Journal of Alloys and Compounds 691 (2017) 841e859

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Review

Electrodeposition of Ni-Fe alloys, composites, and nano coatingseA

review
V. Torabinejad, M. Aliofkhazraei*, 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

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

Article history: Electrodeposition is considered as an easy and cost effective technique for preparation of alloy coating. A
Received 23 April 2016 wide variety of properties for coatings can be achieved by selecting different parameters of electrode-
Received in revised form position. The electrodeposited Ni-Fe coating is employed in many fields such as corrosion, wear, mag-
25 August 2016
netic and electrical applications, and electrocatalytic materials. In this study, as the evaluation of
Accepted 30 August 2016
Available online 31 August 2016
previous researches will be valuable to guide future researches, electrodeposition of Ni-Fe coating was
investigated from different aspects. The electrodeposition process, effective parameters, properties, and
application of Ni-Fe were summarized considering the previous studies.
Keywords:
Coating
© 2016 Elsevier B.V. All rights reserved.
Direct current
Electrodeposition
Ni-Fe
Pulsed current

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
1.1. Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
1.2. Electroplating of Ni and Ni-Fe alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 842
2. Mechanism of Ni-Fe electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 843
3. Baths used in electrodeposition process of Ni-Fe coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
3.1. Sulfate and chloride baths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
3.2. Fluorborate bath . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
3.3. Sulphamate bath . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
3.4. Nonaqueous baths . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
4. Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
4.1. Boric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 844
4.2. Citric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
4.3. L-ascorbic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
4.4. Glycolic acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
4.5. Saccharin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
5. Electrodeposition methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
5.1. DC electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
5.2. PC electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 845
5.3. PRC electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 846
6. Electrodeposition parameters of Ni-Fe alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
6.1. Current density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
6.2. Electrolyte agitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847
6.3. Electrolyte pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847

* Corresponding author.
E-mail addresses: maliofkh@gmail.com, khazraei@modares.ac.ir
(M. Aliofkhazraei).

http://dx.doi.org/10.1016/j.jallcom.2016.08.329
0925-8388/© 2016 Elsevier B.V. All rights reserved.
842 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859

6.4. Pulse frequency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 847

6.5. Duty cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
7. Properties of electrodeposited Ni-Fe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
7.1. Microstructure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 848
7.2. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
7.3. Magnetic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 849
7.4. Electrocatalytic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 850
7.5. Corrosion behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 851
7.6. Wear behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 851
8. Thermal treatment of electrodeposited Ni-Fe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 852
9. Ni-Fe composite coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853
9.1. Effect of Al2O3 particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853
9.2. Effect of SiC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853
9.3. Effect of ZrO2 particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
9.4. Effect of Si3N4 particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
9.5. Effect of In2O3 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
10. Addition of other elements to Ni-Fe coating . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
10.1. Ni-Fe-W . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
10.2. Ni-Fe-Cr . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 854
10.3. Ni-Fe-P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
10.4. Ni-Fe-Mo . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
10.5. Ni-Fe-C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
11. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
12. Future scope and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 855
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856

