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Surface & Coatings Technology 357 (2019) 543–558

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Surface & Coatings Technology


journal homepage: www.elsevier.com/locate/surfcoat

Comparative study on the friction-wear property of As-plated, Nd-YAG laser T


treated, and heat treated electroless Nickel-Phosphorus/Crab shell particle
composite coatings on mild steel

S. Arulvela, , A. Elayaperumala, M.S. Jagatheeshwarana, A. Satheesh kumarb
a
Department of Mechanical Engineering, Anna University, Chennai 600025, Tamil Nadu, India
b
Meera Laser Solution, Ambattur, Chennai, Tamilnadu, India

A R T I C LE I N FO A B S T R A C T

Keywords: Nickel-Phosphorus/Crab shell particle (NiP/CSP) composite coatings were prepared with different weight dis-
Mild steel persions of CSP (0.5 g/l, 1.0 g/l, 1.5 g/l, 2.0 g/l, 2.5 g/l and 3.0 g/l) on mild steel using electroless coating
Electroless coating process. Fabricated coatings were post treated with heat treatment and Nd:YAG laser treatment process and
Nickel-phosphorus followed by a comparative study on surface morphology, surface hardness, phase structure, and friction-wear
Crab shell
property with as-plated NiP and NiP/CSP composite coatings. The result showed the relative changes in the
ND:YAG laser
surface morphology of NiP/CSP composite coatings after Nd:YAG laser treatment. Dendrite structure was ob-
served for laser treated coatings and its formation was affected by the incorporation of CSP in the NiP matrix.
FeNi2P phase was formed for laser treated coatings in addition to the Ni3P and Ni12P5 phases. Higher surface
hardness of 966 Hv0.05 and 941 Hv0.05 was achieved for laser treated NiP and NiP/CSP composite coatings
compared to the heat treatment process and as-plated condition. On comparison with various weight dispersions,
higher surface hardness of 941 Hv0.05 was obtained for NiP/CSP (2.5 g/l) composite coatings as a result of the
high diffusion of Fe element from substrate to the surface. Low friction coefficient was seen for the heat
treatment process followed by the as-plated and laser treatment process. The formation of FeNi2P phase caused
an increase in the friction coefficient for laser treated NiP and NiP/CSP composite coatings. However, there was
an improvement in the wear resistance of laser treated coatings compared to the as-plated and heat treated
coatings.

1. Introduction engineering of steel components. Electroless coating technique is an


autocatalytic chemical reduction process used in various industrial
Friction and wear are the two surface degradation phenomena that applications owing to its good lubricity hardness wear and corrosion
occur during the interaction of two surfaces. Hence, modification of the resistance [2]. Though as plated electroless NiP coating exhibits a better
materials surface could play a vital role on controlling friction and wear wear and corrosion properties, it is improved further by the secondary
of any material. The surface of mild steel had been the subject of in- process and second phase particle incorporation in the electroless nickel
terest for researchers due to its poor friction wear property and so, matrix. The choice of second phase particles depends upon the appli-
modification of the surface of mild steel and determination of its fric- cations, where coating is desired. Reinforcement of soft or solid lu-
tion-wear property are very important. Mild steel is a low carbon steel bricants like WS2, PTFE, MoS2, and graphene usually has a low friction
which was the accepted steel material in several industrial applications coefficient with reduced hardness and, hard particle reinforcement like
due to its better malleability, weld-ability and low cost. A severe wear WC, SiC, and Al2O3 could increases the wear resistance with increased
transition mode places a limit on the use of the mild steel in friction hardness [3–5]. So, the second phase reinforcement particle is opted for
wear applications [1]. To overcome this, it is necessary to modify the electroless composite coating depending upon the operating environ-
surface of mild steel relevant to the tribology application. Despite the ment. Recently, a combination of solid lubricants and ceramics particles
availability of several coating techniques, the electroless deposition is finding preference for use with NiP matrix for providing low friction
process has been the promising technique which finds use in surface coefficient, high wear resistance, and better hardness [6]. Hence, the


Corresponding author.
E-mail address: gs.arulvel.research@gmail.com (A. S.).

https://doi.org/10.1016/j.surfcoat.2018.10.051
Received 29 August 2018; Received in revised form 12 October 2018; Accepted 18 October 2018
Available online 20 October 2018
0257-8972/ © 2018 Elsevier B.V. All rights reserved.
A. S. et al. Surface & Coatings Technology 357 (2019) 543–558

