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State of Art Review on Nickel-Based Electroless Coatings and Materials

Article in Journal of Bio- and Tribo-Corrosion · December 2021

DOI: 10.1007/s40735-021-00568-7

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Journal of Bio- and Tribo-Corrosion (2021) 7:134
https://doi.org/10.1007/s40735-021-00568-7

State of Art Review on Nickel‑Based Electroless Coatings and Materials

Vinod Babu Chintada1 · Ramji Koona2 · M. V. A. Raju Bahubalendruni3

Received: 13 May 2021 / Revised: 26 June 2021 / Accepted: 29 July 2021

© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2021

Abstract
Surface coatings are widely used in various industries to improve the functional performance and robustness. Researchers
considered the electroless-coating technique is one of the prominent methods in the past decade due to its simplicity, low
operating temperature, pores-free, optimized cost and low processing time. Electroless plating is one step method and its
properties are influenced by various parameters such as bath temperature, pH value, and type of surfactant used, concen-
tration of nickel source, reducing agent and secondary nano/micro particles added to the bath to form composite coatings.
The present review aims at the study of various coating materials and existing techniques in the preparation of electroless
Ni coatings for ferrous and nonferrous materials. More focus on Ni–P, Ni–B, and its composite coatings which are formed
by co-deposition of micro (hard) and nano (soft) particles in Ni–P, Ni–B matrix. The influence of process parameters such
as heat treatment temperature, reducing agent concentration, type of surfactant, reinforcement material property (particle
size) to improve mechanical behavior namely hardness, wear, friction coefficient, high-temperature oxidation behavior and
environmental protectivity (corrosion/erosion) have extensively studied and well-described.

Keywords Ni–P composite coatings · Ni–B composite coatings · Corrosion · Wear · Hardness

1 Introduction are vacuum deposition processes and these are used to form
a hard or soft film on the outer surface of machine elements.
The Surface coating is one of the most common engineer- The CVD or PVD technique is used to modify the near-
ing process to cover the surface of the substrate partially or surface structure of the component to improve the properties
completely for decorative and/or function purpose to meet [1].
desired mechanical characteristics. The functional coatings In the molten or semi-molten technique, the material is
are part of mechanical engineering process chain to achieve heated to reach the molten / semi-molten state in order to
better surface properties like hardness, adhesion, wettability, feed over a substrate. This technique is mostly preferred for
wear and corrosion resistance. The classification of func- coating the structural components to attain good thermal,
tional coatings is presented in Fig. 1. corrosion or erosion and wear resistance, however low adhe-
Gaseous functional-coating methods are the most pre- sion property is observed as the major limitation of this pro-
ferred to fabricate the items which are required a thin film for cess. Thermal spraying is a molten state coating technique
mechanical and optical functions. Chemical vapor deposi- where the heated material is sprayed over a surface.
tion (CVD) and physical vapor deposition (PVD) techniques The electroplating and electroless techniques are two
major coating-techniques in the solution state-coating
process. Any higher thickness of coating can be achieved
* Vinod Babu Chintada through this method as it is one of the manor advantages
vinodbabu.chintada@gmail.com over the other process. In the Electrochemical deposition
1
Department of Mechanical Engineering, GMR Institute
technique coherent metal coating is formed on the electrode
of Technology, Rajam, A.P. 532127, India by the reduction of metal cations through using electric cur-
2
Department of Mechanical Engineering, Andhra University,
rent. Electroplating process is one of the economic com-
Visakhapatnam, A.P., India pared to most of the other existing coating techniques. The
3
Multifunctional Materials and Additive Manufacturing
electroless coating is autocatalytic surface-coating method,
Laboratory, Department of Mechanical Engineering, National
Institute of Technology Puducherry, Puducherry, India

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134 Page 2 of 14 Journal of Bio- and Tribo-Corrosion (2021) 7:134

Fig. 1  Classification of
functional-coating methods

through which nickel can be coated on the metal surface in Often the duplex coatings at the same thickness offered
the presence of the chemical reducing agent [2]. better hardness and wear resistance compared with the indi-
The uniform thickness of the coating is formed over intri- vidual ones. These are multilayer coatings formed using the
cate shapes which is the prominent advantage offered by dual electroless bath. These offer better corrosion resistance
the electroless coating at low cost. In order to achieve better at high phosphorus concentration and good hardness at low
hardness, wear and corrosion resistance, electroless Ni–P and medium phosphorus concentrations. The duplex electro-
coatings are best suited for steel, aluminum, copper, and less coating with different proportions with different stack-
plastics. However the desired characteristics are dependent ing offers better mechanical and tribological properties for
on the percentage of the phosphorus concentration in the the coating [8, 13, 14, 50].
coating. Typically low phosphorus (1–4%) for high hardness, This article discusses more details about single pass,
and high phosphorus coatings (> 10.5%) for improvement multi-pass and composite electroless coatings and the influ-
corrosion resistance whereas medium phosphorus (4–10%) ence of process parameters for mechanical characterization.
for combined properties [3–6]. Chapter 2 discusses the base principle of electroless coat-
Ni–B coatings are another important kind of electroless ing and their applications. Chapter 3 explores a detailed
coatings, where borohydride is considered as reducing agent sequence of operations in the electroless coating process.
[7, 8]. As compared with the Ni–P coatings, Ni–B coat- Chapters 4 and 5 describe the influence of Ni–P, Ni–B and
ings show high hardness, wear resistance and low corrosion their composite coating on surface properties and scientific
resistance [9]. The structural and mechanical properties of discussion on research contribution in this domain for the
the coatings are greatly influenced by the boron concentra- last three decades. Chapter 6 and 7 are focused on special
tion. At low boron concentration, the coatings exhibit crys- techniques such as multi-pass electroless coatings and poly
talline structure; whereas at higher concentration amorphous alloy coatings. Finally, the conclusions are made from the
structure is observed [10]. The hardness of the coating can observation and experimental results which were discussed
be improved by increasing the boron concentration. in the existing literature.
Mechanical and tribological properties of the coating can
be further enhanced by reinforcing the second phase parti-
cles at micron, submicron and nano sizes to the Ni–P lattice 2 Electroless Coatings and their
of the electroless coating. Researchers tried with different Applications
composite coatings by reinforcing the hard ceramic second
phase particles into the Ni–P matrix ( ­Al2O3, ­TiO2, ­ZrO2, The electroless-coating technique was discovered by Bren-
SiC, WC, ­SiO2, ­Si3N4 or diamond) to improve the coating ner and Riddell in the year 1946. The principle of the pro-
hardness. The soft particles (PTFE, MoS2, HBN, graphite) cess is formation of Ni-coating on a catalytic surface by con-
are added into the coating to obtain better lubricity property trolling the metallic ions through chemical reduction process
[11, 12]. [7, 9].This process is well used several industrial due to its

