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Electroless Ni-B and Composite Coatings: A Critical Review on

Formation mechanism, Properties, Applications and Future trends

Q. Barati , Seyed Mohammad Mehdi Hadavi

PII: S2468-0230(20)30694-5
DOI: https://doi.org/10.1016/j.surfin.2020.100702
Reference: SURFIN 100702

To appear in: Surfaces and Interfaces

Received date: 31 July 2020

Revised date: 11 September 2020
Accepted date: 12 September 2020

Please cite this article as: Q. Barati , Seyed Mohammad Mehdi Hadavi , Electroless Ni-B and Com-
posite Coatings: A Critical Review on Formation mechanism, Properties, Applications and Future
trends, Surfaces and Interfaces (2020), doi: https://doi.org/10.1016/j.surfin.2020.100702

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 Electroless Ni-B and Composite Coatings: A Critical Review on Formation mechanism,
Properties, Applications and Future trends

Q. Baratia, Seyed Mohammad Mehdi Hadavib*

a- Materials and Metallurgical Engineering Department, Faculty of Engineering, Ferdowsi

University of Mashhad, Mashhad 91775-1111, Iran
b-Department of Materials Engineering, Tarbiat Modares University, Tehran, Iran, P.O. Box:
14115-143, Tehran, Iran
*
Corresponding author email: s.hadavi@modares.ac.ir

Abstract

Because of its unique properties, the electroless method is used as an effective and important
technique to create uniform coatings. Among the coatings that can be made by electroless
process is Ni-B coating due to its excellent properties such as good corrosion resistance, high
wear resistance, high hardness, favorable oxidation resistance and use as an electrocatalyst to
production of renewable energies has recently attracted a lot of attention. Due to the excellent
properties of nickel-boron electroless coatings as well as recent advances in the emergence of
effective Ni-B coatings, scientists have been able to improve the world's emerging challenges
such as wear resistance and the production of renewable energies can exploit the potentials of
these coatings to improve the mentioned properties on various metal surfaces. Because of the
stated attractive properties, a comprehensive review article is needed to gain in-depth knowledge
of the mechanism of creation, microstructure and chemical composition as well as strategies for
improving corrosion resistance, tribological properties and production of renewable energies. In
this review article, after introducing nickel-boron electroless coatings and examining the
microstructure and chemical composition, recent developments in strategies to improvement in
corrosion resistance, tribological properties, and the use of nickel-boron electroless coatings as
electrocatalysts for production of renewable energies has been reviewed. Finally, a summary and
future trend is given.

Keywords: Nickel-boron electroless coatings, Corrosion resistance, Tribological properties,

Renewable energies
1. Introduction

Improving corrosion resistance, tribological properties as well as other surface properties are the
most important strategies for the practical application of many metals in various industries. One
of the most important methods to improving the surface characteristic is to create coatings with
unique properties. To date, there are many methods for creating a coating on engineering
surfaces, including electroless plating[1-4]. The electroless method is a spontaneous process in
which the electrons required for the reduction reaction and the deposition are provided by the
oxidation of the chemical compounds in the solution (reducing agents)[5-9]. The electroless
coating method has many advantages over other coating methods such as electrochemical
deposition, which can be attributed to better surface properties such as wear resistance, hardness
and corrosion resistance[10-13]. In addition, because this method does not use external current, it
can cover a surface with a complex structure uniformly. Other advantages of coatings created by
the electroless method include high deposition rate, good solder ability, high reflectivity and
good magnetic properties. Electroless coatings have recently received a lot of attention in the
commercial and industrial fields for modifying the surface properties of many materials such as
aluminum, steel, copper as well as non-conductive materials such as plastics[14]. In general,
electroless coatings can be divided into three general groups including pure nickel coatings,
nickel alloy coatings and composite coatings. The alloy coatings include nickel-phosphor and
nickel-boron-based coatings and various nanoparticles are used in composite coatings to improve
surface properties. Generally, an electroless coating bath comprises a metal ion source,
complexing agent, reducing agent, stabilizing agent, wetting agent and buffering agent. Coatings
with desire properties can also be created by changing bath parameters such as temperature, pH
and the concentration of components inside the bath.

Because of the favorable characteristic of boron as well as the excellent properties of the
electroless process, creating coatings and improving surface properties by deposition of nickel-
boron-based coatings using the electroless method can be an excellent choice[15-18]. Nickel-
boron electroless coatings, after research in 1989, have been recognized as a great method to
create coatings with excellent properties[19]. The Ni-B electroless coating process results in a
uniform coating, which leads to a significant improvement in surface properties such as
corrosion resistance and wear resistance [20-22]. The exclusive characteristic of nickel-boron
electroless coatings have led them to be used in many applications such as aerospace,
automotive, chemical and electrical industries[23, 24]. In addition to the promising features
which have stated for nickel-boron electroless coatings, because these coatings use more
effective reducing agents, these coatings have better efficiencies and properties than Ni-P
coatings [25-28]. There have been developed numerous methods to improve the properties of
nickel-boron electroless coatings by different scientists, which can be referred to as the use of
different additives, alloying and heat treatment. Given the advantages said in nickel-boron
electroless coatings, and the lack of a comprehensive review article on nickel-boron electroless
coatings, the purpose of this review article is to first comprehensively examine the current
understanding of the formation mechanism of electroless nickel-boron coatings, study of
microstructure and phase composition and further explores various applications and strategies to
improve coating properties including corrosion, wear resistance and hardness.

2. Formation mechanism, morphology and phase structure

The formation mechanism, microstructure and chemical composition can strongly influence the
properties and performance of coatings. In this section, the formation mechanism,
microstructure, phase and chemical composition of Ni-B electroless coatings will be examined.

2.1. Formation mechanism and morphology

Initially, the thermodynamic conditions of the reduction during coating are investigated: The
deposition processes are based on the reduction of metal ions in aqueous solutions according to
the following reaction:

Mez+ + ze- Me (1)

The deposition processes can be divided into three main groups based on the reactions that lead
to the formation of electrons: In the first group, the electrons required for reduction reactions are
provided by dissolution of a metal with less noble thermodynamic potential. This process
continues until the substrate is completely covered by the coating. This deposition process, called
the displacement coating process. In the second group, the electrons needed to perform the
deposition reaction are provided by applying external current. This type of coating is called
electrodeposition process. In the third type, the electrons required to perform the reduction
reaction and to form a coating are provided by the oxidation of the chemical species (reducing
agent). This type of coating is called electroless coating process.

