Mater., 398 (2016) 64-69.
AN
[106] O. Dragos, H. Chiriac, N. Lupu, M. Grigoras, I. Tabakovic, Anomalous Codeposition of
fcc NiFe Nanowires with 5–55% Fe and Their Morphology, Crystal Structure and Magnetic
M

Properties, J. Electrochem. Soc., 163 (2016) D83-D94.

[107] R. Sharif, S. Shamaila, F. Shaheen, S. Naseem, J. Chen, M. Khaleeq-ur-Rahman, K.
D

Hussain, X. Han, Nanotube wall thickness dependent magnetization reversal properties of NiFe
nanotubes, J. Appl. Phys., 113 (2013) 024315.
TE

[108] M. Bedir, O. Bakkaloğlu, I. Karahan, M. Öztaş, A study on electrodeposited Ni x Fe1− x

alloy films, Pramana, 66 (2006) 1093-1104.
EP

[109] M. Alper, H. Kockar, H. Kuru, T. Meydan, Influence of deposition potentials applied in

continuous and pulse waveforms on magnetic properties of electrodeposited nickel–iron films,
C

Sensors and Actuators A: Physical, 129 (2006) 184-187.

[110] H. Seet, X. Li, Z. Zhao, Y. Kong, H. Zheng, W. Ng, Development of high permeability
AC

nanocrystalline permalloy by electrodeposition, J. Appl. Phys., 97 (2005) 10N304.

[111] D. Navas, A. Asenjo, M. Jaafar, K. Pirota, M. Hernandez-Velez, R. Sanz, W. Lee, K.
Nielsch, F. Batallan, M. Vazquez, Magnetic behavior of NixFe (100− x)(65⩽ x⩽ 100) nanowire
arrays, J. Magn. Magn. Mater., 290 (2005) 191-194.
[112] B. Koo, B. Yoo, Electrodeposition of low-stress NiFe thin films from a highly acidic
electrolyte, Surf. Coat. Technol., 205 (2010) 740-744.

50
 ACCEPTED MANUSCRIPT

[113] T. Zhang, P. Zhang, H.-w. Li, Y.-h. Wu, Y.-s. Liu, Fabrication of micro electromagnetic
actuator of high energy density, Mater. Chem. Phys., 108 (2008) 325-330.
[114] M.S. Salem, P. Sergelius, R. Zierold, J.M.M. Moreno, D. Görlitz, K. Nielsch, Magnetic
characterization of nickel-rich NiFe nanowires grown by pulsed electrodeposition, J. Mater.
Chem., 22 (2012) 8549-8557.

PT
[115] H. Kockar, M. Alper, H. Topcu, Effect of potantiostatic waveforms on properties of
electrodeposited NiFe alloy films, The European Physical Journal B-Condensed Matter and

RI
Complex Systems, 42 (2004) 497-501.
[116] R. Kannan, S. Ganesan, T. Selvakumari, An investigation on effects of annealing on

SC
magnetic properties of Ni-Fe-WS electrodeposited coatings in tri sodium citrate bath, IJST, 37
(2013) 181-187.

U
[117] A. Ispas, A. Bund, H. Matsushima, F. Bogani, B. Bozzini, Electrodeposition of NiFe
Alloys in a Magnetic Field, ECS Transactions, 3 (2007) 15-27.
AN
[118] E. Kubo, N. Ooi, H. Aoki, D. Watanabe, J.-H. Jeong, C. Kimura, T. Sugino, Effect of
magnetic field on permeability of electroplated permalloy for microdevices, Jpn. J. Appl. Phys.,
M

49 (2010) 04DB17.
[119] Y.D. Yu, G.Y. Wei, H.F. Guo, J.W. Lou, H.L. Ge, Study on preparation of NiFeP films by
D

pulse electrodeposition, Surf. Eng., 28 (2012) 30-36.

[120] F. Barbir, Transition to renewable energy systems with hydrogen as an energy carrier,
TE

Energy, 34 (2009) 308-312.

[121] F. Orecchini, A. Santiangeli, A. Dell’Era, A technological solution for an everywhere
EP

energy supply with sun, hydrogen, and fuel cells, Journal of fuel cell science and technology, 3
(2006) 75-82.
C

[122] A.S. Batchellor, S.W. Boettcher, Pulse-Electrodeposited Ni–Fe (Oxy)hydroxide Oxygen

Evolution Electrocatalysts with High Geometric and Intrinsic Activities at Large Mass Loadings,
AC

ACS Catalysis, 5 (2015) 6680-6689.