13
Journal of Bio- and Tribo-Corrosion (2021) 7:134 Page 3 of 14 134

bearings, hose couplings, gear assemblies, carburetor parts,

fuel injectors, shock absorbers and exhaust system compo-
nents where Ni-based Electroless-coating proven improve-
ment. Magnetic properties, solderability, wear resistance and
good appearance make these coatings very suitable to the
electronic industry.
The high-speed transfer fiber creates wear on the machin-
eries of textile industry. Hard chrome plating gives the lim-
ited wear resistance so the electroless plating is the better
alternation because of its smooth, abrasion resistance to
components like thread guides, fiber feeds, bobbins, shut-
tles, rapiers, ratchets, and needles which are in contact with
textile fibers. It is also used in foundry tooling and printing
Fig. 2  Industrial applications of surface coatings industry to improve productivity, performance and cost sav-
ing. Various industrial components are coated with electro-
less coatings are shown in Fig. 4.
unique properties, low cost and the uniform thickness of the The electroless Ni–P coatings offer good corrosion resist-
coating. Figure 2 indicates occupancy in different industries. ance in comparison with pure nickel or chromium alloy due
Computer and automotive industries have more occu- to amorphous nature and passivity of the coating. Several
pancy with 20% to attain hardness, wear resistance. The factors highly influence the corrosion resistance such as
electronics occupy with18% and the chemical and oil indus- phosphorus content, porosity, and annealing temperatures
tries occupy with 15% to obtain better magnetic properties [6].
and anticorrosion resistance. Figure 3 represents the occu-
pancy due to functional purpose of the electroless coatings.
Corrosion is one of the most occurring problems in 3 Electroless‑Coating Process
industrial equipment which affects the service life of the
equipment and impacts service & maintenance cost. Elec- The electroless-coating process consists three major stages
troless coatings have a promising commitment for corro- they are preparation of chemical bath, substrate preparation
sion or erosion problem, which are mostly observed in the & submerging and coating process to form the coating over
mechanical equipment in the industries (bearings, conveyor the surface. The electroless-coating process is schematically
systems, rollers, hydraulics, gears). The electroless coating represented in the following Fig. 5.
is preferred to increase the service life of various mechani-
cal components of Oil and Gas industries such as blowout
preventers, brake assemblies, chokes, compressors, pump
housings, logging tools and plungers. The aircraft engine
and outer skin are exposed to the corrosive environmental
conditions where the electroless coatings can prevent the
damage of the components [15].
The corrosion is one of the most occurring problems
in the automotive industry at heat sinks, pistons, engine

Fig. 3  Functional utilization chart of surface coatings Fig. 4  Industries components coated with electroless coatings

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Fig. 5  Steps followed in the