In general, the reaction leading to deposition of the electroless coating involves two half
reactions according to the following reactions:

Mez+ + ze- Me (2)

reducing agent oxidized reducing agentz+ + ze- (3)

The general reaction to create nickel electroless coating can be written as follows:

Ni2+ + reducing agent Ni coating + oxidized form of reducing agent (4)

This reaction will be thermodynamically feasible if the reduction potential of the reduced species
(in this case nickel ions) is more positive than the reduction potential of the oxidized species.
Therefore, reducing species should be selected in such a way that the greatest difference in
reduction potential is achieved [29-31].

Many suggestions have been made for the formation of nickel-boron electroless coatings, one of
which is in good agreement with experimental observations. The main mechanism for the
formation of nickel-boron coatings by electroless can be divided into three main steps [32].

The first step involves the reduction of nickel:

BH-4 + 4H2O B(OH)-4 + 4H + 4H+ +4e- (5)

2 Ni2+ + 4e- 2Ni0 (6)

BH-4 + 2Ni2+ + 4H2O 2Ni0 +B(OH)-4 + 2H2 + 4H+ (7)

The second stage involves boron reduction reaction:

BH4- + H+ BH3 + H2 B + 5/2 H2 (8)

The third step involves the hydrolysis of borohydride:

BH-4 + 4H2O B(OH)-4 + 4H +4H+ + 4e- B(OH)-4 + 4H2 (9)

In addition, in baths in which sodium borohydride is used as a reducing agent, two reduction and
oxidation reactions occur simultaneously on the metal surface to produce coatings. Borohydride
is oxidized according to the following reactions during electroless coating [33, 34]:

BH-4 + 4OH- BO-2 + 2H2O + 2H2 + 4e- (10)

BH4- B + 2H2 + e- (11)

Two different reactions occur in the reduction process, including the reduction of nickel and
hydrogen ions. These two reactions take place competitively. The electrons required for the
reduction reaction of nickel ions are provided by the reaction between borohydride and
hydroxide ions according to the following reactions:

Ni2+ + 2e- Ni (12)

2H2O + 2e- 2OH- + H2 (13)

The coating morphology strongly depends on the coating growth mechanism. In general, the
nickel-boron electroless coating structure is deposited as a nodular structure. This nodular
structure is similar to the cauliflower. The SEM image of the cross-section and the surface of the
Ni-B electroless coating at low and high boron content is shown in Fig. 1. The formation of this
structure is due to the growth mechanism of nickel-boron coatings. Cross-sectional images show
columnar growth. It is also seen that as the amount of boron in the coating increases, the coating
uniformity increases[35].
 Fig. 1) Scanning electron microscopy images of cross-section and cross-section a and c) Low-
boron nickel-coating and b and d) High-boron content [35].

In general, the nickel-boron electroless coating structure consists of several layers of columns,
which decreases with increasing distance from the substrate. The reason for this can be attributed
to the mechanism of column formation in the early stages. Three general types of columns are
distinguishable, including small columns that are initially blocked and do not exceed 2.5 μm in
length; the second layer comprises columns with average sizes of 5 to 6 μm and the third layer
contains the end of the coating[36]. Furthermore, according to the observations of Rao et al,[37],
at the onset of growth, the large number of nuclei are formed due to the high concentration of
reactants on the substrate surface. The growth of crystals overcomes the nucleation, which
results in an ion-free zone near the precipitate. This results in a slower growth rate and
consequently a change in the growth mode. Thus, it can be said that the formation of nickel-
boron electroless coating initially involves the creation of a columnar morphology, which is then
replaced by a nodular one. This morphology results from the formation of a thick diffusion layer
near the deposit. This diffusion layer can reduce the growth rate of columns and lead to the
formation of a nodular layer. This mechanism is schematically illustrated in Figure 2. From Fig.
2 it can be assumed that the diffusion layer between the two nuclei (location A) is thicker than
site B. Therefore, growth in the vertical direction is faster than growth in the horizontal direction.
As the crystallites grow, their growth in the lateral direction is restricted by the adjacent
crystallites. Therefore, the crystallite grows only in the vertical direction[37].

Figure 2) Schematic showing the influence of the diffusion layer on crystal growth a) nucleation
time, b) crystal growth time [37].

Also, the initial formation mechanism of nickel-boron electroless coating has been investigated
by Vitry et al. [38, 39]. The results of their studies showed that the initiation of the process is due
to oxidation of the reducing species on the substrate surface. Furthermore, the deposition process
always begins at the scratches of the surface or at the grain boundaries. Also, the column
morphology is the result of the vertical growth of many initially formed islands. Once the
column morphology is established, the column widths change over time. It was concluded that
the growth rate was more regular at the late stages of the deposition process. In a broader
conclusion, the various steps of electroless coating deposition include the following: Initially, a
very low induction period is required, in which the nickel ions are reduced which are not
nodular., then a thin continuous layer is formed on the surface and then the nodules are formed.
Next we have the coating thickening which starts after 4 minutes. During this time, the coating
thickness does not increase and only the coating density increases. After this stage, there are
various stages of nucleation and growth, each of them is triggered by the refinement of the
columnar structure. Initial re-nucleation occurs within 4 to 7 minutes[39].

Various factors affect the morphology of Ni-B electroless coatings, including ultrasonic agitation
during coating treatment. In general, the use of ultrasonic agitation during coating treatment
affects the chemical and physical properties of electroless Ni coatings. The application of
acoustic field has been shown to have positive effects on electroless Ni coatings. Studies have
shown that the application of ultrasonic agitation leads to increased deposition rate and hardness
of coatings[40-42]. The effect of ultrasonic agitation on the surface morphology of Ni-B
electroless coatings is shown in Fig. 3. As can be seen, the surface texture of the Ni-B coating
created is cauliflower-like without the use of ultrasonic agitation (Fig. 3a). Also, the coating
created at 20 KHz has a similar structure but the surface is smoother. Furthermore, by increasing
the frequency of the ultrasonic field (Fig. 3c), the created surface is smooth. In addition, the use
of ultrasonic waves increases the density of the coating. The use of ultrasonic waves in this case
has led to improved deposition rate efficiency. High deposition rate efficiencies lead to depletion
of reactive species in the coating bath, resulting in new germination phases and ultimately a
denser coating[15]. Also, since the use of ultrasonic waves leads to degas of the solution, the
creation of a denser layer due to the use of ultrasonic waves can be attributed to the lack of
occlusion of hydrogen bubbles[43, 44]. In addition, the use of ultrasonic waves in another study
at different temperatures showed that the use of these waves at all temperatures leads to a
smoother surface morphology[45].