1. Introduction corrosion resistance, and wear and thermal resistance of the sub-
strate material. Electrodeposition process can be performed with
1.1. Preface both types of direct (DC) and pulse current (PC) [6]. In the DC
method current is continuously applied to the system. However, in
The mechanical, thermal, chemical and electrochemical inter- a PC electrodeposition process, the electrical current is alternated
action of a material in a given environment initiate from its surface. swiftly between two different values [7]. The properties of depos-
Therefore, the surface of a material is the most important engi- ited coatings can vary because of pulsating parameters in PC elec-
neering part. Among the standards which are developing contin- trodeposition process. The progress in electronics made it possible
uously for production and manufacturing process, the use of to control the properties of the coating by using the PC instead of
surface modification technologies in the manufacturing process is DC method. The better dispersion of elements in the coating,
inevitable. Since the surface of materials is often under threat of compact and nonporous nanostructure coating, a decrease in ab-
wear and corrosion [1], tribology and corrosion are the most sorption of gasses in coatings, a reduced need for organic additives
essential and important fields in surface technology. The tribolog- and thus a decrease in environmental pollution are advantages of
ical and corrosion phenomena impose huge damages to economy PC electrodeposition process.
and industry. The damages will be irrecoverable if wear and
corrosion phenomena are not controlled correctly. Therefore, the
1.2. Electroplating of Ni and Ni-Fe alloy
surface technology can be considered as a key technology in the
production engineering process. The use of appropriate surface
Because Ni and its alloys have a variety of merits such as good
technologies can prevent the damages or at least delay them. The
corrosion and wear resistance, they have been receiving a great
selection of a proper method to create distinctive surface properties
attention in deposition applications. Almost 12% of Ni consump-
is a complex process as it includes modifying the various charac-
tion in the world is allocated to the electrodeposition of Ni coating
teristics and properties. Furthermore, the selection of suitable
[8]. The use of Ni coating for decorative purposes is the main
process usually requires the economic and environmental in-
application of electroplated Ni coating [9]. The Ni deposits are used
vestigations [2].
in the industry to improve wear and corrosion resistance, to repair
Electrodeposition is an electrochemical process applied for
eroded metals, to change the dimensions of small size pieces, to
surface structure modification. The electrodeposition process is an
improve magnetic properties, to prepare the substrate surface for
old method in surface engineering processes which has a long
glazing or producing the organic coating, and other purposes [10].
history. The electrodeposition technique was firstly applied more
In addition to pure Ni coating, it is possible to produce a Ni-based
than 2000 years ago in several hypothesizes [3,4]. The production
alloy coating by an electrodeposition process. The Ni-Fe alloy
of a galvanic cell with Volta in about 1800 and then progress in
coating is used in order to decrease the cost production and also
electrical motors from 1800 to 1900 led to use electrodeposition
provide soft magnetic properties, good electrical conductivity,
technique as a cost effective process to produce a coating. In this
proper corrosion resistance and special optical properties [11]. This
process, a monolayer or multilayer coating is formed because of the
type of coating is widely used in electronic, sensors, communica-
electrochemical reactions occurred at the electrode/electrolyte
tion and optic industries. There are several processes used to
interface and deposition of ions from the electroplating bath on the
produce Ni-Fe coating as follows: sputtering, molecular beam
surface [5]. The coating may be deposited on the surface to enhance
epitaxy, evaporation and electrodeposition [12]. The special con-
the solderabilty, lubricant properties, electrical conductance,
ditions of temperature and pressure, ultra-high vacuum and
 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
consequently expensive process are disadvantages of former
methods over electrodeposition. 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, 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 to 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 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 the phase diagram, were established experimentally
by Romig and Goldstein [14] from 900 to 300
C by using STEM.
The nickel-rich FeNi3 ordered fcc phase, which has an L12 super-
structure, was first detected by Leech and Sykes [15] using XRD
measurements. A eutectoid reaction was predicted suggesting that
a and Ni3Fe were in equilibrium at low temperatures [16]. The
critical ordering temperature of FeNi3 (516
C at 73 at.% Ni) was
determined by Deen and Woude [17] using Mossbauer spectros-
copy. It is claimed that FeNi and Fe3Ni phases also existed in this
phase diagram below the eutectoid temperature in the two-phase
(aþg0 ) region [16]. Little information concerning the Fe-Ni system
at low temperatures exist due 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 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 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 a and/or g phases since the
deposition condition is a non-equilibrium process [19e22].
Fig. 1. The Fe-Ni phase diagram [23].
843
2. Mechanism of Ni-Fe electrodeposition
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
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 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 be-
tween Fe content of alloy and Ni/Fe ion ratio of the 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 84 wt%.
Hence, the deposition rate of Fe is greater than that of Ni indi-
cating the anomalous deposition. In early studies, the anomalous
deposition was attributed to the deposition of Fe hydroxide on the
surface of the electrode which prevents reduction of Ni ions [25].
According to this mechanism, the reduction of Hþ ions on cathode
surface and thus the local increase of pH value on the surface fa-
cilitates 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 attributed to
the formation of NiOHþ and FeOHþ. The formation of these in-
termediate compounds may be due to hydrolysis of Ni2þ and Fe2þ
and discharging on the cathode surface [28]. Therefore, the high
concentration of FeOHþ ions near the electrode and coverage of
the surface with these ions inhibit the formation of NiOHþ ions. In
a newer model suggested by Matlosz [29], the kinetic rather than