focus of several works which is still on reinforcing hybrid particles with using electroless coating process. The friction-wear property of as-
NiP matrix for improvement of friction wear property [7–10] and also plated NiP/CSP composite coating is compared with the heat treatment
been a success in the past. Hybrid combinations of amorphous phase process and Nd:YAG pulsed laser treatment process to suggest a better
and crystalline phase were observed in crab shell particles as reported secondary post treatment process for NiP and NiP/CSP composite
in author's previous article [11]. The presence of an amorphous phase coatings.
(organic polymer and protein) could enhance the interface strength of
CSP with NiP matrix during the deposition process. Presence of an 2. Materials and method
amine group in CSP also have an advantage of increasing the rate of
deposition arising as a result of the chelating ability, which typically 2.1. Matrix and reinforcement particles
not exists for ceramic particle reinforced NiP coating. The dissolving
phenomenon of CSP also has the advantage of improving the solid so- Crab shell particle (Carpilioidea species) was used as the re-
lution strengthening of NiP matrix in terms of lubrication for friction inforcement particle. Extraction and processing of crab shell particles
wear application. Hence, this work is focused on the utilization of CSP from crab shell have been described in the author's previous article
at various weight percentages as reinforcement with NiP matrix. [11]. Nickel - Phosphorus was used as a matrix for reinforcing crab shell
In spite of reinforcing the second phase particles with NiP matrix, particles through electroless coating process involving several chemical
secondary processes are regularly followed for the enhancement of reactions in an aqueous solution of electroless NiP bath.
surface properties. The low temperatures of electroless NiP coating
process do not have much influence on the strengthening of the inter- 2.2. Particle characterizations
face of matrix and particles. Hence, several authors have reported the
effect of the secondary process on improving the chemical interaction The particle size, elemental composition, and morphology of CSP
between the particle matrix and substrate [12]. Generally in the heat were characterized using a scanning electron microscope (SEM) with
treatment process, both coating and the substrate are heated to a energy dispersive spectrum mapping (EDS) (Hitachi S-3400N).
temperature of 400 °C–600 °C [13] and allowed to cool at a constant Diffraction pattern and EDX analysis of CSP was obtained using high
rate. This leads to the crystallization process and inter-diffusion reac- Resolution Transmission Electron Microscope (HR-TEM) (Tecnai, G2 20
tion between NiP coating and the substrate. Crystallization process is Twin) to discuss the different phases of the constituents of CSP.
initiated with the formation of stable Ni crystallites and followed by the
formation of Meta stable precipitates like Ni3P, NiP, Ni5P, and Ni12P5 2.3. Fabrication of electroless NiP and NiP/CSP composite coatings
[14]. The formation of stable and Meta stable phases during the sec-
ondary heat treatment could enhance the properties such as hardness, Mild steel with an average surface roughness of 0.50 μm with ele-
corrosion resistance, and wear. In the case of the laser treatment, the mental composition shown in Table 1 was used as a substrate material
surface undergoes rapid melting and is followed by rapid self- for the deposition of NiP and NiP/CSP composite coatings.
quenching. This produces a structure with ultra-fine grains on the The chemical reactions and the formation mechanism of NiP and
coating surface and increases the bonding strength between the coating NiP/CSP composite coating on mild steel have been referred to in the
and the substrate. Therefore, the laser treatment process had been the author's previous article [16]. A typical bath composition and para-
widely accepted secondary treatment process for improving hardness, meters used for the fabrication of electroless NiP and NiP/CSP com-
wear, and corrosion resistance. A study of the laser treatment on cor- posite coatings are shown in Table 2.
rosion and wear properties has been reported by various authors and Prior to the coating process, specimen was pre-treated at room
concluded that the laser treated coatings is superior to heat treated temperature with the procedure shown in the flow chart (Fig. 1). Fol-
coatings [15]. In addition, laser treatment leads to the formation of lowing the pretreatment process, the specimen was immersed in an
both the amorphous phase and the crystalline phase in the structure of alkaline electroless bath with pH in the range of 7 to 7.5, which was
NiP coating. This phase combination certainly improves the friction- monitored using digital pH meter. Ph was maintained at the same level
wear property of NiP coating. However, laser treatment induces a crack throughout the coating process using glacial acetic acid.
formation on the surface, which is considered as a drawback of using
the laser treatment process for friction-wear and corrosion application. 2.4. Heat treatment and Nd:YAG laser treatment process
This crack certainly plays a significant role in the introduction of the
fracture phenomenon during the sliding of two surfaces. Hence, it is The fabricated coating samples were heat treated to 400 °C using a
very important to discuss the comparative study of using various sec- conventional furnace at a heating rate of 0.5 °C and allowed to cool
ondary processes on the fabricated electroless composite coatings in [16]. Nd:YAG laser was used as the source for the laser treatment
terms of friction-wear behavior. process with the parameters shown in Table 3. All samples were treated
In author's previous article, friction-wear property of heat treated with a constant laser power of 150 W at a constant scanning speed of
electroless NiP/CSP composite coating was determined at various load 30 mm s−1 of the laser beam. Argon gas was used for reducing the
conditions [16]. The conclusion reached was that crab shell particles surface oxidation that resulted during the laser processing.
can be effectively used for controlling adhesive wear under a high load
condition. However, a detailed study on the effect of various weight 2.5. Hardness analyses
percentages of CSP in NiP matrix on microstructure, coating thickness,
hardness, and friction-wear property has not reported in respect of as- Surface hardness of fabricated NiP and NIP/CSP composite coatings
plated, Nd:YAG pulsed laser treatment, and heat treatment process. (as-plated, heat treated, and Laser treated) was measured on the surface
Hence, this work presents the study on the friction-wear property of of the coatings using a micro Vickers hardness tester (ECONOMET VH
NiP/CSP composite coating with various dispersions of CSP fabricated 1D) under a load of 50 g at a dwell time of 15 s.