Figure 3) Optical microscope images of the surface of Ni-B electroless coatings a) without the
use of ultrasonic waves, b) by using ultrasonic waves during coating and the frequency of 20
KHz, and c) by using waves ultrasonic during coating and frequency of 35 KHz[15].
In addition, bath replenishment can affect the coating morphology. As the concentration of bath
components, including reducing agents and stabilizers, decreases during coating treatment, the
deposition rate decreases. Therefore, bath replenishment is necessary in order to create a coating
with the desired quality and high deposition rate [46]. Delaunois et al. [29], have investigated the
effect of bath replenishment on reducing agent and stabilizing species. The study was that
sodium borohydride and thallium nitrate were added to the solution every 30 minutes. The
results showed that by applying bath replenishment, a sticky, high-density and continuous
coating is created with a thickness of about 90. However, when the bath composition remained
constant during deposition, the coating thickness was only 56 mm [29].

2.2. Phase structure

Because boron has a very low solubility in nickel, it will be very difficult to penetrate in the
temperature range of the nickel-boron electroless coating deposition. Therefore, the phase
structure of the coating created by the XRD method will be different from the expected
equilibrium structure of the nickel-boron phase diagram. From a macroscopic point of view, the
nickel-boron coating is the supersaturated solid solution of boron in nickel. According to the
observations, the phase structure of the nickel-boron electroless coating at low concentrations of
boron is microcrystalline and then gradually increases to amorphous with increasing boron
content up to 5 to 6 wt.%. The XRD spectra of nickel-boron electroless coatings without heat
treatment at different boron concentrations are shown in Fig. 4. It is observed that at
concentrations above 5% boron, the structure is completely amorphous. However, by heat
treatment on the nickel-boron electroless coating, the phase structure becomes crystalline.
Different phases (Ni, Ni2B, Ni3B and Ni4B) can be created by heat treatment depending on the
amount of boron and thermal history. In general, the crystallinity increases with increasing
temperature and heat treatment time. This can be seen in Fig. 5[47].
Figure 4) XRD patterns of nickel-boron electroless coatings at different concentrations of boron
a) 3.01, b) 5.54 and c) 6.25 wt.% [47].
 Fig. 5) XRD spectra of nickel-boron electroless coatings without heat treatment and heat
treatment at different temperatures [48].

Furthermore, the effect of heat treatment as well as the amount of boron content on the crystal
structure of nickel-boron electroless coating is shown in Fig.6. In both cases, mid B and high B,
crystal structure is amorphous. But by performing heat treatment on both coatings, a crystalline
structure is created. However, after heat treatment, there is a difference between mid B and high
B coatings. There are Ni3B phases in mid B coating, but in high B coating, in addition to Ni3B,
there are also Ni2B phases, which is due to the presence of more content of B [49, 50]. Also, with
increasing value of B, very low amounts of Ni phase appear, which is the result of chemical
modification of the surface as a result of heat treatment [35].

Figure 6) XRD patterns data of mid- and high-boron coatings with and without application of
heat treatment[35].

3. Components of nickel-boron electroless coating bath.

In the electroless nickel-boron bath, there are various components that each have a specific
function, and the synergistic effect of these components and the function of these components
will create a uniform coating on the substrate surface. In electroless coatings, metal ions are
reduced to metal by the action of reducing, which are electron donors. In general, these
components are listed below.

 Reducing agents
 Nickel ion source
  Complexing agents
 Surfactants
 Stabilizing agent
 Buffering agents

3.1. Nickel ion source

In general, any nickel salt can be used as a source of nickel in the electroless nickel- boron
coating bath. But many studies have used NiCl2.6H2O as the source of nickel ions. In some
sources, nickel sulfate is also used as nickel ion source.

3.2. Reducing agents

The reducing agent produces the electrons needed for the reduction reaction. A large number of
reducing agents can be used in nickel-boron baths. However, many sources have used
dimethylene borane (DMAB) and sodium borohydride (NaBH4) as a reducing agent in the
nickel-boron electroless coating bath. The high potency of sodium brohydrate as a reducing
agent has made it an attractive reducing agent for nickel-boron coatings. Sodium borohydride has
a higher reducing agent ability than DMAB. The high efficiency of NaBH4 can be attributed to
the fact that it can provide more electrons. It can provide up to 8 electrons of metal ions during
the coating so that the ions can be resurfaced and deposited. In addition, baths with NaBH 4 are
more economical as a reducing agent. The only drawback of NaBH4 as a reducing agent is that it
is hydrolyzed when exposed to acidic and base environments. This makes it necessary to adjust
the pH value during coating. So, it can be said that DMAB is stable in acidic and basic solutions
and NaBH4 is only applicable in acidic solutions. Coatings made in baths containing NaBH4
have been reported to have better properties as compared to other reducing agents. These
properties include higher hardness and better mechanical properties [19, 51].

3.3. Complexing agent

The main purpose of adding complexing agents to the coating bath is to avoid abrupt reduction
of the pH of the bath, to prevent the deposition of coating agents such as nickel salt, as well as to
facilitate the formation of metastable complex compounds in order to minimize the amount of
free Ni ions in the coating bath. As well, in alkaline solutions, the complexing agent by forming
a complex with metal ions prevents the deposition of non-solvent hydroxides. In addition, it has
been reported that reducing agents have a significant influence on the reaction mechanism and
rate of coating formation. Typically, in the early stages, the rate of coating formation increases
with increasing complexing agent content and then decreases. In order to find a suitable
complexing agnet for a coating bath containing NaBH4, Gorbonova et al.[32] used different
complexing agents. The results of their studies showed that ethylene diamine (EDA) is the most
suitable complexing agent. EDA is now used as a complexing agent in many nickel-boron baths.
Optimal EDA concentration in coating baths of 90 g/l has also been reported [39].

3.4. Surfactants

In general, surfactants are used to improve wettability, which reduces the surface tension of the
coating bath solution. Proper use of surfactants in the coating bath results in a uniform
distribution of coating agents in the bath. In general, in an electroless nickel-boron coating bath,
the addition of sufficient amounts of surfactants results in improved deposition rates.