the chemical reaction is emphasized. Hence, it is assumed that the
reduction reaction of both Ni and Fe ions occurs in two steps as
follows:
M(II)þe/M(I)ads step (1)
M(I)adsþe/M step (2)
In the first step, the reduction of Fe2þ and Ni2þ ions to Feþ and
þ
Ni occurs respectively, and these intermediate species are adsor-
bed 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 Feþ compared to Niþ ions is higher and thus many areas of
the surface are covered with Fe ions. The covering of electrode
Fig. 2. The content of Fe as a function of Ni/Fe ion ratio in the electrolyte [24,33e35].
844 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
surface with Feþ prohibit 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 been confirmed by electrochemical
impedance spectroscopy measurements [32].
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 elec-
trodeposition 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 in-
creases 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
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 bath
[37,38]. Moreover, the chloride baths alone is also used in electro-
deposition of Ni-Fe alloy. The coatings produced in chloride baths
compared to the one prepared in sulfate baths is harder and have
more stresses in its structure. The reason for this effect is unclear in
many studies concerned the internal stress of electrodeposits
[39e41]. Furthermore, the corrosion resistance of 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 independent of Fe2þ con-
centrations, although their values in chloride baths were higher by
about 20%. The higher limiting current for Hþ in the sulfate bath
rather than chloride bath was the main reason of latter. Accord-
ingly, significant decrease in the overpotential of Ni-Fe in chloride
baths attributed to the catalysis effect of chloride through the for-
mation of a Cl bridge between the 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 metal ion concentration and so-
lution pH to change [43].
3.2. Fluorborate bath
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
products in the coating can affect the properties of the coating. For
instance, the properties of coating deposited from a bath con-
taining citrate additives can be changed due to the presence of
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 over-
come these problems fluorborate baths can be used in the elec-
trodeposition process. In this case, the problems issued from the
presence of additive agents such as saccharine and sulfur will 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
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 azodi-
sulfonate are the major defects of these baths. The high concen-
tration of Ni sulphamate leads to decreased hydrolysis, but the
intensified formation of azodisulfonate impurities. 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 which decreases the
ductility and compressive stresses [44,45].
3.4. Nonaqueous baths
The Ni-Fe alloys are usually deposited from aqueous baths. The
discharging process of Hþ ions and formation of hydrogen during
electrodeposition process is the most important drawback of
aqueous bath. It has been observed that hydrogen discharging in
the electrodeposition process degrades some of the deposit prop-
erties. Therefore, the use of an appropriate solvent without active
hydrogen or a solvent, in which the hydrogen bonds are stronger
than that of water bonds, 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 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 density. These
properties cause the increased stability of ethylene glycol in sus-
pensions. In this electrolyte, since the chance of hydrogen releasing
decreases, a coating with low content of 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.
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
consumed to form hydrogen. This reaction decreases the current
efficiency and leads to an increase in the pH value of cathode sur-
face and thus affects the kinetics of reduction reactions for metallic
ions. Boric acid improves the range of required current density for
electrodeposition 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 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
metallic ions by the formation of some complexes with Ni [53]. This
mechanism has been 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 possible. Therefore, the increase in the pH
value of the cathodic areas occurs in nobler potentials. The pres-
ence of boric acid in an electroplating bath inhibits pH raise and
 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
also the required potential range for the electrodeposition process
is extended without hydroxide deposition.
4.2. Citric acid
Citric acid is used in Ni-Fe electroplating baths as a complexing
agent. Citric acid is a complex agent for Fe3þ, Ni2þ and Fe2þions. The
stability of the produced complexes decreases in the order of Fe3þ,
Ni2þ and Fe2þ. The addition of citric acid to the sulfate baths leads to
deposition of the high content of Fe on the cathode surface; how-
ever, the current efficiency decreases significantly [56]. The results
indicate that the local increase in the pH value of the cathode
surface leads to 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 ¼ 3), the content of Fe in the coating is very
low and a high quantity of Fe3þ ions is formed in the solution. Since
the stability of Fe3þ ions is higher than that of Fe2þ, the Fe2þ ions
exit from the complex mode and thus the equilibrium chemical
reaction occurs in a direction to form Fe3þ ions [57]. The com-
plexing effect of citrate ions shifts the reduction potential of Ni-Fe
alloy to the more 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
2þ 3þ
L-ascorbic acid prevents the oxidation of Fe /Fe during
electrodeposition process. The presence of this acid in electro-
plating 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 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 chemical composition of the coating, although it prevents
oxidation of Fe2þ ions and thus hinder decrement in the concen-
tration of these ions [25].
4.4. Glycolic acid
Glycolic acid with sodium citrate is used in chloride baths. Ac-
cording to the results of previous works, the presence of glycolic
acid in the bath shifted the reduction potential of Ni-Fe alloy to-
ward more negative values. Furthermore, the nucleation rate
increased with the presence of this 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 are formed on the surface which they
continue to grow with the same growth rate. Furthermore, 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 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 found that internal stress of Ni-Fe
coating is reduced with saccharin concentration. Different mecha-
nisms 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
845
Fig. 3. The effect of saccharin addition on the internal stresses of Ni-Fe alloy [42].