Table 1
Chemical composition of mild steel in weight percentage.
Element (wt%) Carbon Copper Iron Manganese Phosphorous Silicon Sulfur

Mild steel 0.25–0.29% 0.20% 98% 1.03% 0.040% 0.280% 0.50%

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Table 2 with various grades and finally polished with a velvet cloth under the
Bath parameters of electroless bath. suspension of alumina powder.
Component Concentration
2.7. Phase structure analysis
Nickel sulfate 20 g/l
Sodium hypophosphite 23 g/l
The phase structure of coatings was determined using X- ray dif-
Sodium citrate 13 g/l
Lead acetate 0.001 g/l
fractometer (XRD) using CuKα radiation with wavelength of 1.54 Å in a
Acetic acid 3–5 ml diffraction angle of 2theta from 10° to 70° at a step size of 0.02.
Crab shell particle (CSP) 0.5 g/l, 1.0 g/l, 1.5 g/l, 2.0 g/l, 2.5 g/l and 3.0 g/l
Agitation speed 350 rpm 2.8. Friction-wear characterization
Temperature 80 °C–90 °C

Friction and wear behavior were tested against hardened EN-31


steel using a pin on disc apparatus (DUCOM) with a constant sliding
velocity of 0.7 m s−1 at load of 14.71 N in dry sliding condition at room
temperature. The preliminary step prior to friction-wear test and wear
rate calculation has been referred to in the author's previous article
[16]. SEM images of the wear track were used for characterizing the
wear mechanism occurred during the dry sliding test.

3. Result and discussion

3.1. Particle characterization (SEM and TEM analysis)

Surface morphology of CSP (Carpilioidea species) obtained using


SEM is shown in Fig. 2. The particles exhibited a non-uniform surface
morphology with varying particle sizes (Fig. 2a).
The average particle size of CSP was between 5 and 18 μm. EDS
mapping confirmed the existence of C, Ca, Mg, Si, O and P in CSP,
which implied a hybrid combination of inorganic and organic elements.
The spectrum depicted Ca and O as major constituents of CSP and
elements like Mg, Si and P were presented as impurities. The presence
of carbon indicated the presence of organic constituents such as chitin
polymer and protein matrix, which is combined with the inorganic
elements.
Fig. 3 shows the morphology, EDX, and diffraction pattern of CSP
obtained using TEM. The presences of both inorganic and organic
constituents were seen in the morphology of CSP along with non-uni-
form particle size (Fig. 3a). A transparent white region indicated the
presence of organic elements while the dark region showed the pre-
sence of inorganic elements. Both these regions were found randomly
distributed in the CSP, indicating the distribution of amorphous and
crystalline phases. The obtained diffraction pattern of CSP is shown in
Fig. 3b. The diffraction pattern of CSP exhibited a random distribution
of various crystal orientations. This was due to the presence of elements
Ca, Mg, Si and organic constituents. The presence of these elements was
also confirmed through EDX analysis as shown in Fig. 3c. The random
Fig. 1. Flowchart of pretreatment procedure before coating process. orientation of bright spots within the diffraction ring evidences that
crab shell particles was a combination of polycrystalline and amor-
Table 3 phous structure.
LASER hardening parameter.
3.2. Surface morphology study
Parameters Type/units

Laser type Nd:YAG Fig. 4 depicts the surface morphology of NiP, and NiP/CSP (as-
Power 150 W plated, heat treated, and laser treated) composite coatings. As-plated
Frequency 12 Hz
NiP coating exhibited a typical cauliflower nodular structure (Fig. 4a),
Pulse duration 6 μS
Wave length 1064 nm
which is consistent with many articles [17].
Laser spot dia 4 mm No morphological change was observed for heat treated NiP coat-
Scanning speed 30 mm s−1 ings apart from the refined grain boundaries (Fig. 4b). The strong re-
fined grain boundaries were presumably related to the transformation
of the amorphous phase to the crystalline phase during the heat treat-
2.6. Microstructure ment process. To discuss the grain boundary refinement, grain
boundary width of as-plated and heat treated NiP coating measured
Surface morphology and cross section images of NiP and NIP/CSP using SEM is shown in the inlay image of Fig. 4a and b. The grain
composite coatings were obtained using a scanning electron microscope boundary width of as-plated NiP coating was about 1 μm, which is high
(SEM) with EDS mapping (Hitachi S-3400N). A cross section of the test compared to that of 0.1 μm of heat treated NiP coating. The refinement
specimen was mounted and mechanically polished using SiC papers of the grain boundary width was presumably related to the grain

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Fig. 2. a) SEM image of CSP and b) EDS mapping of CSP.

boundary diffusion phenomenon caused during the heat treatment diffusion of atoms across the grain boundary and restrict the growth of
process. During the transformation of amorphous phase to the crystal- the grain boundary width for heat treated NiP coating. Hence, this
line phase, Meta stable phases are induced in the coatings and these phenomenon caused refined grain boundaries for the heat treated NiP
phases act as impurities. These impurities certainly enhance the coatings. The role of impurities on grain boundary diffusion has also

Fig. 3. a) TEM image of CSP, b) Diffraction pattern of CSP and c) EDX pattern of CSP.