3.5. Stabilizers

In spite of the use of effective complexing agents in the coating bath, the solution shows little
stability and deposits of metal powder are observed in the coating solution. In order to reduce the
deposition of metallic powders in the coating bath, a material called stabilizers is used. It has
been reported that appropriate amounts of stabilizers are necessary to control the reduction
reaction in a nickel-boron coating bath. During the nickel-boron electroless reaction, stabilizers
are adsorbed on the surface of different particles and thus results in the reduction of nickel ions
on them. There are a number of stabilizers available that have shown excellent performance.
Careful selection of the stabilizer is important. Some studies have shown that mercapto
benzothiazole is effective in stabilizing the coating bath. But, the use of these stabilizers results
in a lower deposition rate. Thallium compounds such as thallium nitrate are desirable stabilizers
to stabilize the coating bath. Furthermore, with these stabilizers the deposition rate is still
high[52, 53]. The use of stabilizers can also have negative effects, including increased internal
stresses, increased coating porosity, reduced corrosion resistance, reduced deposition rate and
increased coating gloss. The amount of these stabilizers should be kept as low as possible in
order to prevent these disadvantages. Because many stabilizers have a negative impact on the
environment, research has recently expanded to provide newer lead-free stabilizers that are not
harmful to the environment. For example, Bonin et al. [16] used bismuth salts as a stabilizer in
Ni-B alkaline baths and concluded that the use of this stabilizer results in significant
improvements in coating properties.

4. Nickel-boron electroless coating baths

In general, electroless nickel-boron coating baths can be divided into acidic and alkaline baths,
which will discuss these baths separately.

4.1. Acidic baths

In acidic baths, dimethylamine borane is commonly used as a reducing agent. The usual
chemical composition of a nickel-boric acid bath is given in Table 1. Usually in these baths the
amount of boron is between 1% and 4%[54]. The coatings created by these baths because they
are harder than nickel-phosphor coatings are commonly used in applications that require high
hardness. coating rate of this bath is 15-20 µm/h.

Table 1: Chemical composition and parameters of Ni-B acidic bath

Composition amount Parameter Range

NiCl2.6H2O 30 g/l pH 5-6
diethylamine borane 3 g/l
methanol 40 g/l Temperature 50-60° C
dimethylamine borane 4 g/l
sodium acetate 20 g/l
sodium succinate 20 g/l
sodium citrate 10 g/l

4.2. Alkaline baths

Other bath used for nickel-boron electroless coatings are alkaline baths. In this case, hot and cold
baths can be used. The chemical composition and parameters used to create the coating using hot
and cold baths are given in Tables 2 and 3, respectively. The deposition rate of the coating
created in hot and cold baths is 20-25 µm/h and 7-12 µm/h, respectively. In general, because the
bath becomes unstable at high temperatures, low temperature baths are preferred for industrial
use.

Table 2: Chemical composition and parameters of Ni-B alkaline hot bath

Composition amount Parameter Range

NiCl2.6H2O 30 g/l pH 14
ethylenediamine 60 g/l
sodium borohydride 1.2 g/l Temperature 90° C
thallium nitrate 0.07 g/l
sodium hydroxide 40 g/l

Table 3: Chemical composition and parameters of Ni-B alkaline cold bath

Composition amount Parameter Range

Nickel sulfate 30 g/l pH Upper 7
dimethylamine borane 3 g/l
ammonium citrate 15 g/l Temperature 25-35 ° C
ammonium chloride 15 g/l
2-metcaptobenzothiazole 0.0002 g/l

5. Properties of Ni-B electroless coatings

Nickel-boron electroless coatings have favorable properties that have led to the industrial use of
many of these coatings. By changing the coating variables and consequently changing the
amount of boron in the coating as well as by the heat treatment, it is possible to change the
coating properties to the desired one. In this section, the properties of nickel-boron electroless
coatings are summarized. Nickel-boron electroless coating has a high uniformity which can be
used to coatings the complex industrial components. In this case, the uniformity of the coatings
created by the electroless deposition method is much better than the coatings obtained by the
electrochemical deposition method. The coating density of nickel-boron electroless in 5% boron
is 8.25 g/cm3. The melting point of the nickel-boron electroless coatings is between the melting
point of pure nickel (1445 °C) and the melting point of the Ni /Ni3B eutectic compound (1093
°C). The melting point decreases with increasing boron content in the coating. Also, the
electrical resistance of electroless nickel-boron coating is higher than pure nickel coating. The
deposited nickel-boron electroless coating has ferromagnetic properties. As for the mechanical
properties of the Ni-B electroless coating, it can be said that these properties strongly depend on
the amount of boron inside the coating as well as the heat treatment. The ductility value of
nickel-boron electroless coatings is about 20% of high phosphorus nickel-phosphor coatings. In
this section, the effect of various factors on some important properties of Ni-B electroless
coatings will be discussed.

5.1. Corrosion resistance

Corrosion is one of the most important destructive mechanisms in different industries that causes
many financial and personal losses annually. There are many methods to stop or reduce the rate
of corrosion. In the meantime, one of the most important ways is application of coatings.
Different coatings have been developed by different researchers to increase the corrosion
resistance of different substrates. Unfortunately, many metal coatings are inherently porous and
non-uniform and have less corrosion resistance. This problem can often be overcome by the
emergence of electroless coatings[55]. Ni-B electroless coatings have become important because
of their good corrosion resistance. Ni-B electroless coatings are more noble than various
substrates such as steel, aluminum and magnesium and improve the corrosion resistance of the
substrate by creating a dense layer. On the other hand, these coatings are amorphous and, due to
the amorphous nature, in many environments exhibit better corrosion resistance than nickel and
chromium alloy coatings. Amorphous alloys have better corrosion resistance than crystalline one
in different environments because they do not have corrosion-prone locations (like grain
boundaries) therefore are not corrosion-prone. The results of Wang et al.'s study [47] in order to
study the effect of Ni-B electroless coating on the corrosion resistance of magnesium substrate
showed that the creation of electroless coating leads to a significant improvement in corrosion
resistance and corrosion current density reduced form 28.54 µA.cm-2 for the substrate to 0.256
µA.cm-2 for electroless coating, indicating the ability of the Ni-B electroless coating to create a
protective layer to improve corrosion resistance. Various variables can influence the corrosion
resistance of Ni-B electroless coatings. In this section, the influence of these variables on the
corrosion resistance of Ni-B electroless coating is reviewed.
5.1.1. The effect of additives on corrosion resistance