frequency of nucleation sites [61]. The addition of additive agents
such as saccharine affects the cathodic polarization behavior. Ac-
cording 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 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 (<3 g/l) shiny surface with
nano-size grains, 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 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 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
values had a noticeable effect on the chemical composition of de-
posit and increased the Fe content [22].
5. Electrodeposition methods
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 advantages of DC over PC and PRC method are: (i) simple
and economically affordable process and (ii) the sufficient tech-
nological knowledge.
5.2. PC electrodeposition
In the PC electrodeposition the current in a periodic manner
reaches zero (Fig. 4). In this case, negatively charged layer is formed
on the cathode surface. The thickness of this layer increases to a
846 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
Fig. 4. The various modes of current density for electrodeposition; (a) DC, (b) PC and (c) PRC.
particular extent and then remains constant. This layer hinders
diffusion of ions. The 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 (tempera-
ture, composition, and pH) which are effective in any type of
electrodeposition process, peak current density (Ipeak), 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 are calculated according to Equations (1) and (2),
respectively:
1 joining these bubbles and formation of porosity in DC elec-
f ¼
toff þ ton
ton
d% ¼  100
toff þ ton
where, f is the pulse frequency and d% is pulse duty cycle in each
pulse. The average current density can be defined as follows:
ton
Iavg ¼  Ipeak ¼ d%  Ipeak
toff þ ton
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 pa-
rameters [65].
In general, the advantages of pulse current in comparison to
direct current is summarized as follows:
(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
pulse is fully completed, the next pulse will start immedi-
ately [66]. This condition leads to an increase in the nucle-
ation rate and a decrease in growth rate, which in turn cause
the formation of a more compact structure [67].
(2) The ability to control the chemical composition and micro-
structure: The change in pulse parameters such as Ipeak, duty
cycle and frequency make it possible to control the adsorp-
tion and desorption of various species in the electrolyte
[68,69]. Therefore, the microstructure, chemical composition
and properties of coatings can be controlled in PC electro-
deposition [70].
(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 to two factors; (i) during electrodeposition pro-
cess, the released gases on the cathodic such as oxygen and
hydrogen have enough time to leave the surface of the
cathode and 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
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 form
a larger bubble is impossible. Nevertheless, the possibility of
(1) trodeposition process is high.
(4) Increasing the content of ceramic particles in nanocomposite
electrodeposition [71e73]: Once the electrodeposition pro-
cess starts, a negative charge layer is formed on the cathode
(2)
in the presence of ceramic particles suspended in an elec-
trolyte. This layer acts as a barrier between ceramic charged
nanoparticles and surface of the electrode. Within PC elec-
trodeposition, this negatively charged layer is discharged
during pulse off-time in pulse current electrodeposition
process. In this case, diffusion of ceramic particles into the
(3) 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 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 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 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 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 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 com-
parison to DC deposited one. Clearly, the internal stress increases
 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
Fig. 5. The effect of current mode on the internal stress of Ni-Fe coating [78].
with current density due to more hydrogen evolution in the cath-
ode surface; however, the internal stress is lower in the PRC [78].
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 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 pro-
cess [19,79,80]. This behavior has been reported in various elec-
troplating baths and discussed repeatedly in the literature
[81e84]. This behavior can be explained by Fe deposition mech-
anism. Deposition of Ni is activation controlled, while the depo-
sition of Fe is controlled by diffusion in an anomalous deposition
[85]. Horkan [39] proved the reduction of Fe content in electrolyte
around the cathode surface. This author also suggested that the
decrease in Fe content in the electrolyte is controlled by a diffu-
sion 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
studies, regarding the increase in current density and assuming
the increase in pH values of cathode surface, the decrease in Fe
Fig. 6. Effect of current density on the chemical composition of Ni-Fe coatings elec-
trodeposited from baths with different metallic ion ratios [42].
847
content in electrolyte around the cathode by an increase in cur-
rent density is attributed to the formation of metallic hydroxides
[25,57]. Nevertheless, some 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 effective
parameter [84].
6.2. Electrolyte agitation
The stirring of the solution has a significant effect on the
chemical composition of alloys deposited with anomalous deposi-
tion. 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. 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 so-
lution toward the cathode surface [86]. It should be noted that the
raising the agitation rate to a certain value leads to increase in Fe
content, while more 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 ef-
fect on the hydrogen evolution rate. The 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 cathode [82,84].
6.3. Electrolyte pH
The electroplating baths with pH values in the range of 2e3.5
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 formation of FeOHþ.
According to Matlosz [29] mechanism, the covering of the surface
with FeOHþ 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.
6.4. Pulse frequency
The adsorption and desorption of various ions in the electro-
lyte can be controlled by changing the PC variables such as Ipeak,
duty cycle, and frequency [5,87,88]. Therefore, the control of
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 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 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 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
848 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859