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Fig. 4. SEM images of NiP coating in a) As-plated, b) Heat treated, and c) Laser treated conditions.

been discussed in a recent article [18]. confirm the element present in the surface of Laser treated NiP coating,
A typical sharp parabolic needle like structure was formed for Laser EDS analysis is shown in Fig. 5. EDS mapping clearly shown the pre-
treated NiP coating. This was found to be uniformly distributed sence of Ni, P, and Fe elements for Laser treated NiP coating. The
throughout its morphology (Fig. 4c). This structure, termed as a den- presence of Fe elements are due to the diffusion phenomenon caused
drite structure is the result of the rapid solidification and cooling of the during the laser treatment process.
coatings during the laser treatment process. The formation of dendrite The cross section image of as-plated, heat treated and laser treated
structure also indicates a faster growth of nickel crystal towards the NiP coating is shown in the Fig. 6. No cracks, voids and pores were
crystallographic direction. The central core of the dendrite structure detected across the cross section of as-plated NiP coating and heat
indicates the Ni phases (Ni3P, Ni12P5), which had a better interface with treated NiP coating (Fig. 6a and b), whereas, pores were seen in the
the primary α-Ni. These phases are the primary reason for limiting the cross section of the laser treated NiP coating (Fig. 6c). There was an
growth of the dendrites in the morphology structure. This structure increase in the coating thickness of 54 μm for laser treated NiP coating
almost matched with the morphology of NiCrBSi hard facings [19], compared to the 18 μm of as-plated NiP coating and 20 μm of the heat
whereas, laser treated NiP coating is not reported elsewhere. To treated NiP coating. The increase in the coating thickness was related to

Fig. 5. EDS mapping image of laser treated NiP coating.

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Fig. 6. Cross section SEM images of NiP coating in a) As-plated, b) Heat treated, and c) Laser treated conditions.

the faster growth of Ni as discussed earlier for the dendrite structure. Fig. 7 shows the EDS mapping across the cross section of the laser
The growth of NiP matrix arising as a result of the rapid solidification treated NiP coating. Elemental mapping of laser treated NiP coating
caused the formation of pores. evidenced the presence of Ni, P, and Fe elements, which are the

Fig. 7. SEM and EDS mapping image of the cross section of laser treated NiP coating.

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Fig. 8. SEM images of NiP/CSP composite coating of a) As-plated (0.5 g/l), a1)As-plated (2.5 g/l), b) Heat treated (0.5 g/l), b1) Heat treated (2.5 g/l), c) Laser treated
(0.5 g/l) and c1) Laser treated (2.5 g/l).

constituents of NiP coating and the mild steel substrate. Diffusion of Fe globules following an increase in the addition of CSP (0.5 g/l to 2.5 g/l)
elements from the substrate to the upper surface of the coating was also in the bath. Among the various weight dispersed NiP/CSP composite
observed. This indicates the occurrence of effective rapid solidification coatings, NiP/CSP (2.5 g/l) composite coating exhibited more nickel
and diffusion phenomenon during the laser treatment. globules due to the high weight dispersion of CSP in the NiP matrix
A change in the morphology of as-plated NiP/CSP composite (Fig. 8a1). The high dispersion of CSP caused a higher catalytic nature
coating was seen after the initial (0.5 g/l) dispersion of CSP in the in the bath, generating more nickel globules in the surface of NiP/CSP
electroless bath (Fig. 8a). Formation of smooth spherical nickel globules (2.5 g/l) composite coating. The increase in the catalytic nature caused
are seen on the surface of NiP/CSP (0.5 g/l) composite coating. The an increase in the rate of deposition of nickel and other constitution
reinforcement of CSP had led to two phenomena, namely, the formation ions of the CSP. Fig. 9 shows the cross section images of as-plated, heat
of spherical nickel globules and the increase in the coating rate. The treated and laser treated NiP/CSP composite coatings. All coatings were
formation of nickel globules was presumably related to the increase in uniformly distributed over the mild steel surface. To discuss the coating
the nucleation site created by the CSP. The tendency of CSP for in- thickness related to the rate of deposition, coating thickness measured
creasing the nucleation site has been reported in the author's previous across the cross section of the coatings is shown in the Table 4.
article [16]. Along with the spherical nickel globules, CSP reinforced There was a considerable increase in the coating thickness for as-
with NiP matrix was also observed in the morphology of as-plated NiP/ plated NiP/CSP composite coating with increasing the weight disper-
CSP (0.5 g/l) composite coating. There was an increase in the nickel sion of CSP from 0.5 g/l to 2.5 g/l in the bath. A high coating thickness

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Fig. 9. Cross section SEM images of a) As-plated (0.5 g/l), a1) As-plated (2.5 g/l), b) Heat treated (0.5 g/l), b1) Heat treated (2.5 g/l), c) Laser treated (0.5 g/l) and c1)
Laser treated (2.5 g/l).