Various additives have been added to the coating and the corrosion resistance influenced by
these additives has been studied. One of the most important of these additives are ceramic
nanoparticles. Various nanoparticles have been used to improve the corrosion resistance of Ni-B-
electroless coatings. The use of nanoparticles in coatings generally results in increased coating
density and thus improved corrosion resistance. One of these nanoparticles is TiO2
nanoparticles[56, 57]. In order to improve the corrosion resistance of Ni-B electroless coating,
Nicksefat et al.[56] used TiO2 nanoparticles. They used EIS and polarization methods to
investigate corrosion resistance. The effect of adding TiO2 nanoparticles on coating corrosion
resistance in polarization and nyquist curves is shown in Fig. 7. The corrosion current density of
Ni-B coating was 1.2 μA.cm-2 which was 6 times lower than the substrate corrosion current
density. The reason is that the amorphous coating acts as a protective layer and improves
corrosion resistance. On the other hand, with respect to the Nyquist curves, it can be seen that the
creation of Ni-B-TiO2 nanocomposite coatings increases the diameter of the Nyquist curve and
consequently improves the corrosion resistance of the coating. The improved corrosion
resistance of the nanocomposite coating is due to the fact that the nanoparticles form a barrier
layer, filling the very small pores in the coating, thereby increasing the density and increasing the
corrosion resistance. On the other hand, it is believed that when particles are deposited
simultaneously, this results in an acceleration in the process of passivation and thus improves the
corrosion resistance of the nanocomposite coatings [58, 59].
 Fig. 7) Polarization curves for different samples and b) Nyqusit curves for Ni-B and
nanocomposite coatings[56].

Another nanoparticle used by researchers to improve the corrosion resistance of electroless Ni-B
coatings is CeO2 nanoparticles. The nanoparticles have also been used to improve the corrosion
resistance of other coatings [60, 61]. Pancrecious eta al [62], used CeO2 nanoparticles to improve
the corrosion resistance of Ni-B electroless coatings. Examination of the corrosion resistance by
the Nyquist curves (Fig. 8) showed that adding CeO2 nanoparticles to the coating increased the
Nyquist curve diameter and consequently reduced the ion penetration to the substrate surface and
improved the corrosion resistance. It was also shown that increasing the concentration of
nanoparticles inside the coating slightly reduced the corrosion resistance. The phase curve shown
in Figure 6b can also be used to investigate the corrosion behavior and mechanism. It is seen that
there is only one time constant (one peak) in the substrate and Ni-B coating, but the frequency
ranges for Ni-B coating shifts to lower values due to the presence of a nobler layer. However, in
the case of nanocomposite coatings, two time constants overlap at intermediate and low
frequencies. The higher protective properties of CeO2 nanoparticles in the coating can be
attributed to the neutralization of these nanoparticles to the environment's corrosive ions. These
particles also lead to zigzag crossing paths of corrosive ions to the substrate[63]. In addition, the
ionic state conversion of cerium ions from Ce3+ to Ce4+ exposed to corrosive media can lead to
increased corrosion resistance.
 Fig. 8) a) Nyquist curves and b) Bode-phase curves of different coatings and nanocomposite
coatings[62].

Further neutral nanoparticles have also been used to improve the corrosion behavior of Ni-B
electroless coatings. Other types of nanoparticles include Si3N4, which has been used by
Krishnaveni et al.[64] to improve corrosion resistance. Si3N4 nanoparticles are very hard
particles that maintain their strength up to 1200 °C and exhibit excellent dimensional stability
and excellent oxidation resistance. These nanoparticles have also been used successfully in other
coating systems [65-67]. Corrosion behavior of Ni-B electroless coating composited with Si3N4
nanoparticles by electrochemical methods showed that addition of this nanoparticle to the
coating resulted in a decrease of corrosion current density from 8.41 μA.cm-2 for Ni-B coating to
4.42 μA.cm-2 for Ni-B-Si3N4 coating. Insertion of Si3N4 nanoparticles into the coating leads to a
change in the microstructure of the coating. Application of nanoparticles showed better corrosion
resistance than micro-particles. The reason for this was that the use of nanoparticles resulted in
the filling of all the fine and coarse pores in the coating, resulting in a further increase in coating
density [64]. SiC nanoparticles have also been used to improve the corrosion resistance of Ni-B
electroless coatings [68]. The creation of Ni-B-SiC nanocomposite coating resulted in a more
positive corrosion potential as well as a decrease in the corrosion current density, which indicates
improved corrosion resistance due to the addition of SiC nanoparticles. In this case, inert
nanoparticles lead to lower substrate dissolution rates by reducing the amount of metal coating
area exposed to corrosive medium [69, 70]. In addition to the studies mentioned, other hard
nanoparticles such as B4C [71] and Al2O3 [72] have also been used by various researchers to
improve coating microstructure and corrosion resistance, which has shown to improve corrosion
resistance [73, 74].

Other additives include a third alloying element and the creation of a Ni-B electroless alloy
coating [75]. The SnCl2 additive in Ni-B electroless coating has been used to improve the
corrosion resistance of the coating[75]. The results of this study showed that the use of Sn leads
to improved corrosion resistance. This can be explained by the fact that during the electroless
process, Sn particles are distributed at the grain boundaries, which reduces the number of defects
in the coating, thereby increasing the coating density and ultimately improving the corrosion
resistance[57]. In addition, coating bath additives also influence the microstructure and chemical
composition and consequently the corrosion resistance of the coating. The effect of NaBH4 and
thallium acetate concentrations on the corrosion resistance of coatings has been investigated by
Anik et al. [48]. The results showed that by increasing the NaBH4 content the charge transfer
resistance increased and consequently the corrosion resistance improved. It also decreases
corrosion resistance by increasing thallium acetate in the coating. The effect of NaBH 4
concentration on the corrosion resistance of electroless nickel-boron coating has also been
investigated by Baskaran et al.[76]. As mentioned, stabilizers are one of the most important
components of the bath. Bonin et al.[77] used tin chloride as an additive and stabilizer to
improve the corrosion resistance of nickel-boron coatings. Coating was carried out at different
concentrations of SnCl2, and it was concluded that SnCl2 not only stabilized the coating bath but
also increased the growth rate of the coating. It also improves the corrosion resistance of the
coating by applying SnCl2. In addition, soft particles can also be used in coatings to improve
corrosion resistance. PTFE particles were investigated by Wan et al. [78] to improve the
corrosion resistance and tribological properties of Ni-B electroless coatings. The results showed
that adding PTFE to the coating improved the corrosion resistance. The reason for the improved
corrosion resistance is the presence of neutral particles in the coating and consequently the
reduction of the penetration of corrosive ions into the substrate.