[123] Q. Luo, M. Peng, X. Sun, Y. Luo, A.M. Asiri, Efficient electrochemical water splitting
catalyzed by electrodeposited NiFe nanosheets film, Int. J. Hydrogen Energy, 41 (2016) 8785-
8792.
[124] K.H. Kim, J.Y. Zheng, W. Shin, Y.S. Kang, Preparation of dendritic NiFe films by
electrodeposition for oxygen evolution, Rsc Advances, 2 (2012) 4759-4767.

51
 ACCEPTED MANUSCRIPT

[125] R. Solmaz, G. Kardaş, Electrochemical deposition and characterization of NiFe coatings as

electrocatalytic materials for alkaline water electrolysis, Electrochim. Acta, 54 (2009) 3726-
3734.
[126] S.H. Ahn, I. Choi, H.-Y. Park, S.J. Hwang, S.J. Yoo, E. Cho, H.-J. Kim, D. Henkensmeier,
S.W. Nam, S.-K. Kim, Effect of morphology of electrodeposited Ni catalysts on the behavior of

PT
bubbles generated during the oxygen evolution reaction in alkaline water electrolysis, Chem.
Commun., 49 (2013) 9323-9325.

RI
[127] J. Landon, E. Demeter, N. İnoğlu, C. Keturakis, I.E. Wachs, R. Vasić, A.I. Frenkel, J.R.
Kitchin, Spectroscopic characterization of mixed Fe–Ni oxide electrocatalysts for the oxygen

SC
evolution reaction in alkaline electrolytes, Acs Catalysis, 2 (2012) 1793-1801.
[128] Y. Ullal, A.C. Hegde, Electrodeposition and electro-catalytic study of nanocrystalline Ni–

U
Fe alloy, Int. J. Hydrogen Energy, 39 (2014) 10485-10492.
[129] J. Li, W. Tang, H. Yang, Z. Dong, J. Huang, S. Li, J. Wang, J. Jin, J. Ma, Enhanced-
AN
electrocatalytic activity of Ni1-xFex alloy supported on polyethyleneimine functionalized MoS2
nanosheets for hydrazine oxidation, RSC Advances, 4 (2014) 1988-1995.
M

[130] J. Wang, Z. Dong, J. Huang, J. Li, X. Jin, J. Niu, J. Sun, J. Jin, J. Ma, Filling carbon
nanotubes with Ni–Fe alloys via methylbenzene-oriented constant current electrodeposition for
D

hydrazine electrocatalysis, Appl. Surf. Sci., 270 (2013) 128-132.

[131] H. Yang, X. Zhong, Z. Dong, J. Wang, J. Jin, J. Ma, A highly active hydrazine fuel cell
TE

catalyst consisting of a Ni–Fe nanoparticle alloy plated on carbon materials by pulse reversal,
RSC Advances, 2 (2012) 5038-5040.
EP

[132] R. Starosta, A. Zielinski, Effect of chemical composition on corrosion and wear behaviour
of the composite Ni–Fe–Al2O3 coatings, J. Mater. Process. Technol., 157-158 (2004) 434-441.
C

[133] V. TORABINEJAD, A.S. ROUHAGHDAM, M. ALIOFKHAZRAEI, M.

ALLAHYARZADEH, Ni–Fe–Al2O3 electrodeposited nanocomposite coating with functionally
AC

graded microstructure, Bull. Mater. Sci., 39 (2016) 857-864.

[134] H. Ataee-Esfahani, M.R. Vaezi, L. Nikzad, B. Yazdani, S.K. Sadrnezhaad, Influence of
SiC nanoparticles and saccharin on the structure and properties of electrodeposited Ni–Fe/SiC
nanocomposite coatings, J. Alloys Compd., 484 (2009) 540-544.

52
 ACCEPTED MANUSCRIPT

[135] V. Torabinejad, M. Aliofkhazraei, A.S. Rouhaghdam, M. Allahyarzadeh, Ni–Fe–Mn–

(nano) Al2O3 Coating with Modulated Composition and Grain Size, Transactions of the Indian
Institute of Metals, (2016) Inpress doi: 10.1007/s12666-016-0913-9.
[136] S. Hadian, D. Gabe, Residual stresses in electrodeposits of nickel and nickel–iron alloys,
Surf. Coat. Technol., 122 (1999) 118-135.