electroless coating

3.1 Preparation of Chemical Bath Ni+2 + 2e− → Ni

The preparation of a chemical solution which maintains con-
2H+ + 2e− → H2
stant pH value for a long time where the substrate is to be
placed for the coating purpose. In electroless nickel coat-
ings, nickel chloride (NiCl) and nickel sulfate ­(NiSO4) are H2 Po2 + 2H+ + e− → P + 2H2 O
used as the sources of metal ions. Different types of reducing
agents are used based on the type of coating required; they are
Sodium hypophosphite (­ NaPO2H2) and sodium borohydride
­(NaBH4) to form Ni–P and Ni–B coatings. The surfactant acts 4 Ni–P/composite Coatings and their
as wetting agent in the chemical bath and the organic acids Characterization
or their salts are used as complexing agents to prevent the
decomposition of chemical bath and to control the reactions. Researchers have tried with different hard particles with
A small amount of accelerator is added to the chemical bath Ni–P matrix to improve various mechanical properties of
to improve the deposition rate which separates the hydrogen different substrates. ­Al2O3, SiC, and CNT are mostly used
from hypophosphite and caused to absorb the phosphorus on as reinforcement materials in Ni–P composite coatings on
a catalytic surface. The stabilizer and the buffer are added to different substrate materials to improve hardness and wear
stabilize the solution and to maintain constant pH for long strength followed by corrosive resistance. Table 1 lists the
time. The electroless composite coating was formed by add- research literature on Ni–P composite coating for various
ing the second phase hard ceramic particles and soft particles substrates. In Table 1, ­sub1 to ­sub14 represents for substrate
for chemical bath after completion of 30–60 min of coating materials in the following order: Mild steel, AISI 1020 Steel
process. plate, AISI 1045 Steel, Steel, Carbon steel, Low carbon
steel, Medium carbon steel, Copper, 6061 Aluminum alloy,
3.2 Substrate Preparation and Submerging 5083 Aluminum alloy, 7075 Aluminum alloy, Cast iron,st37
Steel, ­100Cr6 Hard steel.
Pretreatment is required to clean the substrate in order to
remove the oil and dirt particles for better deposition of the 4.1 Ni–P–Al2O3 Coating
coating. There are several standard pretreatment methods are
existed to clean the substrate. These metallic substrates are Co-deposition of ­Al2O3 particles into Ni–P matrix result
dipped into the prepared chemical bath after pretreatment in enhancement of the tribological and mechanical proper-
process. ties of the coating [16–19]. It is also observed that further
heat treatment of coated substrate and particle concentra-
3.3 Coating Process tion highly influences the hardness. The higher dispersion
strengthening effect of A ­ l2O3 improves hardness of Ni–P
The chemical bath maintained at the elevated temperature composite coating up to 10% on mild steel substrate [11].
of 85–95 °C for a standard time period of 2–4 h to get the The heat treatment at 400 °C of Ni–P–Al2O3is also had
required thickness of the coat over the dipped substrate mate- proven the increment in hardness of the coating up to 15%.
rial at the final stage of the coating process. However, the time Properties and structure of the Ni–P and Ni–P composite
period basically is maintained to get required thickness of coat coatings are significantly affected by the heat treatment tem-
with uniform deposition rate. The chemical reactions are dur- perature and time. Structural changes in Ni–P coatings are
ing the coating process as follows. observed in the heat treatment temperature range between
Anodic Reaction: Oxidation of ­H2PO2 200 and 700 °C [20, 21, 22 and 23]. Properties (microhard-
ness, wear and corrosion resistance) of the electroless nickel
H2 PO2 + H2 O → H2 PO3 2H+ + 2e− coating will not much affected by the lower heat treatment
temperatures of the order of 200 °C due to the incomplete
Cathodic Reaction formation phosphide. Phase transmission of the coating

13
Journal of Bio- and Tribo-Corrosion (2021) 7:134 Page 5 of 14 134

Table 1  Research literature on Ni–P composite coating for various substrates

Substrate Reinforced particles in Ni–P matrix
Al2O3 SiC SiO2 ZnO TiO2 CNT TiN, Si3N4 PTFE

Sub1 [9, 10] a,b [15] a, c [28, 34]a,b,c [49, 50]a,b

Sub2
Sub3 [11] a, b [16] a [34]a,b
Sub4 [12]a,b [44]a,b
Sub5 [40, 43]a,b,c
Sub6 [13] a,b [39]a,c [69]c
Sub7 [48] c [41]c
Sub8 [14] a,c [17] a [35]a,c [14]a,c [45]a,b,c
Sub9 [18]a,b,c
Sub10
Sub11 [55]b
Sub12 [19]a,b
Sub13 [37]c
Sub14

a, b and c represent the hardness, wear and corrosion resistance of the coatings

from amorphous to crystalline at 350–400 °C heat treatment 4.2 Ni–P‑SiC Coatings

temperature range significantly improves the microhardness,
corrosion resistance, adhesion, structure and morphology SiC is one of the most used ceramic reinforcement which
of the coatings. Formation of coarse ­Ni3P phase at above offers high strength with good corrosion and erosion resist-
400 °C annealing temperature retards the microhardness of ance than many other materials. Ni–P–SiC composite coat-
the coating [24]. Therefore, lower microhardness value is ing is formed by co-deposition of different sizes of SiC par-
observed in the coating at 500 °C annealing temperature. ticles at different concentrations levels in electroless bath to
Recommended heat treatment temperature for Ni–P and improve the properties of the coating [25–28]. The hardness
Ni–B coating is 350 °C to 450 °C, respectively, to attain of the coating on mild steel is improved by adding SiC par-
maximum microhardness. There was 12% of improvement ticles into the Ni–P matrix; there is further improvement in
observed in hardness by the co-deposition of ­Al2O3 parti- hardness of 112% with heat treatment process at the temper-
cles into Ni–P coating on Mild steel [16]. However, a rapid ature 400 °C due to phase transition. The phase change from
increment of 220% in the hardness achieved through further semi-coherent ­Ni3P to non-coherent ­Ni3P beyond 400 °C
heat treatment process of the coated 1020 steel substrate due to that decreases microhardness of the coatings [28].
due to phase change [17]. There is no much variation in On 1045 steel substrate composite coating is formed by the
corrosion resistance with the addition of small amounts of co-deposition of SiC micro particles gives better hardness,
alumina nanoparticles into the composite coating compared Compared to composite coating formed by the reinforcement
with Ni–P coatings. The porosity of the coating considerably of nano-SiC particles. Hardness improvement from nano to
increases with increasing of A ­ l2O3 particle concentration micro size particles is 137% and after heat treatment pro-
due to this corrosion resistance of the coating decreases. The cess the further improvement of hardness is observed 99%.
binding force between Nickel and Phosphorous is reduced by Superfine SiC particles did not influence the hardness of the
increasing ­Al2O3 concentration and it increases the porosity coating same thing is observed when the particle size was
of coating and thus corrosion ability is reduced. Particle con- reduced from 50 to 1000 nm. The hardness of Ni–P–SiC
centration in the coating also depends on complexing agent coating on the copper substrate is decreased beyond 400 °C
which present in the chemical bath. The wear resistance of heat treatment temperature due to grain growth and presence
the Ni–P coating is increased by the embodiment of A ­ l2O 3 of free carbon [26]. Reinforcement of SiC particles into the
particles due to the formation of the metal oxide layer which coating matrix significantly enhances the corrosion resist-
reduces the direct contact of the coating with the opposite ance of the Ni–P coating. Ni–P–SiC coating formed at 2 g/L
surface [18, 19]. SiC concentration provide better corrosion protection to the
mild steel substrate [29]. Ni–P–SiC coating formed at 1 g/L
SiC nanoparticles concentration offers higher corrosion
protection to the copper materials [30]. Ni–P–SiC coating