5.1.2. Effect of operational variables

In addition to the application of nanoparticles within the coating, the operational variables also
influence the corrosion resistance, which can be affected by the coating temperature, heat
treatment [79, 80] and the chemical composition of the coating bath[48]. In this section, the
influence of these variables on the corrosion resistance is discussed. The influence of coating
temperature bath and heat treatment on the corrosion resistance of coatings was investigated by
Abdel Hamid et al. [79]. The polarization curves for coatings formed at operating temperatures
of 60 and 80 °C as well as heat treatment at temperatures of 250 and 400 °C are shown in Fig. 9.
The curves show that the coating temperature and heat treatment have a significant effect on the
corrosion resistance of the coatings. The results showed that by increasing the coating
temperature bath from 60 to 80 °C, the corrosion current density increased from 7.1 µA.cm-2 to
19 µA.cm-2. This is due to the smaller grain size of the coating at 60 °C than that of the coating at
80 °C. Smaller particle size results in increased coating density and consequently improved
corrosion resistance. It also improves the corrosion resistance of the coating by increasing heat
treatment from 250 to 400 °C. In this case, the corrosion current density of the heat treatment
coating at 400 °C is about 9.5 times lower than that of the heat treatment coating at 250 °C.
 Figure 9) a) polarization curves of Ni-B samples coated at 60 °C and b) coated at 80 °C [79].

The effect of heat treatment relative to the non-heat treatment coating has also been investigated.
In general, with heat treatment, the coating changes from amorphous to crystalline structure,
which results in reduced corrosion resistance. For example, in one study it was shown that heat
treatment of the Ni2B and Ni3B phases results in the formation of regions with different
thermodynamic potentials and thus Reduces corrosion resistance[52, 81]. In addition, heat
treatment results in thermal stresses due to the difference in expansion coefficient between the
coating and the substrate. The high amount of these stresses results in increased cracks in the
coating. The presence of cracks after heat treatment results in galvanic coupling between the
coating and the substrate, which results in reduced corrosion resistance. These cracks are also
pathways for the passage of corrosive ions to the substrate, resulting in reduced corrosion
resistance. Also in another study, the effect of vacuum heat treatment on the corrosion resistance
of the electroless nickel-boron coating was investigated and it was found that the vacuum heat
treatment also reduced the corrosion resistance and for steel, heat treatment in vacuum the
corrosion current density increases from 4.85 μA/cm2 to 11.27 μA/cm2 [82].

5.2. Oxidation behaviour

Other applications of nickel-boron electroless coatings include improved oxidation resistance.

Although studies on the oxidation resistance of electroless nickel-boron coatings are limited[83-
85], in this section the oxidation resistance of these coatings is discussed. Studies have been
conducted to compare the oxidation resistance of electroless nickel-boron and nickel-phosphor
coatings and it has been concluded that the oxidation of both of these coatings follows the
parabolic law and oxidation rates of Ni-P coatings is more than Ni- B due to the lower amount of
Ni in the Ni-P coating[86]. This result has also been confirmed by other researchers and found
that Ni-B oxidation at 600 and 700 ° C is lower than Ni-P [83]. The oxidation behavior of Ni-B
and Ni-W-B coatings created by the electroless method was performed by Eraslan et al. [83] and
these results were compared with the Ni-P electroless coating. In their study, the oxidation
behavior of coatings was investigated by monitoring the oxide properties and the influence of
iron on the structure by GDOES analysis. The results showed that the oxidation behavior
depends not only on the coating but also on the diffusion processes occurring between the
substrate and the coating. For Ni-P coating, at 700 °C, iron begins to participate in the oxide
structure, which results in reduced oxide protection. In boron-containing coatings, boron
depletion was observed in the coating and the formation of nickel borates. In general, it was
concluded that the oxidation behavior of Ni-W-B coating was similar to Ni-B coating, except
that the presence of tungsten reduced the penetration of iron to the surface and delayed the
formation of iron oxide. Therefore, it can be concluded that the presence of tungsten improves
oxidation resistance. The thickness curves of the diffusive layer at 600 °C during different
oxidation times are shown in Fig. 10. It is observed that the thickness of the diffusion layer and
the diffusion of iron decrease due to the presence of tungsten. The very strong bond between Ni-
W and Fe-W provides an important barrier to the diffusion pathway and prevents the outward
penetration of iron[83]. In another study, the kinetics and mechanism of thermal oxidation of Ni-
B electroless coatings were investigated. It was shown that the oxidation behavior is mainly
determined by the properties of boron oxide. At temperatures above 300 ° C, oxidation is
performed by boron oxide sublimation. The addition of tungsten slightly increases the oxidation
rate, but the addition of boron leads to a significant increase in the oxidation rate. In the study, it
was suggested that glass salts are formed as a result of a reaction between low-melting boron
oxide and metal oxides. Therefore, the presence of boron in the structure directly affects the
kinetics and mechanism of oxidation[84].
 Fig. 10) diffusion layer thickness for various oxidized samples at temperatures of 600 and 700
°C [83].

5.3. Wear and hardness

The wear resistance and hardness of the coatings can also be improved by using different
additives as well as by changing the coating variables and performing heat treatment. In this
section, strategies to improve the wear resistance and hardness of nickel-boron coatings will be
examined.