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].

not effective on the chemical composition of the Ni-Fe coating. 7. Properties of electrodeposited Ni-Fe
The change in grain size is a known influence of frequency vari-
ation on the coating microstructure [70]. The pulse duration is 7.1. Microstructure
very short in high frequencies. Therefore, the time of charging and
discharging process in pulse on-time and off-time is very short. The XRD patterns of Ni-Fe coatings with different Fe content is
Under such a condition, the nucleation rate increases and growth depicted in Fig. 8. As shown, the characteristic peaks of FCC phase
rate decreases which in turn results in the formation of a compact are clear and increasing Fe to 43 wt% affects the intensity of (1 1 1)
structure [66,90]. This behavior was also observed in the previous and (2 0 0). In comparison, increasing the Fe to 58 wt% in the
reports [24]. In fact, when the nuclei are formed on the surface the deposited coating leads to the appearance of a new peak at (1 1 0)
grain growth is limited due to the repeated interruption of current which is the characteristic peak of BCC phase. This observation
(high frequencies) and thus, so many nuclei are formed on the determined the approximate range of phase stability in electro-
surface which eventually leads to a decrease in grain size [5]. The deposited Ni-Fe coatings. This patterns illustrates that Ni1-xFex alloy
influence of pulse frequency on the microstructure of Ni-Fe has at x<58% is FCC phase, while at 58% < x<65% mixed state of FCC and
received less attention in the literature. The possible effect of this BCC is observed. Finally, at x>65% the only phase is BCC [86].
parameter on the resultant properties of the coatings may be The deposition of Ni-Fe alloys results in a solid solution alloy.
attractive for many field of science and technology. 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
6.5. Duty cycle content causes lattice distortion and thus lattice defects such as
vacancies and dislocations are developed in the coating structure.
The chemical composition, grain size and texture of the coating When the number of dislocations reaches to a certain value, the low
can be affected by variation of the duty cycle. In PC electrodepo- angle boundaries are formed which leads to grain refinement of
sition of Ni-Fe alloy, the decrease in duty cycle increases Fe coating structure. The effect of Fe content on the grain size of the
deposition. This phenomenon was confirmed in several recent coating is shown in Fig. 9. When Fe content in Ni-Fe coating is lower
studies [19,91]. The mechanism of Fe deposition in Ni-Fe coating is than 25 wt%, the grain size decreases with a decrease in the Fe
an anomalous process and thus the events observed can be content of the coating. However, the variation of grain size with Fe
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 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-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 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 electrode-
position, the off-time of a 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 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. 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. Fig. 8. The XRD results of electrodeposited Ni-Fe alloys with different Fe content [86].
 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
Fig. 9. The effect of Fe content on the grain size of Ni-Fe deposit [24,33e35].
content is negligible in Fe contents of 25e40 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
[35,94e96]. Furthermore, the grain size of Ni-Fe alloy usually is in
the nanoregime although grain size may be varied by variation of
electrodeposition parameters.
7.2. Mechanical properties
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 re-
sults 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 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 20e40 wt%, while more contents of Fe and thus for-
mation 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 increase
of strength in the nanostructured alloy in comparison to the
microcrystalline alloy [98]. 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 electro-
deposited Ni. This increment is the result of the hardening effect of
the substitutional solid solution. The other point of tensile plots is
Fig. 10. Engineering stress-strain curves of tensile tests for electrodeposited Ni-Fe
alloys and Ni at a strain rate of 10-41/s [98].
849
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 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 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, clearly exceeding the stresses ob-
tained for the continuous tensile test. This phenomenon is named
as yield point phenomenon [101]. Yield points are often ascribed to
a lack of mobile dislocations [102]; however, the main reason for
this observation is unclear in literature for Ni-Fe alloy.
7.3. Magnetic properties
The chemical composition of the alloy, electroplating bath,
applied potential, and the addition of additive agents are the pa-
rameters which can control the magnetic properties of an elec-
troplated Ni-Fe coating [103,104]. The effect of these parameters on
the magnetic properties of the coating was investigated in the
previous studies. The coercivity, magnetic flux density, saturation
magnetization, magnetic remanence, permeability, anisotropy, and
squareness are the magnetic properties which have been investi-
gated [105e107]. The coercivity and magnetic flux density are 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 proper-
ties of the coating [108e111]. Therefore, many investigations have
been done to 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 coatings, so that the alloy coating provides better magnetic
properties when the Fe content of the coating is almost 19e24 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 per-
centage of Fe and an increase in the percentage of Ni in the coating;
Fig. 11. Stressestrain curves of Ni-Fe during loadeunload tensile test. The black dashed
line represents the continuous tensile experiment [101].
850 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859