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134 Page 6 of 14 Journal of Bio- and Tribo-Corrosion (2021) 7:134

developed at 1 g/L SiC particle concentration on AZ 31 that copper substrate hardness was increased from 4.42GPa
magnesium alloy offers excellent corrosion resistance. Cor- to 10.98GPa. EIS Studies reveal that medium phosphorus
rosion resistance of the Ni–PSiC coating is further enhances Ni–P–SiO2 coating offers better corrosion resistance in 4
by conducting heat treatment process at 300 °C tempera- wt% of NaCl solution for 2 to 4 weeks, this was confirmed
ture [31]. Ni–P–SiC coating formed at 4 g/L concentration by low double layer capacitance (Cdl) and very high charge
of SiC particles provides good corrosion protection to the transfer resistance (­Rct) of the coating [34]. Ni–P–SiO2
AZ91D magnesium alloy. At this level, uniform distribution coating shows better wear and hardness properties when
of SiC particles in the coating matrix results better corro- heat treatment is done at 400 °C compared with 200 °C
sion protection [32]. SiC nanoparticles corrosion resistance and 600 °C. Microhardness of the coating is improved by
is higher than the Z­ rO2 and T­ iO2 nanoparticles. Therefore, 340% at 400 °C annealing temperature on 1045 mild steel
corrosion resistance of the Ni–PSiC coating is higher than substrate. Brittle nature of Ni–P matrix due to coarse grain
the Ni–P–TiO2–ZrO2 coatings as deposited and heat treated size at 600 °C temperature decreases the hardness of the
condition [33]. On AISI 1045 steel substrate composite coat- coating. Wear resistance is the function of hardness so bet-
ing is formed by the co-deposition of SiC nanoparticles into ter resistance to wear is obtained at 400 °C heat treatment
Ni–P matrix gives better cavitation erosion resistance than temperature [35].
the SiC microparticles co-deposition in both distilled water
and 3.5% NaCl solution even after heat treatment also [27]. 4.4 Ni–P–ZnO Coatings
The Ni–P–SiC coating on mild steel offers a good corrosion
resistance at 400 °C annealing temperature, further incre- Researchers tried with ZnO particles as reinforcing material
ment in temperature results the formation of nickel silicate, in Ni–P composite coatings due to its enormous biocompat-
which makes the coatings non-homogeneous and the cor- ibility, semi-conductivity and piezoelectric properties. The
rosion resistance is decreased due to the formation of more concentration of ZnO particles in the electroless bath has a
number of micro shells in the coatings. Higher concentration great impact on properties of the electroless surface coat-
of nano-SiC (greater than 2 g/L in a chemical bath) reduces ing [36]. Optimal concentration (0.5 g/L) of ZnO particles
the charge transfer resistance, improves the corrosion current in electroless bath results in 60% improvement in micro-
densities and double layer capacitance, which further leads hardness of Ni–P-ZnO coating on mild steel compared with
to diminished corrosion resistance [25]. uncoated substrate [37]. Electrochemically active area of the
For aluminum materials, Soleimani tried Ni–P–SiC coat- coated surface is decreased by increasing the ZnO particle
ing and found the wear resistance is improved upto 69% and concentration in the Ni–P matrix, results in improved cor-
also observed significant improvement in the friction coef- rosion resistance of the Ni–P–ZnO coating. Higher concen-
ficient upto 30% [28]. The higher electromechanical resist- tration of ZnO particles decomposes the electroless bath,
ance of SiC is the significant reason for increasing the corro- so that Ni–P–ZnO coating is formed on St37 steel substrate
sion resistance of the composite coating compared with pure at the optimum concentration of the particles (2 g/L) offer
Ni–P coatings. Y.C.Wu studied wear resistance of Ni–P–SiC better corrosion resistance [38]. AFM studies confirmed
composite coating on cast iron, and found it is higher than Ni–P coatings surface roughness is increased by adding ZnO
Ni–P coating. Heat treatment at 400 °C increases hardness particles. The Ni–P–ZnO coating shows globule structure,
and thus results in minimized wear rate of the coating [12]. agglomeration of ZnO particles into small size globules
and these form a large size of island of composite coating
4.3 Ni–P–SiO2 Coatings and leads to improved surface roughness from 8.20 nm to
39.45 nm [2].
The low value of Hamaker constant (1.6 in water) and the
tendency to form hydration layers of S ­ iO2, the agglomera- 4.5 Ni–P–TiN Coatings
tion of ­SiO2 nanoparticles decreases gradually and results
in uniform dispersion of particles thus S
­ iO2 nanocomposite TiN offered better hardness and corrosion resistance as
is chosen as one of the preferred reinforcement materials compared with many other reinforced (­ Al2O3, SiC, S ­ iO2,
in the Ni–P composite coatings. Increment in phosphorus and ZnO) ceramic particles in the electroless coating. Mafi
concentration enhances the surface roughness and grain tried at two different heat treatment temperatures 200 °C and
sizes of the coatings; the surface roughness of the high 400 °C and observed at 200 °C the corrosion resistance is
phosphorus coating is reduced by the addition of nano S ­ iO2 improved without any influencing the microhardness due to
particles. Addition of optimum quantity of nano S ­ iO2 par- no-change in the amorphous structure of the coating. How-
ticles (2 g/L) to medium phosphorus Ni–P coating refines ever, at 400 °C the structural change in the coating caused
the nodular structure and avoids the porosity of the coating for 90% improvement in microhardness with diffused corro-
on the substrate. Mohammad Islam experimentally found sive resistance [39]. Reinforcement of TiN nanoparticles in