5.3.1. The effect of various additives

Various additives such as different nanoparticles have been used by various researchers to
improve the wear resistance and hardness of nickel-boron electroless coatings. In general,
materials with the lower grains size, such as Ni-B nanocrystalline deposits, are harder than large-
sized deposits. Under these conditions, as the grain size decreases, the number of grain
boundaries increases, which prevents the dislocations movement and increases hardness [87].
The hardness of the electroless coatings increases with the addition of hard particles and it is
believed that the increase in hardness is a function of the amount of particle entry into the
coating and is not a function of the intrinsic hardness of the imported particles [82]. One of the
most important nanoparticles used is SiC nanoparticles used by Georgiza et al.[68] to improve
the microhardness of nickel-boron electroless coatings. They concluded that adding SiC to the
coating resulted in increased coating hardness. The increased hardness of the coating can be
attributed to the morphology change due to the addition of nanoparticles. There are two ways to
movement of a dislocation from the particle. One way is to cut the particle-and the second is to
orbit the particle. The first mechanism is when the interface between the particle and the matrix
is coherent and the second mechanism is dominant when the particle is larger and the interface
with the sample is non-coherent [59]. Therefore, it can be stated that a harder coating is created
when small particles are introduced into the coating and better dispersed in the coating. B4C
nanoparticles have also been used to improve tribological properties. The adding B4C
nanoparticles to the coating has shown to increase the coating hardness from 620 Vickers in Ni-
B coating to 870 Vickers in Ni-B-B4C nanocomposite coating [71]. In addition to the intrinsic
hardness of B4C nanoparticles, this nanoparticle acts as a barrier on the coating and results in a
plastic deformation in the Ni-B matrix, resulting in increased coating hardness. Because of their
high surface energy, the nanoparticles are intended to agglomeration in the coating, which
reduces the performance of these nanoparticles in improving the mechanical properties of the
coating. Therefore, it is important to adopt methods to prevent agglomeration of particles in the
coating. Niksefat et al,[56] used the ultrasonic assisted electroless deposition method to prevent
nanoparticle agglomeration to produce Ni-B-TiO2 nanocomposite coating. They also rotated the
substrate at 300 rpm to increase the amount of nanoparticles in the coating. The microhardness
and friction coefficient of nanocomposite coatings were investigated. The incorporation of TiO2
nanoparticles into the coating resulted in increased hardness of the coating due to dispersive
reinforcement effects and grain modification[83]. The friction coefficient was also increased by
adding hard nanoparticles to the coating. The reason was that the nanoparticles were uniformly
distributed in the nanocomposite coating and resulted in the filling of the coatings pores. This
prevents lubricant flow in these spaces and thus results in increased friction coefficient. Also,
other added nanoparticles such as CeO2 [62] in the coating lead to increased hardness of nickel-
boron coatings due to the described mechanism. Also, wear resistance studies by adding CeO2
nanoparticles showed that adding nanoparticles to the coating leads to a decrease in the wear
rate. It was observed that the wear rate increases with increasing load value. At higher loads,
nanocomposite coatings show much lower wear rates. The type of used nanoparticles also may
affect the coating hardness. EKMEKCI et al [72] investigated the effect of different
nanoparticles on the hardness of Ni-B electroless coating. The hardness of different
nanocomposite coatings is shown in Fig. 11. It can be seen from the figure that nanocomposites
with all nanoparticles resulted in increased hardness of the coating. It is also seen that Al2O3
nanoparticles lead to the highest hardness and TiO2 nanoparticles have the lowest hardness. The
reason for this difference can be attributed to the higher compressive strength and higher
modulus of elasticity of Al2O3 nanoparticles [85].

Fig. 11) The hardness of Ni-B electroless coating as a function of the type of nanoparticles[72].

Carbon nanotubes have also been used in nickel-boron electroless coatings and coating
properties have been investigated. Yazdani et al[88]. developed a nickel-boron electroless
coating in the presence of CNT nanoparticles of varying concentrations and investigated the
mechanical properties of the coatings. It was found that by increasing the concentration of CNT
in the coating bath to 0.6 g/l, the microhardness increased and then decreased. The reason for the
increase in hardness up to 0.6 g /l can be attributed to the uniform distribution of CNT particles
in the coating. The further agglomeration of the nanoparticles occurs with further increase of the
particles up to 1 g/l, which reduces the hardness. Also the friction coefficient curves showed that
addition of CNT particles resulted in decrease of friction coefficient.

In addition to hard nanoparticles, soft particles can also be incorporated into the coating,
resulting in improved tribological properties. In general, for industrial applications, a low friction
coefficient is preferred[89]. One of the particles that can lead to reduced friction coefficient are
PTFE particles which used in other coating systems[90]. Also, in the coating of electroless
nickel-boron Wan et al [78] used PTFE particles to reduce the friction coefficient. It was
observed that the uncoated substrate had the highest coefficient of friction and by applying
nickel-boron coating, the coefficient of friction was reduced. A further decrease in the coefficient
of friction is also observed by adding PTFE particles. In addition, the coefficient of friction also
depends on the amount of PTFE in the coating and as the amount of PTFE in the coating
increases, the coefficient of friction decreases further. In another study, the effect of zinc acetate
as an additive to Ni-B electroless bath on coating hardness was investigated[91]. It was observed
that the highest hardness was obtained at a concentration of 1 g/l zinc acetate, and as the
concentration increased, the hardness of the coating decreased. This is due to the decrease in
boron content in the coating as the concentration of zinc acetate increases, which also increases
the wear rate.

5.3.2. Effect of heat treatment

Heat treatment is one of the most important operating variables that can affect tribological
properties. The influence of heat treatment on tribological properties has been investigated by
various researchers. As stated above, in general, heat treatment results in a change of state from
amorphous to crystalline. The XRD spectra of the as-deposited nickel-boron coating and the heat
treatment at 400 ° C for 1 hour are shown in Fig. 12a. It can be seen that without heat treatment,
the phase structure is amorphous, and with heat treatment the structure is changed to crystalline
and the Ni3B phase is formed. This result has also been shown in other studies[53, 82]. The
effect of heat treatment on coating hardness is also shown in Fig. 12b. Since the structure is
affected by the heat treatment, then it can be expected that the mechanical properties of the
coating will also be affected by the heat treatment. Many researchers have attributed the increase
in hardness due to heat treatment to the grain boundaries relative to the amorphous initial state
and thus to the Hall-Petch effect[92, 93]. It is undeniable that the Hall-Petch effect gives rise to
hardness, but another point to consider is the increase in softness due to the increase in grain size
due to heat treatment at 400 °C. Therefore, the major contribution of the increase in hardness due
to heat treatment can be attributed to the phase shift to the orthorhombic Ni3B structure. This is
also observed in the phase shift from austenite to Fe3C[94]. It was also observed that the Young's
modulus increased as a result of heat treatment[95]. The effect of heat treatment on coating
hardness has also been investigated by various other researchers. One study has shown that heat
treatment at 450 °C results in the formation of Ni2B and Ni3B crystalline phases, which increases
the hardness of the coating [56]. Heat treatment has also resulted in a reduction in friction
coefficient, which can be attributed to the precipitation hardening phenomenon and the creation
of phase structures[50, 96-98].

Figure 12) a) XRD spectra of nickel-boron electroless coatings with and without heat treatment,
b) influence of heat treatment on coating hardness[95]
As can be seen, heat treatment affects the hardness of the coatings. But the unknown question is
the effect of heat treatment temperature on the tribological properties of the Ni-B electroless
coating. The influence of heat treatment temperature on the tribological properties of nickel-
boron electroless coating was investigated by Gilley et al.[97]. In this study, the coatings were
annealed under oxygen flow for 3 h at different temperatures. The hardness and wear rate results
of all samples are presented in Table 4. The difference in tribological properties between
annealed samples at low and high temperatures can be attributed to the compositional and
morphological variations in this temperature range.