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 magnetic proper-
ties. 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].
The presence of sodium saccharin which as a strain reducer
agent in electrolyte leads to a decrease in the grain size, which in
turn decreases the coercivity and subsequently enhances the
magnetic properties of the coating [22](see Fig. 13).
The annealing process is also effective on the magnetic prop-
erties 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]. Therefore, an increase in annealing tempera-
ture increases saturation magnetization and magnetic flux density. Fig. 13. The effect of saccharine on Fe concentration and saturated magnetization [22].
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
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 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 inde-
pendent of the direction of the magnetic field [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 properties of a coating can be influ-
enced by the increase in Fe content, which results in saturated
magnetization state [119].

7.4. Electrocatalytic properties

Finding an appropriate, cost effective, and eco-friendly replace-

ment for fossil fuels is necessary. The electrical energies generated by

Fig. 14. The Effect of magnetic field on the coercivity [118].

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 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. Different materials are
used as a catalyzer to produce hydrogen. For instance, water elec-
trolysis reaction in alkaline solutions occurs within two stages as
follows: Hydrogen evolution reaction (HER) and oxygen evolution
reaction (OER). In order to increase efficiency of the electrolysis cell,
Fig. 12. Effect of Fe content on the magnetic saturation and coercivity of Ni-Fe alloy
[77]. these reactions should occur at lower values of overpotential. The
 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
overpotential of oxygen 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 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 Ni
[124e126]. 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 entrance of Fe
into the electrodes (as Fe oxide or Fe hydroxide) changes the elec-
trical properties of electrodes so that these variations enhances the
activity of OER [127]. Ullal and coworkers [128] investigated various
Ni-Fe coatings deposited with different current densities. They re-
ported that coating with 35 wt% Ni provides a high efficiency for OER
and HER. According 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 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 alloy are used
for oxidation of hydrazine [130]. This alloy is embedded in nanotubes
using the electrodeposition process in the presence of methyl-
benzene. 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 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].
7.5. Corrosion behavior
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 Star-
osta et al. [132], the corrosion rate has a proportional relation while
the corrosion potential is inversely proportional to iron content. For
instance, the difference between corrosion potentials for nickel and
Nie19% Fe coatings were small but it rose to over 330 mV for
Fig. 15. Cyclic voltammetric measurements of MWCNT- and graphene-based alloys in
0.1 M hydrazine hydratee0.015 M KOHe1 M NaCl solution, 60
C, 20 mV s1 [131].
851
Nie29% Fe and Nie41% Fe. Torabinejad et al. [133], taking this fact
into consideration, deposited functionally 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 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 nano-
particles 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 mecha-
nisms effective in improving the corrosion resistance will be
explained in the next sections.
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 com-
posite 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. 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 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
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 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.
Fig. 16. Variation of Fe content across the functionally graded Ni-Fe-Al2O3 coating at
different frequencies [133].
852 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859

observed after annealing process in the view of the mechanical

Fig. 17. The effect of SiC nanoparticles on the corrosion behavior of permalloy [134].
behavior of Ni-Fe coating. Mechanical properties of the electro-
plated 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 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 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
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 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 to Fig. 19(a), an in-
crease at temperature enhanced the coating brittleness. The in-
crease in annealing temperature to 300
C promotes the
mechanical properties. The grain size and also precipitation of
sulfur in grain boundaries are increased with temperature at tem-
peratures above 300
C; thus, Fe sulfides and Ni sulfides are formed.
The effect of annealing treatment on the 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

Fig. 18. Variation of microhardness across the functionally graded Ni-Fe-Al2O3 coating.
Retrieved from Ref. [133].