13
Journal of Bio- and Tribo-Corrosion (2021) 7:134 Page 7 of 14 134

Ni–P matrix improves the microhardness of Ni–P coating on diminished hardness value due to agglomeration of ­Ni3P and
AZ91D magnesium alloy by 12% in as deposited conditions Ni crystallites as they incoherent the matrix. The author also
and 30% in heat treat conditions. Self-recovering property experimented with low phosphorus Ni–P–Si3N4 coating on
of the composite coating results in better corrosion for long- mild steel and observed good corrosion resistance [49, 50].
term corrosion immersion test [40].
4.8 Other Ni–P Composite Coatings
4.6 Ni–P‑CNT Coatings
Gawad has experimented with three different coatings
In the recent days, the research is more focused on carbon (Ni–P, Ni–P–TiO2 and Ni–PAl2O3) on a copper substrate
nanotubes (CNT) in various industrial applications because and observed (Ni–P–Al2O3 > Ni–P–TiO2 > Ni–P) for hard-
of its unique structure and novel properties such as effective ness and corrosive resistance, 44% enhanced hardness is
load transfer resistance and electrochemical properties [41]. obtained for ­Al2O3 compared to ­TiO2 reinforcement [19].
The concentration of CNT needs to be optimal to improve Subakova tried T ­ iO2 with two different modes (particle and
the hardness of Ni–P coating. The concentration exceeds solution) on rectangular nickel foil to examine corrosive and
1.1 g/L results reduction in the hardness of the coating. mechanical behavior. He observed that 5% improvement in
CNT reinforced Ni–P composite coatings have been tried microhardness for ­TiO2 particles whereas ­TiO2 solution had
on various steel to improve the micro harness value. Wear offered significant improvement of 12% in micro-hardness.
resistance is observed to be minimum up to the 1.1 g/L CNT He also proved that T ­ iO2 solution is better in improving
concentration in the electroless bath this was confirmed by the corrosive resistance [51]. Presence of Ti enhances the
wear scar depth value 6.6 µm of the coating. This one is corrosion resistance of the Ni–P–TiO2 coating compared
because of the concentration of CNT in nickel matrix blocks with Ni–P coating. But it is found less when compared to
the dislocation movement of nickel matrix results in decreas- Ni–P–Si3N4, Ni–PCeO2 due to lower Cdl value [52]. Hard-
ing the plastic deformation [42–44]. SWNT are high stiff and ness and Young's modulus of Ni–P coating greatly influ-
toughened CNTs used as reinforcement in combination with ence by reinforcement of diamond particles [53]. Hamdy
Ni–P coatings. Ni–P-SWNT annealed at 400 °C has signifi- tried two different (Ni–P–W, Ni–P–Al2O3) coatings on low
cantly improves the hardness to 40% than deposited condi- carbon steels and confirmed better corrosion resistance
tion, and 75% improvement in hardness observed with Ni–P- observed in former coating [54]. Electroless nickel coatings
CNT. Yang also tried Ni–P-SWNT on low carbon steels to offer good corrosion and wear resistance and high friction
improve the corrosion resistance due to their better chemical coefficient which is undesirable where lubricating properties
properties [45, 46]. Fuming tried with different agitation are required. PTFE second phase particles added with Ni–P
techniques such as (mechanical stirring, magnetic stirring, mitigate this limitation [55, 56]. Ni–P–rGO coating on low
and ultrasonic vibrations) to improve the micro-hardness of carbon steel improves micro-hardness of the substrate and
the coating. In that uniform distribution of the CNT in the a hardness value of 761HV was observed for Ni–P–rGO
Ni–P matrix with the ultrasonic vibration agitation technique coating formed in the electroless bath containing 50 mg/L
results increase in the microhardness of Ni–P-CNT coat- graphene oxide (rGO). Nobel shifting of corrosion poten-
ing on steel substrate [47]. Kuo Lee investigated with two tial from − 426 to − 311 mV confirms higher corrosion
different coatings (Ni–P-TiO2 and Ni–P-CNT) on AA5083 resistance of the Ni–P–rGO coating formed at the optimal
aluminum alloy substrates and identified high phosphorus concentration [57].
Ni–P-CNT tends to better corrosion resistance [48]. Metallization of plastic parts, electroless plating method
is extensively used due to its economic and easy operation.
4.7 Ni–P–Si3N4 Coatings Azhar Equbal tried different ways for metallization of ABS
plastic using the electroless coating to improve the electri-
Silicon nitride particles are chosen as reinforcement mate- cal conductivity of the plastic material. Form his observa-
rial in electroless composite coatings due to their higher tions electroless copper coating formed on Al seeded ABS
hot hardness, good resistance to high-temperature oxidation, substrate formed in the hydrofluoric acid bath, which offers
excellent wear, and corrosion resistance. 1 g/L particles of better electrical conductivity compared to chromic acid and
­Si3N4 are added to the electroless bath to prepare Ni–P-Si3N4 sulfuric acid ­(H2SO4) / hydrogen peroxide ­(H2O2) mixture
composite coating and tested on a mild steel substrate. Addi- etched ABS substrates. Higher deposition of copper in the
tion of second phase silicon nitride particles improves the Al region and better conductivity of Al and Cu improves
microhardness of the coating by 10% without any heat treat- the electrical conductivity of the substrate material [58].
ment and 22% while heat treated at 400 °C due to phase Electroless coating and arc discharge methods are used to
transition. Balaraju et.al., also tried at above 400 °C anneal- deposit nickel on beech wood substrate. Higher deposition
ing temperatures to study the coating behavior and observed of nickel and uniform grain structure of the coating on the