PT
[137] H. Li, F. Jiang, S. Ni, L. Li, G. Sha, X. Liao, S.P. Ringer, H. Choo, P.K. Liaw, A. Misra,
Mechanical behaviors of as-deposited and annealed nanostructured Ni–Fe alloys, Scripta Mater.,

RI
65 (2011) 1-4.
[138] H.Q. Li, F. Ebrahimi, An investigation of thermal stability and microhardness of

SC
electrodeposited nanocrystalline nickel-21% iron alloys, Acta Mater., 51 (2003) 3905-3913.
[139] F. Ebrahimi, H. Li, Grain growth in electrodeposited nanocrystalline fcc Ni–Fe alloys,

U
Scripta Mater., 55 (2006) 263-266.
[140] N. Mukaibo, Y. Shimizu, Y. Fukai, T. Hiroi, Heat Treatment for the Stabilization of
AN
Hydrogen and Vacancies in Electrodeposited Ni-Fe Alloy Films, Materials Transactions, 49
(2008) 2815-2822.
M

[141] M. Thuvander, M. Abraham, A. Cerezo, G. Smith, Thermal stability of electrodeposited

nanocrystalline nickel and iron–nickel alloys, Mater. Sci. Technol., 17 (2001) 961-970.
D

[142] A.D. Pogrebnyak, A.P. Shpak, N.A. Azarenkov, V.M. Beresnev, Structures and properties
of hard and superhard nanocomposite coatings, Physics-Uspekhi, 52 (2009) 29.
TE

[143] S. Kasturibai, G.P. Kalaignan, Characterizations of electrodeposited Ni–CeO2

nanocomposite coatings, Mater. Chem. Phys., 147 (2014) 1042-1048.
EP

[144] B. Bakhit, A. Akbari, Effect of particle size and co-deposition technique on hardness and
corrosion properties of Ni–Co/SiC composite coatings, Surf. Coat. Technol., 206 (2012) 4964-
C

4975.
[145] M. Sajjadnejad, M. Ghorbani, A. Afshar, Microstructure-corrosion resistance relationship
AC

of direct and pulse current electrodeposited Zn-TiO2 nanocomposite coatings, Ceram. Int., 41
(2015) 217-224.
[146] B.M. Praveen, T.V. Venkatesha, Electrodeposition and properties of Zn-nanosized TiO2
composite coatings, Appl. Surf. Sci., 254 (2008) 2418-2424.
[147] Y. Marita, I.I. Yaacob, A. Korsunsky, Characterization of Ni-Fe⁄Si[sub 3]N[sub 4]
Nanocomposite Coatings Deposited by Electroplating, (2009) 106-116.

53
 ACCEPTED MANUSCRIPT

[148] X. Li, Z. Li, Nano-sized Si 3 N 4 reinforced NiFe nanocomposites by electroplating,

Materials Science and Engineering: A, 358 (2003) 107-113.
[149] P. Esther, C. Joseph Kennady, Effect of sodium tungstate on the properties of
electrodeposited nanocrystalline ni-fe-w films, J. Non Oxide Glas, 1 (2010) 35-44.
[150] K.R. Sriraman, S. Ganesh Sundara Raman, S.K. Seshadri, Corrosion behaviour of

PT
electrodeposited nanocrystalline Ni–W and Ni–Fe–W alloys, Materials Science and Engineering:
A, 460-461 (2007) 39-45.

RI
[151] S.-J. Mun, M. Kim, T.-H. Yim, J.-H. Lee, T. Kang, Mechanical and Structural
Characteristics of Electrodeposited Ni–Fe–W Alloy after Heat-Treatment, J. Electrochem. Soc.,

SC
157 (2010) D177.
[152] J. Ahmad, K. Asami, A. Takeuchi, D.V. Louzguine, A. Inoue, High Strength Ni-Fe-W and

U
Ni-Fe-W-P Alloys Produced by Electrodeposition, MATERIALS TRANSACTIONS, 44 (2003)
1942-1947.
AN
[153] K.R. Sriraman, S.G. Sundara Raman, S.K. Seshadri, Synthesis and evaluation of hardness
and sliding wear resistance of electrodeposited nanocrystalline Ni–Fe–W alloys, Mater. Sci.
M

Technol., 22 (2006) 14-20.

[154] Q.J. Zhong, L.B. Yu, Y. Xiao, J.F. Gu, Q.D. Zhong, J.B. Jiang, Q.Y. Zhou, The
D

Electrodeposition of Ni-Fe-Cr Alloy Coatings on Mild Steel Surfaces and Evaluation of

Corrosion Resistance, in: Advanced Materials Research, Trans Tech Publ, 2013, pp. 948-952.
TE

[155] H. Adelkhani, M.R. Arshadi, Properties of Fe–Ni–Cr alloy coatings by using direct and
pulse current electrodeposition, J. Alloys Compd., 476 (2009) 234-237.
EP

[156] V. Torabinejad, M. Aliofkhazraei, A. Sabour Rouhaghdam, M. Allahyarzadeh, Corrosion

properties of Ni‐Fe‐Cr (III) multilayer coating synthesized via pulse duty cycle variation, Mater.
C

Corros., (2016) Inpress doi: 10.1002/maco.201609071.