Table 4) Results of Tribological Properties of Annealed Samples at Different Temperatures[97]

Sample friction coefficient Wear rate ( mm2/Nm)

As received 0.55 4.3 10-8
250 ° C 0.58 4.8 10-8
400 ° C 0.9 N/A
550 ° C 0.17 2.7 10-7
700 ° C 0.06 2.1 10-7

Alloying can also severely affect the hardness and abrasion properties of the coating. The effect
of heat treatment temperature and the addition of tungsten and molybdenum alloys on the
hardness of nickel-boron electroless has been studied by Mukhopadhyay et al.[99]. In their study,
heat treatment temperatures of 350, 400 and 450 °C were considered. It was shown that in the as-
deposited state the most hardness was related to Ni-B-W coating and the addition of
molybdenum had no effect on the coating hardness because it could be due to high stress
produced during growth [100]. Heat treatment also increased the hardness of Ni-B and Ni-BW
coatings at 350 °C and increased the hardness of Ni-B-W coatings to 400 °C, but increased the
heat treatment temperature by up to 450 ° C, the hardness of Ni-B-W coating was lower than that
of Ni-B coating.

5.4. Electrocatalytic properties

In addition to corrosion resistance and tribological behavior, Nickel-boron coatings can have
favorable electrocatalytic properties which led to application in fuel cells[26], use as a hydrazine
oxidation electrocatalyst[101], and use as hydrogen and oxygen evolution reactions
electrocatalysts [102-106]. Scientists are looking for new energies to grow because of the
overcrowded population and declining fossil fuel resources. One of these energies is hydrogen
energy. To date, many nanostructures and materials have been used as electrocatalysts for
hydrogen production. Among the advanced materials on which recent research is undertaken,
boride-base materials can be mentioned. Electroless coating method is also one of the most
suitable and important methods for the creation of boride-based electrocatalysts. In this method,
coatings are typically applied to various substrates. These coatings can be used as excellent
electrocatalysts because of their excellent properties. These properties include self-support,
binder-free, and low interfacial strength[107]. For example, Zhang et al[102] created Ni-B
coatings using the electroless method and used this coating to electrocatalyst the HER reaction at
different pH values. The coatings were formed at different concentrations of nickel and boron
and it was concluded that the Ni-B0.54 coating had the best electrocatalytic properties. The LSV
curves for studying the electrocatalytic activity of coatings with different concentrations of
nickel-boron ratio as well as in different environments are shown in Fig. 13. The overpotential
required to generate a current density of 10 mA.cm-2 for the Ni-B0.54 electrodes in acidic
medium is 45 mV, in PBS medium is 54 mV and in alkaline medium is 135 mV. The superior
performance of this electrode in comparison to other electrodes reported in different
environments indicates the suitability of the electroless method to create a suitable electrocatalyst
for hydrogen production. Also, electrocatalytic properties can be further improved by Ni-B alloy
coating and Ni-Co-B alloy coating by electroless method. The Ni-Co-B nanostructured
amorphous coating on the OER reaction electrocatalyst was developed by Wang et al.[103]. At
optimum conditions, the electrode showed excellent electrocatalytic properties that required an
OER reaction of 300 mV to generate the current density of 10 mA.cm-2. Also, the Tafel slope of
this electrode was 113 mV.dec-1 and this electrode showed excellent electrocatalytic stability for
50 h. These results indicate that boride-based electrodes created by the Electroless method can
also be used as bi-functional electrocatalysts for overall water splitting[108].
 Figure 13) LSV curves for (a) Ni-B samples generated at different concentrations, (b) in acidic
medium, (c) in neutral medium, and (d) in alkaline medium[102].

6. Applications
As seen in review studies, Ni-B electroless coatings exhibit promising properties. It was also
seen that with the introduction of different particles as well as changing the coating and heat
treatment variables, the properties of coatings such as corrosion resistance, hardness and abrasion
resistance can be further improved. Ni-B electroless coatings also show other properties such as
good magnetic properties, low resistance and good electrocatalytic activity. Therefore, these
coatings can have different applications. Ni-B coatings created by the electroless method have
become very important industrially to improve the surface properties of various metals [14]. Due
to their excellent properties, these coatings have found special applications in various industries
such as chemical, oil and gas, defense, nuclear, automobile, electronics, hydrogen production,
etc. [ 11, 15-17].

7. Concluding remarks and future trends

In this review article, various aspects of nickel-boron electroless coatings are discussed and the
advantages of electroless coatings over other methods are also discussed. Initially, the
mechanism of formation, microstructure and chemical composition were discussed, followed by
a variety of applications such as improved corrosion resistance, improved tribological properties,
improved oxidation resistance, as well as the use of these coatings as electrocatalysts for
production of renewable energy was discussed. Also, the recent developments in stated property
improvement strategies was discussed. Overall, according to the discussions in this paper, it can
be stated that the use of different nanoparticles in the coating leads to an increase in coating
density and thus to improvement in corrosion resistance of the coating. The use of heat treatment
also results in the formation of crystalline phases, thereby reducing corrosion resistance and
improving the hardness of the coating. According to the studies, the following can be suggested
for future studies and to improve the mentioned properties:

 As has been seen, coating alloys improves corrosion resistance. Therefore, the use of
other alloying elements in nickel-boron electroless coatings such as iron, molybdenum,
cobalt and copper is suggested to improve the corrosion resistance. It is also suggested to
use other hard ceramic nanoparticles and soft nanoparticles to improve corrosion
resistance.
 In general, to improve the tribological properties, high hardness and low friction
coefficient are preferred. The use of hard nanoparticles in the coating increases the
hardness as well as increases the friction coefficient and, on the contrary, the use of soft
nanoparticles results in the reduction of the hardness and the reduction of the friction
coefficient. Therefore, the simultaneous application of hard and soft nanoparticles in
nickel-boron electroless coatings will reduce the friction coefficient and increase the
hardness, leading to further improvement in the tribological properties. So for future
studies, soft and hard particle types can be applied simultaneously in nickel-boron
electroless coatings, resulting in improved tribological properties.
  As has been seen, the oxidation behavior as well as the use of nickel-boron coatings as
electrocatalysts for the production of renewable energies is in the early stages of research.
Further studies on the oxidation behavior and further improvement in the oxidation
behavior as well as further studies to improve the electrocatalytic properties of the nickel-
boron coatings can be of great importance.

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Declaration of interests
☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.