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substrate resulted in higher measured RF electric at given Table 2  Research literature on Ni–B coating for various substrates
RF electric field [59]. Substrate Type of coating
Wear resistance of the Ni–P coating on martensite stain
Ni–B Ni–B–TiO2 Ni–B–Ni–P
steel improved by heat treatment process carried at 320 °C
for 9 h and 400 °C for 1 h. Formation of hard crystalline Mild steel [70, 73−75]a,b [73]a [8]a,b,c
­Ni3P during the annealing process acts as the third body at Copper [76, 77] a
the contact surface results lower wear rate compared to hard Mg alloy [81]a,c
chromium steel. Nickel oxide layer formed during the heat
a, b and c represent the microhardness, wear and corrosion resistance
treatment process acts a natural lubricant which results in
of the coatings
17% improvement in friction coefficient compared to hard
chromium plating [60]. As deposited and heat treated condi-
tions corrosion resistance of the Ni–P–Ti coating increases 5 Ni–B Coatings
with increasing the Ti concentration up to 11.8 wt% [61].
Ni–P–Ti coatings presence of Ti acts as barrier for corro- Ni–B is the most used coating next to Ni–P coating due to its
sion, which results better corrosion protection to the AISI capability of enhancing mechanical and chemical properties.
1018 steel [62]. Addition of NiTi particles into the Ni–P- Researchers also tried Ni–B composite coatings and multi-
coatings prevents the crack propagation, which reduces the layered Ni–B–Ni–P coatings on mild steel and magnesium
surface interaction with corrosion environment and improves alloys.
the corrosion resistance [63]. Hanachi. M et.al, found that Table 2 indicates Ni–B and its composite coatings on
increase in phosphorus concentration and heat treatment mild steel, copper and mg alloy to improve hardness, wear
temperature improves the corrosion resistance of the Ni–(X) and corrosion resistance. Reducing agent concentration
P–GO coatings [64]. and bath temperatures are influencing the deposition rate
of the coating. Deposition rate of the Ni–B coating formed
4.9 Influence of Surfactant on Ni–P Composite from the low temperature (45 ± 1 °C) bath is low compared
Coatings to that obtained from high-temperature bath (95 ± 1 °C).
Crystalline structure observed in the coatings formed from
Type of surfactant used in the coating process affects the lower sodium borohydride ­(NaBH4) bath, where as obtained
deposition rate of the secondary particles. Addition of sur- using a higher concentration of ­NaBH4 possess a mixture
factant into the electroless bath increases the surface charge of amorphous and crystalline phases [70, 71]. Heat treat-
transfer resistance and wettability, which enhances the sta- ment process carried at 300 0C temperature improves the
bility of deposited particles [65]. Increase in net positive micro-hardness of the Ni–B coating. Phase transition of
charge of the particles leads to enhance the electrostatic nickel crystals into nickel boride, i.e., ­Ni2B, ­Ni3B, and ­Ni4B3
adsorption of secondary particles on the cathode surface. at 300 0C annealing temperature improves the hardness of
Therefore, the selection of surfactant plays a crucial role to Ni–B coating from11.5 ± 0.26 GPa to 13.8 ± 0.29 GPa [72].
prevent the agglomeration of nanoparticles [66]. Deposi- Formations of nickel crystals and nickel boride phases had
tion efficiency and dispersion stability of the nanoparticles been confirmed by XRD analysis at different temperatures.
are strongly influenced by the nature of surfactant added Ni–P–TiO2 coating formed at 2 g/l T ­ iO2 nano particles con-
into the electroless bath. Mostly three types of surfactants centration shows higher micro-hardness value, further addi-
(cationic, anionic and polymeric) are used in electroless tion of particles results decrease in mechanical properties
coatings to improve the wettability of the co-deposited par- due agglomeration of nanoparticles and improper coating
ticles for better deposition [67]. Among the three types of integrity [73]. J.N.Balaraju confirms that heat treated Ni–B
surfactants, anionic surfactant offers less deposition rate coating at ­4000C for 1 h offers higher hardness and wear
compared to non-ionic surfactant. Most of the researchers’ resistance due to precipitation of Ni and ­Ni2B phase [74].
opinioned optimum concentration of surfactants is highly Shu tested the combination of T ­ iO2 nanoparticles with Ni–B
recommended to deposit maximum amount of second phase coating to improve the corrosion resistance and hardness
particles into nickel matrix to attain desired mechanical and of the Ni–B coating on a mild steel substrate. Adding the
chemical properties of the composite coating [68]. Mafi second phase hard ceramic particles to Ni–B matrix further
experimented Ni–P-PTFE coatings on low carbon steel in improves the wear resistance and hardness of the coatings.
the presence of three different surfactants namely SDS, PVP, Co-deposition of nano diamond particles into Ni–B matrix
and CTAB and observed that coating formed in presence of improves the micro-hardness and decreases the deposition
CTAB and PVP surfactant offers better corrosion resistance rate of Ni–B coating on steel substrate. Luiza investigated
due to uniform distribution of PTFE particles in the coating the behavior of Ni–B coating on mild steel substrate formed
[69]. in presence of four lead-based stabilizers namely tungstate,