Table 4 of 29 μm was achieved for as-plated NiP/CSP (2.5 g/l) composite


Coating thickness measured across the cross section. coating among the other as-plated NiP/CSP composite coatings. The
S. no Samples As-plated (μm) Heat treated (μm) Laser treated increase in the coating thickness was due to the increase in the rate of
(μm) deposition which was the result of the catalytic effect created by the
CSP in the NiP bath. Elemental mapping across the surface of as-plated
1 NiP 18 20 54
NiP/CSP (2.5 g/l) composite coating (Fig. 10) confirmed the presence of
2 NiP/CSP (0.5 g/l) 22 23 52
3 NiP/CSP (1.0 g/l) 24 24 50
Ni, P, Ca, Mg, and Fe elements, which are the constituents of NiP ma-
4 NiP/CSP (1.5 g/l) 25 25 48 trix, CSP, and mild steel substrate. Instability of the bath was observed
5 NiP/CSP (2.0 g/l) 27 28 44 with increasing the weight dispersion of CSP to 3 g/l in the bath, which
6 NiP/CSP (2.5 g/l) 29 29 40 had an effect on the deposition process for the NiP/CSP (3 g/l) com-
7 NiP/CSP (3.0 g/l) 20 19 18
posite coating. Bath instability turning the NiP bath from green color to
black color was also observed during the deposition of NiP/CSP (3 g/l)
composite coating.
Not much change was seen in the surface morphology and coating

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Fig. 10. SEM and EDS mapping image of as-plated NiP/CSP (2.5 g/l) composite coating.

thickness of heat treated NiP/CSP composite coating when compared to result of the inter-metallic shrinkage that occurred around the dendrites
the as-plated NiP/CSP composite coating in respect to the various dis- during the growth of the Ni. The low hardness values of NiP/CSP
persions of CSP in the bath (Fig. 8b). However, laser treated NiP/CSP (2.5 g/l) composite coating caused crack formation in the coatings.
composite coating exhibited a structural change in the surface mor- However, the depth of the crack did not reach the substrate material.
phology (Fig. 8c). There was a formation of dendrites structure, which Elemental mapping of laser treated NiP/CSP (2.5 g/l) composite coating
is similar to the laser treated NiP coating. However, there was the oc- clearly showed the presence of elements Ni, P, Mg, Fe, and Ca elements
currence of a greater reduction in the growth of dendrites due to the across the cross section and porosity around the dendrites (Fig. 11).
reinforcement of CSP. The restriction in dendrites growth could be due
to two reasons: one was the formation of Meta stable phases and other
was the co-mixture of the inter-dendrite liquids (Ca, Mg, and Si) during 3.3. Phase structure characterization
the melting and solidification. Dissolving nature of CSP constitutes like
Ca, Mg, and Si in the NiP matrix during the coating process is discussed NiP is a eutectic alloy which induces phase changes during the
application of thermal stress. Hence, it is important to study the effect
in the previous article [16]. These reinforced elements tend to melt
during the laser treatment and increase the density of the nickel liquid. of phase changes before and after the heat treatment and the laser
treatment process. The XRD pattern obtained for NiP and NiP/CSP (as-
Hence, the high density created by the constituent elements of CSP
restricts the growth of the Ni dendrites during the solidification. On plated, heat treated and laser treated) composite coatings are shown in
Fig. 12.
increasing the weight dispersion of CSP, there was a continuous de-
crease in the growth of Ni dendrites. Low dendrite growth was seen for As-plated NiP coating exhibited a typical amorphous structure
presented as one broad diffraction peak NiP (111) at angle 2θ = 45.5°,
laser treated NiP/CSP (2.5 g/l) composite coating as a result of the in-
crease in both Meta stable phases and density of intermetallic liquid indicating the solid solution of phosphorus in Ni matrix [20]. There was
a phase structure change in the NiP coating following the heat treat-
created by the high dispersion of CSP (Fig. 8c1). The restriction in
dendrite growth resulted in a decrease in the coating thickness for laser ment and laser treatment process. Heat treated NiP coating exhibited a
micro-crystalline structure with various Meta stable phases (Fig. 12a).
treated NiP/CSP composite coatings. Hence, a low coating thickness of
36 μm was obtained for laser treated NiP/CSP (2.5 g/l) composite The pattern of heat treated NiP coating showed several sharp peaks at
angle 2θ = 45°, 37°, 50°, and 62° evidencing the formation of phases
coating compared to the other laser treated NiP/CSP (0.5 g/l) compo-
like Ni (111), Ni12P5 (112), and Ni3P (103) respectively. These phases
site coatings.
had led to precipitation hardening in the coating, which was the pri-
The cross section of laser treated NiP/CSP (0.5 g/l) composite
mary reason for the increase in the hardness of heat treated NiP coat-
coating and NiP/CSP (2.5 g/l) composite coating are shown in Fig. 9c
ings. The XRD pattern obtained for the laser treated NiP coating evi-
and c1. Numerous pores and voids formed around the dendrites are
denced the formation of both amorphous and crystalline phase
seen across the cross section of the laser treated NiP/CSP (0.5 g/l)
composite coating. On increasing the weight dispersion of CSP, there structures. The peak at angle 2θ = 42° indicated the existences of
amorphous Ni12P5 phase. The formation of amorphous Ni12P5 phase
was an increase in the pores due to the decreased hardness of the NiP/
CSP composite coating prior to the laser processing. NiP/CSP (2.5 g/l) was due to the re-calescence effect caused during the rapid solidifica-
tion. Various peaks at angle 2θ = 32°, 36.5°, and 43° represents mi-
composite coating exhibited many pores, voids, and cracks across the
cross section of the coatings. The formation of pores and voids was the crocrystalline Ni3P (111) and Ni (111) phases. The formation of Ni3P
(111) confirmed the effective solid solution of nickel and phosphorus