8. Thermal treatment of electrodeposited Ni-Fe

The applications of Ni-Fe coatings are greatly influenced due to

the presence of internal stresses in the coating structure. An in-
crease 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 coating
structure leads to the development of some defects such as va-
cancies, 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)
Fig. 19. (a) The typical Tensile test stressestrain curves of Ni-20%Fe [92], (b)
annealing treatment of coating. The effect of saccharin additive has
Compressive stressestrain curves of the as-deposited (AD) and annealed (AN) at
been investigated in several studies, and a ductility reduction was 250
C Ni-23%Fe [137].
 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
leads to a decrease in 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 size metals, the movement of dislocations plays a
dominant role in plastic deformation. The production and disper-
sion of dislocation initiate from grain boundaries and then inter-
granular 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-
Cottrell locks which act as a barrier against the other dislocations,
leading to the enhanced strain hardening. The decrease in dislo-
cation density in the grain boundaries of the annealed coating in-
dicates 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].
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 sta-
bility 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 signifi-
cantly through heat treatment at 100
C; although the heat treat-
ment process is not effective on the grain size. The relaxation of
grain boundaries is the most common event at 100
C. The grain size
increases in the temperature range of 100e264
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 with
temperature are negligible at temperature below 327
C, while
above that a fast grain growth occurs. According to previous in-
vestigations [98,139], the grain growth in this range of 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 increases in this region and
thus a bimodal structure is formed [139].
9. Ni-Fe composite coating
The Ni-Fe composite coating produced by electrodeposition
process has been rarely investigated. The presence of second phase
Fig. 20. The effect of annealing temperature on the grain size of Ni-Fe alloys
[139e141].
853
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 particles leads to a subsequent rise in the
number of locked dislocations and thus, according to Orowan ef-
fect, the required stress for movement of dislocations will be
increased [142]. However, the interfacial intersections in the pres-
ence 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. 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 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 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 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 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 be described as follows:
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 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 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
functionally graded coatings have been produced in recent studies
[91]. The constant variation in duty cycle results in a gradual in-
crease in alumina content from interface toward the surface. The
maximum content of particles is in the outer layer at the minimum
duty cycle.
9.2. Effect of SiC
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
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 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 random microstruc-
ture [78].
854 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
Table 1
The bath condition for different Ni-Fe composite coatings.
Coating Bath composition
Ni-Fe- 250 g/l NiSO4$7H2O, 40g/l H3BO3, 0e50g/l FeCl2$4H2O, special chemicals 0.6g/l IM-PEX NF and
Al2O3 0.1g/l IMPEX NZ
Ni-Fe-SiC 112g/l NiSO4$6H2O, 5g/l FeSO4$7H2O, 2g/l H3BO3, 0.5 g/lsodiumdodecylsulfate, 1g/l L-ascorbic
acid
Ni-Fe- 100g/l H4N2NiO6S2$4H2O, 4g/l FeSO4$7H2O, 30g/l H3BO3 (Ethylene glycol solution)
ZrO2
Ni-Fe- NiSO4$7H2O, FeSO4$7H2O, NiCl2$6H2O H3BO3, Saccharina
Si3N4
Ni-Fe- 100g/l H4N2NiO6S2$4H2O, 4g/l FeSO4$7H2O, 30g/l H3BO3
In2O
a
The quantity of chemical compounds didn't mentioned in the reference.
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
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 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 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. An in-
crease 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 microhard-
ness. 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 offered by conducting
Si3N4 particles [48].
9.5. Effect of In2O3 nanoparticles
Indium oxide particles have a good electrical conductance,
because of their small band gap energy and a high number of car-
riers in comparison to other ceramic particles. In addition, these
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, hard-
ness, magnetic properties, and electrical conductance. The current
density is not effective on the content of embedded nanoparticles
in this coating [46].
10. Addition of other elements to Ni-Fe coating
10.1. Ni-Fe-W
The W metal cannot deposit alone with electrodeposition
pH Temperature Particle Particle size Ref.
(
C) concentration (g/L) (mm)
3 55 50e250 0.5e5 [132]
4 50 0e25 0.05 [134]
3 34 5 <0.1 [47]
3 55 50 0.086 [20]
3 34 2 <0.1 [46]
technique and requires a metal from Fe group for this purpose
[149,150]. The presence of an oxide layer as an intermediate phase
for 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 occur-
rence of parallel reactions leads to the formation of a heteropoly-
tungstate film on the surface. Some microcrack can be generated
on the surface due to the presence of high stresses in 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 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 tempera-