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Journal of Bio- and Tribo-Corrosion (2021) 7:134 Page 9 of 14 134

sulfate, nitrate, and chloride. Higher deposition rate (26 μm lattice refines the grain structure results 4% improvement in
/ hour) observed in the coating formed in tungstate bath and micro-hardness. The positive shift of corrosion potential due
coating with lower surface roughness value formed in nitrate to the decrease in the potential gap between bare alloy and
bath [75]. Improvement in specific wear rate of Ni–B and coating results better corrosion resistance of the duplex coating
heat treated Ni–B coatings are similar when the applied load compared to Ni–P coating [82]. The deposition rate of Ni–P
increases from 20 to 40 N. Formation of nickel bromide coating on pipeline steel increased with increasing the deposi-
phase during heat treatment process reduces the specific tion time. The maximum deposition rate of 15 μm/ hr observed
wear rate of the coating for all applied loads compared to up to 4 h deposition time beyond this decrease in trend
deposited conditions [76]. SiC particles offer resistance to observed due decomposition of a chemical bath. In addition
plastic deformation and thus improve the micro-hardness of to corrosion and erosion resistance, Ni–P coating improves
the Ni–B–SiC coating on a steel substrate by 180%. Rein- the microhardness of the substrate from 1.7GPa to 5.4GPa
forcement of SiC particles to the Ni–B matrix decreases the [83]. Ni–P/Ni–B duplex coatings with Ni–B as outer layer
metallic prone area, which results 21% improvement in cor- provides higher hardness and wear resistance than the Ni–P
rosion resistance of the Ni–P–SiC coating compared to Ni–B outer layered duplex, conventional Ni–P, Ni–B, bilayer Ni–P
coating [77]. Reinforcement of tungsten into the Ni–B coat- and Ni–B coatings. Higher hardness of the Ni–B layer results
ing improves the microhardness. At the same time, decreases better hardness and wear resistance to the Ni–B outer layered
its resistance to corrosion [78]. Microhardness of the plasma duplex coatings [84]. Microhardness of the duplex coating
nitride higher boron Ni–B coating is higher than the heat follows the following order; Ni-high P/Ni–B > Ni–B > Ni-
treated Ni–B coatings due to the formation of denser boron Medium P/Ni–B > Ni-Low P/Ni–B coatings [85]. Duplex
structure. Wear rate in plasma nitride Ni–B coatings are 14 Ni–P/Ni–Mo–P coating with ternary Ni–Mo–P as outer layer
times higher than the annealed coatings [79]. proves high hardness, large elastic modulus, low porosity and
excellent corrosion resistance than the Ni–P and Ni–P outer
layer duplex coatings [86]. Ni–Mo–P outer layered duplex
6 Ni–P–Ni–B Duplex Coatings Ni–P/Ni–Mo–P coating offer better corrosion protection to
the steel material than the Ni–P coatings. Microhardness and
Ni–B coatings offer better hardness and wear resistance with corrosion resistance of the multi-layer coating are extensively
poor corrosion resistance than Ni–P coating. To get opti- improved by laser annealing at 14 mm/s scanning velocity
mal properties, researchers experimented with Ni–P–Ni–B [87]. Compared to single layered Ni–P and Ni–B coatings,
duplex coatings using a dual bath. Ni–B–Ni–P coatings pro- multi-pass Ni–P/Ni–B coatings offers good hardness, wear and
vide better hardness compared with Ni–B and Ni–P coatings corrosion resistance. Mechanical and tribological properties of
[80]. The duplex coating with Ni–B as an outer layer on mild the duplex coatings further enhanced by the addition of sec-
steel substrate increases the micro-hardness value by 9%. ondary ceramic particles SiC, A ­ l2O3, ­TiO2, CNT, S­ i3N4, TiC
Heat treatment of Ni–P–Ni–B coating at 450 °C confirms particles to the outer layer [88]. Corrosion resistance of the
that 60% improvement in the hardness due to the formation high boron- medium phosphorus multi-pass coating in pres-
of both nickel phosphide and nickel boride phases. Specific ence of sulphuric acid electrolyte is higher than the Ni–P mono
wear rate of Ni–P–Ni–B coating is high due to the hard Ni–B layer coating. After heat treatment process also same corro-
outer layer [13]. Zhang applied Ni–P–Ni–B duplex coat- sion behavior is observed in the duplex coatings [89]. Micro-
ing on magnesium alloy by dual bath and witnessed 29% hardness of the Ni–P inner layered Ni–Co–Al2O3(60 g/L)
improvement in hardness when compared to Ni–P coat- coating is 20% higher than the Ni–Co–Al2O3(60 g/L) mono
ing. Further heat treatment process carried out at 350 °C layered coating. Compared to Ni–Co–Al2O3(60 g/L) coat-
confirms 68% improvement in hardness of the coating. The ing, duplex Ni–Co–Al2O3(60 g/L) coating with Ni–P as inner
duplex coating offers good wear resistance and microhard- layer offers better resistance to corrosion [90]. Microhardness
ness when the Ni–B as an outer layer, whereas the corrosion of the duplex Ni–P/Ni–P–W coatings is higher than the ter-
resistance is higher when the Ni–P is outer layer [14]. nary Ni–P–W and Ni–P coatings. Less porosity in the Ni–P/
Microhardness of multi-pass Ni–B-Ni–P coating on AZ91D Ni–P–W coating results better carrion resistance. Corrosion
magnesium alloy is 30% lower than Ni–B coating and 25% resistance of the coated samples was follows the following
higher than Ni–P coating alone. Ni–B coating on Mg alloy order Ni–P < Ni–P–W < Ni–P/Ni–P–W [91]. Ni–P/Ni–B
shows lower corrosion resistance due to its crystalline nature duplex coatings corrosion resistance was improved by the
but Ni–B as an inner layer and high Phosphorus Ni–P as an reinforcement of B ­ 4C into the Ni–B matrix. Uniformly dis-
outer layer results better corrosion resistance of the multi-pass tributed ­B4C particles reduces the metal interaction with cor-
coating compared to individual Ni–P and Ni–B coatings [81]. rosion environment, which results better corrosion resistance
Magnesium alloy microhardness improved to 400% using to the Ni–B–B4C outer layer duplex coating [92]. Compared to
Ni–Zn–CuP/Ni–P duplex coating. Presence of Zn in Ni–P Ni–P coatings, Ni–W–P/Ni–P-nano Z ­ rO2 multi-pass coatings