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Fig. 11. SEM and EDS mapping image of laser treated NiP/CSP (2.5 g/l) composite coating.

elements. Additional peaks were formed for laser treated NiP coating at increase in the peak shift was seen with increasing the weight disper-
various angle of 2θ = 36.5° and 67.5° in contrast to heat treated coat- sion from 0.5 g/l to 2.5 g/l of CSP in the bath. This was the result of the
ings. These peaks indicated the presence of FeNi2P phase. The forma- maximum replacement of nickel ions by the constituent's elements (Mg
tion of FeNi2P phase was due to the inter-diffusion phenomenon that and Ca) of CSP, which increases internal stress and precipitate forma-
took place between the two liquids (Ni and P) and Fe constitutions of tion [16]. The peak around an angle 2θ = 56° of heat treated NiP/CSP
the substrate during the laser processing. The diffusion of Fe solute in (2.5 g/l) composite coatings indicated the presence of Mg, while the
two alloying liquid (Ni and P) could have led to the weaker atomic peak at an angle 2θ = 24° represented the existence of Ca elements
interaction, thus decreasing the crystallization process. This induced an (Fig. 12c). The presence of peaks Mg and Ca evidences the effective
amorphous structure for the laser treated NiP coating. solid solution of elements of CSP with the NiP matrix.
The patterns of as-plated NiP/CSP composite coatings shown in The XRD pattern of laser treated NiP/CSP composite coatings
Fig. 12b and c are almost similar to the amorphous structure of as- showed a typical peak of Ni3P and FeNi2P formed at an angle of 36.5°,
plated NiP coating. The initial dispersion of crab shell particles (0.50 g/ 45°, and 47.8°. This was similar to the laser treated NiP coating.
l) had no effect on the crystallographic structure of as-plated NiP/CSP However, there was a slight shift in the angle for Ni3P and FeNi2P
(0.50 g/l) composite coatings. However, with increasing the weight phases from a higher angle to a lower angle for laser treated NiP/CSP
dispersion of CSP to 2.5 g/l in the bath, there was a slight shift in the composite coatings. The presence of Mg and Ca was seen at angle of
peak of NiP (111) for as-plated NiP/CSP (2.5 g/l) composite coating. 57.5° and 24° respectively. The existence of these peaks confirmed the
The peak shift from angle 45.5° of NiP coating to 42.5° of as-plated NiP/ solid solution strengthening of CSP elements in the NiP matrix. Apart
CSP (2.5 g/l) composite coating indicates the increase in the internal from the peak shift, the presence of Ca and Mg elements played a major
stress created by the CSP in the NiP matrix. Peaks obtained at angle role in the formation of the FeNi2P phase. As discussed earlier, the
26.8°, 62.5°, and 42.5° also confirm the existence of element Ca, Mg, formation of FeNi2P phase was the result of the diffusion of Fe elements
and NiP, which are the constituents of NiP matrix and CSP. On com- from the substrate to the coating surface. The diffusion is depended on
parison with as-plated and heat treatment, laser treatment had greatly the hardness of the coatings, on account of which, the maximum
influenced the change in crystallographic structure of NiP/CSP com- hardness of NiP coating resulted in a low diffusion of Fe elements. This
posite coatings. Heat treated NiP/CSP composite coating exhibited a caused a low distribution of FeNi2P phases in the laser treated NiP
microcrystalline structure, which is in sharp contrast to the amorphous coating compared to the laser treated NiP/CSP composite coatings. The
structure of as-plated NiP/CSP composite coating. The sharp diffraction formation and distribution of FeNi2P phase increased with the initial
peak at an angle 44° evidenced the existence of face center cubic Ni dispersion of CSP (0.5 g/l) in the coating. This was due to the decrease
(111) and microcrystalline structure. Dispersion of CSP (0.50 g/l) in the in the hardness of as-plated NiP/CSP composite coating. On comparison
NiP matrix has led to the formation of more Meta stable phases and with various weight dispersion, laser treated NiP/CSP (2.5 g/l) com-
peak shift phenomenon (Fig. 12b). Meta stable phases like Ni12P5 (112) posite coating presented more FeNi2P peaks. This was due to the lower
and Ni3P (103) formulated at various angle of 2θ = 64° and 22.5° are hardness of as-plated NiP/CSP (2.5 g/l) composite coating, which al-
due to the heat treatment process. The shift in the peak of Ni (111) lowed the diffusion of more Fe elements from the substrate to the
plane to the lower angle was also evidenced for heat treated NiP/CSP surface.
(0.5 g/l) composite coatings with the initial dispersion of CSP (0.5 g/l)
in the bath, when compared to the heat treated NiP coating. Gradual

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Fig. 12. XRD diffraction pattern of As-plated, Heat treated and laser treated of a) NiP coating, b) NiP/CSP (0.50 g/l) composite coating, and c) NiP/CSP (0.50 g/l)
composite coating.

Fig. 13. Micro hardness of mild steel, NiP, and NiP/CSP composite coatings (As-plated, Heat treated and laser treated).