[157] K. Sridharan, K. Sheppard, Electrochemical characterization of Fe-Ni-P alloy
AC

electrodeposition, J. Appl. Electrochem., 27 (1997) 1198-1206.

[158] W. Hu, Y. Zhang, D. Song, Z. Zhou, Y. Wang, Electrode properties of amorphous nickel-
iron-molybdenum alloy as a hydrogen electrocatalyst in alkaline solution, Mater. Chem. Phys.,
41 (1995) 141-145.
[159] F. Crnkovic, Electrochemical and morphological studies of electrodeposited Ni–Fe–Mo–
Zn alloys tailored for water electrolysis, Int. J. Hydrogen Energy, 29 (2004) 249-254.

54
 ACCEPTED MANUSCRIPT

[160] M. Ghorbani, A. Iraji zad, A. Dolati, R. Ghasempour, The effect of the Cr and Mo on the
physical properties of electrodeposited Ni–Fe alloy films, J. Alloys Compd., 386 (2005) 43-46.
[161] R.K. Shervedani, A.R. Madram, Kinetics of hydrogen evolution reaction on
nanocrystalline electrodeposited Ni62Fe35C3 cathode in alkaline solution by electrochemical
impedance spectroscopy, Electrochim. Acta, 53 (2007) 426-433.

PT
[162] L.J. Song, H.M. Meng, Effect of carbon content on Ni–Fe–C electrodes for hydrogen
evolution reaction in seawater, Int. J. Hydrogen Energy, 35 (2010) 10060-10066.

RI
[163] K. Msellak, J.P. Chopart, O. Jbara, O. Aaboubi, J. Amblard, Magnetic field effects on Ni–
Fe alloys codeposition, J. Magn. Magn. Mater., 281 (2004) 295-304.

SC
[164] F.E. Rasmussen, J.T. Ravnkilde, P.T. Tang, O. Hansen, S. Bouwstra, Electroplating and
characterization of cobalt–nickel–iron and nickel–iron for magnetic microsystems applications,

U
Sensors and Actuators A: Physical, 92 (2001) 242-248.
[165] X. Sun, Y. Zheng, Z. Li, M. Yu, Q. Yuan, X. Li, H. Zhang, Design and fabrication of
AN
flexible parylene-based inductors with electroplated NiFe magnetic core for wireless power
transmission system, in: Nano/Micro Engineered and Molecular Systems (NEMS), 2012 7th
M

IEEE International Conference on, IEEE, 2012, pp. 238-242.

[166] Y. Jiang, S. Yao, W. Zhang, [Ni 80 Fe 20/Cu/Co/Cu] spin-valve multilayers
D

electrodeposited on NiFe buffer layers, Thin Solid Films, 516 (2008) 3210-3216.
[167] S. Tumanski, Modern magnetic materials-the review, Organ, 4 (2010) 10.
TE

[168] Y. Shen, H.H. Hng, J.T. Oh, Synthesis and characterization of high-energy ball milled Ni–
15% Fe–5% Mo, J. Alloys Compd., 379 (2004) 266-271.
EP

[169] M. Lan, H. Li, W. Huang, G. Xu, Y. Li, Effect of cathode vibration and heat treatment on
electromagnetic properties of flake-shaped diatomite coated with Ni–Fe alloy by electroplating,
C

J. Magn. Magn. Mater., 377 (2015) 243-251.

[170] M. Alper, P. Aplin, K. Attenborough, D. Dingley, R. Hart, S. Lane, D. Lashmore, W.
AC

Schwarzacher, Growth and characterization of electrodeposited Cu/Cu-Ni-Co alloy superlattices,

J. Magn. Magn. Mater., 126 (1993) 8-11.
[171] M.A. Phillips, B.M. Clemens, W.D. Nix, A model for dislocation behavior during
deformation of Al/Al3Sc (fcc/L12) metallic multilayers, Acta Mater., 51 (2003) 3157-3170.
[172] A. Marlot, P. Kern, D. Landolt, Pulse plating of Ni–Mo alloys from Ni-rich electrolytes,
Electrochim. Acta, 48 (2002) 29-36.

55
 ACCEPTED MANUSCRIPT

[173] X. Lu, C. Zhao, Electrodeposition of hierarchically structured three-dimensional nickel–

iron electrodes for efficient oxygen evolution at high current densities, Nature communications,
6 (2015).

PT
RI
U SC
AN
M
D
TE
C EP
AC

56