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offers higher hardness and corrosion resistance. Formation of high compared with Ni–W–P coating due to the formation
hard crystalline phase after heat treatment process significantly of meta-stable NiP and ­Ni5P2 phases at all annealing tem-
improves the properties of the duplex coating [93]. peratures [97, 98]. Ni–W–P coating on mild steel annealed
below 300 °C improves the microhardness due to increase
in the degree of crystallization, in this hard ­Ni3P protect the
7 Poly Alloy Electroless Coatings matrix from plastic deformation and thus results in improved
microhardness. Ni–W–P coatings also offered better corro-
Poly alloy coatings usually prepared by adding multiple rein- sion resistance when the coating annealed at 700 °C [99].
forcement materials to the matrix (Ni–P, Ni–B, and Cu–P) Higher co-deposition of SiC nanoparticles into the Ni–Co–P
to attain better mechanical and chemical properties. Table 3 matrix refines the grain size of the Ni–Co–P composite coat-
lists the cited research literature on various Ni- and Cu-based ing on ASCM20 + 5Fe alloy offers better hardness and wear
poly alloy coatings on steels. resistance without affecting the corrosive resistance. The
Properties of electroless coatings mainly depend on con- author also tested with A ­ l2O3 reinforcement and attained
centration of phosphorus or boron and further addition of higher corrosive resistance [100]. Liu analyzed three differ-
metal elements like Fe, Co, Cu, Zn, Mo, Sn, W, etc. Poly ent configurations of Ni–P–TiO2, Ni–P–Cg, Ni–P–Cg–TiO2
alloy Ni–Zn–P–TiO2 coatings show better microhardness coatings on carbon steel. Ni–P–Cg–TiO2 offered better cor-
than Ni–Zn–P ternary coatings. Further heat treatment car- rosion resistance and low coefficient of friction than other
ried out at 400 °C improves the hardness of both the coat- two due to the interaction between Cg–TiO2 and its capa-
ings while tested on low carbon steels, due to the formation bility to reduce the pores in electroless Ni–P matrix [101].
of meta-stable ­Ni12P5 and ­Ni3P phase. The ­TiO2 reinforce- Few researchers have also tried on Cu-based coatings
ment is proven very effective in improving the corrosion to improve thermal properties of the substrate. Soheila-
resistance by filling the tiny pores present in the Ni–P–Zn Faraji tried four different configurations Cu–P, Cu–P–SiC,
matrix [94]. Balarju experimented with Ni–Cu–P, Ni–W–P Cu–P–Cg and Cu–P–Cg–SiC. Cu–P–SiC offers better hard-
and Ni–W–Cu–P coatings on mild steel for improvement ness and corrosion resistance than other three coatings.
in micro-hardness out of which Ni–W–P coating is better His study revealed that the size of particles also influences
than other two coatings as deposited and annealed at 400 °C. the corrosion resistance and hardness of the coatings [98].
Ni–Cu–P is proven as the better coating to attain high sur- Lower double layer capacitance of Cu–P–nano-SiC coat-
face roughness and Ni–W–Cu–P offered better corrosion ings is an evidence for higher corrosion resistance than the
resistance due do minimum corrosion current densities [95]. Cu–P–micro SiC coatings. Co-deposition of SiC particles
Adhesion strength of the Ni–W–P–Nb2O5 coating on sin- retains the plastic deformation of Cu–P matrix which results
tered NdFeB substrate increased with increasing the N ­ b 2O 5 improvement in hardness of the composite coating. Corro-
particle concentration up to 15 g/L in the electroless bath, sion resistance of the Cu–P coating in NaCl and HCl solu-
beyond this particle concentration lower adhesion strength tions is improved while adding the SiC particles to Cu–P
is observed due to increase in brittle nature of the coating. matrix [102–105].
The Ni–W–P–Nb2O5 coating formed at optimal condition
(15 g/L) shows maximum microhardness value of 625 HV.
The positive shift of corrosion potential from -0.536 mV to 8 Conclusions
-0.480 mV confirms that increasing the corrosion resistance
of the ternary coating [96]. Mukhopadhyay and Balaraju Electroless coatings have been proven with significant
were co-deposited ­Al2O3into Ni–W–P coating on low car- improvement in hardness, corrosion and wear resistance
bon steels and observed an improvement in the hardness for various metallic substrates. Most of the Ni–P and Ni–B
due to reduction of phosphorous concentration in presence composite coatings are examined on various steel substrates.
of ­Al2O3. Phase transformation studies revealed that, ther- Few researchers also tried up with the copper-based compos-
mal stability and the hardness of the composite coating is ite coating to improve the surface properties of the substrate.

Table 3  Research literature on Substrate Ni–P–Zn–TiO2 Ni–W–Cu–P Ni–W–P–Al2O3 Ni–P–Cg–TiO2 Cu–P–SiC

various Ni- and Cu-based poly
alloy coatings Low carbon steel [94]a,c [97]a,c
Mild steel [95]a
Steel sheet [102, 103]c
Galvanized carbon steel [101]a,b,c
Carbon steel [104]c

a, b and c represent the microhardness, wear and corrosion resistance of the coatings

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