3.4. Microhardness analysis As for the as-plated NiP/CSP composite coating, there was a decrease in
the hardness with the incorporation of CSP (0.50 g/l) into the NiP
The surface hardness of mild steel, NiP, and NiP/CSP composite matrix. There was a continuous decline in the hardness of as-plated
coating (as-plated, heat treated, and Laser treated) measured using a NiP/CSP composite coating due to the increase in the weight dispersion
Vickers hardness tester is shown in Fig. 13. (0.50 g/l to 2.5 g/l) of CSP in the electroless NiP bath. This was due to
It was clearly evident that the surface hardness of mild steel is in- the defect substitutional solid solution strengthening mechanism, which
creased after NiP and NiP/CSP coating in the as-plated condition itself. has been discussed in the author's previous articles [16]. In electroless

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Fig. 14. Friction coefficient of mild steel, NiP, and NiP/CSP composite coatings (As-plated, Heat treated and laser treated).

coating process, the solution state of Ni and P elements forms the solid of the coatings.
NiP matrix on the substrate. Hence, the solubility of reinforcement A comparison with as-plated and heat treated, laser treated NiP/CSP
particles plays a significant role in defining the hardness of the coatings. (0.5 g/l) composite coating presented a high surface hardness of
Similar to this, the dissolved Ca, Mg, and Si elements in the NiP bath 662 HV0.05 with the initial dispersion of CSP (0.5 g/l) in the NiP. There
tend to replace several Ni atoms in certain positions of the lattice, was an increasing trend in the hardness value for laser treated NiP/CSP
making the NiP matrix softer. This phenomenon leads to a decrease in composite coatings following an increase in the weight dispersion of
the hardness of as-plated NiP/CSP composite coatings in respect to the CSP from 0.5 g/l to 2.5 g/l in the bath, which is in contrast to the as-
various weight dispersion of CSP in the bath. The solubility nature of plated NiP/CSP composite coating. The increase in the hardness after
CSP has been discussed in the author's previous article [11]. Due to this laser treatment is due to the formation of Ni3P and FeNi2P phases as
feature, the presence of Ca, Mg, and Si is increased in the NiP bath due discussed earlier for the laser treated NiP coating. The formation of
to increase in the weight dispersion of CSP. This caused a decrease in these phases was increased considerably with increasing the addition of
the hardness of as-plated NiP/CSP composite coating with increasing CSP with NiP matrix. Among the various weight dispersions, NiP/CSP
the weight dispersion of CSP from 0.50 g/l to 2.5 g/l. The decrease or (2.5 g/l) composite coating presented a high hardness value. This was
increase in the hardness of the coatings owing to the hardness of re- due to the increase in the formation and refinement of Ni3P and FeNi2P
inforcement particles has been referred in many articles [21,22]. dendrites phases in the coating. The low hardness of as-plated NiP/CSP
There was an increase in the hardness of NiP and NiP/CSP com- (2.5 g/l) composite coating was the primary cause for the diffusion of
posite coating (0.50 g/l, 1.0 g/l, 1.5 g/l, 2.0 g/l and 2.5 g/l) following more Fe elements to the surface of the coatings during the laser pro-
the heat treatment process, when compared to the as-plated coatings. cessing. These Fe elements tend to solidify with the NiP matrix and
However, there was no change in the decreasing sequence of hardness form as a FeNi2P phase in the coatings which resulted in the increase in
values of heat treated NiP/CSP composite coating with increasing the hardness value. Hence, the distribution of more FeNi2P phase had been
weight dispersion of CSP from 0.5 g/l to 2.5 g/l similar to the as-plated the reason for the higher hardness of laser treated NiP/CSP (2.5 g/l)
NiP/CSP composite coating. Among the various weight dispersions of composite coating.
CSP, heat treated NiP/CSP (0.5 g/l) composite coating presented a
higher hardness value. An increase in the weight dispersion from 0.5 g/l 3.5. Friction-wear study
to 2.5 g/l caused a considerable decrease in the hardness of the coatings
due to the reinforcement of soft CSP in the matrix as discussed earlier Fig. 14 shows the average friction coefficient measured for mild
for the as-plated NiP/CSP composite coating. Heat treatment caused a steel, NiP and NiP/CSP (as-plated, heat treated, and Laser treated)
phase transformation of coatings from amorphous to crystalline struc- composite coatings. High friction coefficient was exhibited for mild
ture, which played a huge role in the hardness of the coatings [23]. steel on sliding against hardened EN-31 steel in comparison with NiP
During the phase transformation, there was a formation of Meta stable and NiP/CSP composite coatings. A decrease in the friction coefficient
Ni3P precipitates, which was considered as the reason for the increase after NiP and NiP/CSP composite coatings on mild steel was evident.
in the hardness for heat treated NiP/CSP composite coating when The increase in the friction coefficient of mild steel indicated the high
compared to the as-plated NiP/CSP composite coating. These pre- wearing out of material from the mild steel. The wear rate calculated
cipitates are generally formed as Ni–Ni3P interfaces, generally in- using the mass loss is presented in Fig. 15. From the Figure, it is clear
creasing the interfacial free energy of Ni3P as discussed in the previous that mild steel exhibited a high wear rate when compared to the NiP
article [16]. The inclusion of Ca and Mg atoms could cause a decrease in and NiP/CSP composite coatings. Hence, modification of the surface of
the interface strength of Ni and Ni3P as the result with a decrease in the mild steel was seen as important for controlling friction and wear rate.
hardness for heat treated NiP/CSP composite coatings. The inclusion of As plated NiP coating exhibits a friction coefficient of 0.31 which is
CSP constituent between Ni and Ni3P was intensified on increasing the comparatively less than the uncoated mild steel. The low friction
CSP in the bath. Hence, the maximum dispersion of CSP (2.5 g/l) coefficients of as-plated NiP coating are due to the lubrication created
achieved a low hardness compared to the minimum dispersion of CSP in by the nickel during the sliding against EN-31 steel and as a result of
the bath. which, wear rate of the NiP coating was also reduced.
Hardness of laser treated NiP coating increased to 966 HV0.05 from To discuss the wear mechanism, SEM image of the wear track of NiP
507 HV0.05 of as-plated NiP coating. The increase in hardness was and NiP/CSP composite coating was taken and shown in Fig. 16. Ad-
caused by the formation of hard dendrites phases Ni3P and FeNi2P in hesive and abrasive wear as the dominant wear mechanism for as
the coating. The rapid growth of dendrite was the result of rapid soli- plated NiP coating (Fig. 16a). Ploughing furrows, abrasive grooves, and
dification, which caused microstructural changes in the laser treated scratches are visible in the wear track of as-plated NiP coating, which
coatings. This dendrites caused a fine crystalline structure by restricting indicates the characteristic of abrasive wear. This could be due to third
the growth of the grains of Ni matrix, thereby, increasing the hardness body particles called wear debris removed during the sliding. Along