ture increase to 500
C during heat treatment can lead to an in-
crease in hardness while by exceeding this temperature the
hardness value is decreased [150].
10.2. Ni-Fe-Cr
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 resis-
tance. To apply trivalent chromium, Cr(III), which has fewer risks
compared to Cr(VI), the chloride bath is used in the electrodepo-
sition process. FeCl2, NiCl2, and CrCl3 as well as some other addi-
tives, 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 been
investigated [154,155]. The content of Cr in these coatings often is in
the range of 2e14 wt% 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 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, provides the condition for
deposition of Cr on the substrate [154]. The increase in pulse fre-
quency 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 fre-
quency. A decrease in duty cycle leads to an increase in the Cr
content in the chemical composition of the coating. The reduction
 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
reaction of trivalent Cr occurs in two steps. At the initial step, the
reduction of Cr3þ to Cr2þ occurs and then next reduction reaction
converts Cr2þ to Cr. At lower duty cycles, which the pulse toff is long,
Cr2þ ions have sufficient time to exit 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 signifi-
cant 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
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 grain
growth at temperatures above 350
C [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 use of phos-
phorus 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 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 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 is the formation
of impurities in coating structure [157].
10.4. Ni-Fe-Mo
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
applications and HER [158]. The results show that this alloy pro-
vides a good stability and 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
surface area is created. The high activity of produced structure
provides a favorable HER condition [159].
Permalloy is widely used for applications that need soft magnetic
properties. The electrical 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 Permal-
loy can be built up from 180 to 240 Umcm 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 varia-
tions such as a change in grain 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
855
reaction because of its high 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 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 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 preferred places for HER, leading to the
reduced values of overpotential.
11. Applications
Nowadays, the main use of Ni-Fe is related to its magnetic
properties. The magnetic properties of the coating can be improved
by a decrease in coercivity and an increase in saturated current
density and saturated magnetization. Some of the industrial ap-
plications of Ni-Fe deposits are 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 devices with medium response sensitivity, mea-
surement transducers, pulse transformers, thyristor protective
chokes, transducer cores, relay parts, stator laminations for step-
ping motors in quartz watches, shielding for low temperature ap-
plications (e.g. liquid helium or nitrogen), storage chokes, flux
conductors and pole pieces in magnetic valves, printer, electro
valves, magnetic heads for tape recorders [51,52,58,160,163e167].
The above mentioned applications have used extensively in prac-
tical applications, however there are some ongoing applications
that 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 electro-
magnetic 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 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].
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
coatings produced by electrodeposition process have been
considered recently for fabrication of NiFe2O4 spinel [35]. Electro-
deposition process is a cost effective process which is ideal for
coating the components with complex geometry. In order to pro-
duce the NiFe2O4 spinel, the thermal oxidation process for Ni-Fe
coatings is performed at high temperatures. The heat 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.
12. Future scope and conclusion
This article summarized different aspects of Ni-Fe electrode-
position and its properties. The process, effective parameters and
856 V. Torabinejad et al. / Journal of Alloys and Compounds 691 (2017) 841e859
Fig. 21. Examples of different Ni-Fe based coatings applied on components in various industries.
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.
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
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 used in electro-
valves, relay parts and printers as a coating or electroformed ma-
terial. In these 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 ef-
forts have dedicated. Increasing 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 elec-
trodeposition parameters. Addition of other elements and ceramic
particles to the Ni-Fe matrix have 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. 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. Superior resistance to
wear and corrosion may also be achieved by manipulation of pulsed
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 me-
chanical properties and appropriate corrosion resistance
[170e172]. 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 re-
searchers. In addition, electrochemical aspects of PC electrodepo-
sition is more important in 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 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 used in future.
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