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Fig. 15. Wear rate of mild steel, NiP, and NiP/CSP composite coatings (As-plated, Heat treated and laser treated).

with grooves, there was a shallow region in the wear track which in- with the iron in EN-31 resulted in an incompatible sliding surface,
dicated the existence of adhesive wear. Generally, NiP coatings are thereby causing a slight reduction in the adhesive wear and friction
subjected to severe adhesive wear on sliding against the carbon steel. coefficient of heat treated NiP coating. Typical characteristics of abra-
This is due to the high force of attraction between the nickel atoms from sive wear were also seen in the wear track of heat treated NiP coating
NiP coating and iron from the counterface. Hence, in the as-plated (Fig. 16b). Along with the abrasive wear, adhesive wear marks were
condition or at a high load condition, NiP coatings fail to sustain the spotted in the wear track but were very low compared to the as-plated
adhesive wear. As a result, the wear rate of as-plated NiP coating is high NiP coating. Primary cracks started generating on the wear track of heat
when compared to the heat treated and laser treated NiP coating. treated NiP coating due to the existence of crystalline nature in the
Heat treated NiP coating and laser treated NiP coating have shown a coatings.
low friction coefficient of 0.24 and 0.37 when compared to as-plated Laser treated NiP coating presented a lower wear rate and a slight
NiP coating. The low friction coefficient of heat treated NiP coating was increase in the friction coefficient when compared to the heat treated
due to improved hardness created by the Ni3P precipitates. The pre- NiP coating. The increase in the friction coefficient arose as a result of
sence of Ni3P phase in the soft Ni matrix could act as a hard precipitate the phase transformation of the coatings and formation of dendrites
and reduce the material (Ni) transfer from the coating to the EN-31 structure. The sliding interaction of FeNi2P phase in the NiP coating and
counterface. In general, nickel and iron have a high mutual solubility iron from the counterface resulted in an increase in the friction coef-
[24] indicating the substantial attractive forces between atoms of nickel ficient. The distribution of Ni3P, Ni12P5, and FeNi2P phase in the
and iron, as a result of which, adhesive wear was severe in the case of crystallographic structure played a vital role on decreasing the wear
as-plated NiP coating. However, in the case of heat treated NiP coating, rate of laser treated NiP coating. The formation of these phases de-
mutual solubility of nickel and iron obtained through the formation creases the mutual solubility of nickel with the iron of the counterface
Ni3P precipitates was low. Hence, the interaction of Ni3P precipitates during the sliding, thereby reducing the compatibility of two sliding

Fig. 16. SEM image of the wear track of (a–c) As-plated, Heat treated and laser treated NiP coating and (d–e) As-plated, Heat treated and laser treated NiP/CSP
(2.5 g/l) composite coating.

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surface (nickel and iron) as discussed earlier. The increase in the in- treated NiP/CSP composite coatings. There was a considerable increase
compatibility of two surfaces caused a substantial reduction in the wear in the friction coefficient with increase in the weight dispersion of CSP
rate of laser treated NiP coating. No cracks were seen in the wear track from 0.50 g/l to 2.5 g/l in the bath. The interaction of iron phase with
of laser treated NiP coating in contrast to the heat treated NiP coatings the iron elements of the counterface had increased the friction force
(Fig. 16c). The existence of the crystalline and amorphous phase tran- during the sliding as discussed earlier. Hence, the formation of FeNi2P
sition across grain-matrix interfaces of laser treated NiP coating limits phase in the NiP/CSP composite coatings had a great influence on the
the formation of cracks during their interaction with the counterface. increase in the friction coefficient. Among the various weight disper-
Wear track also evidenced the initiation of material removal due to the sions of CSP, NiP/CSP (2.5 g/l) composite coatings presented a high
soft matrix components (alpha nickel). Partial damage was also seen for friction coefficient of 0.65. This is because, the formation of FeNi2P
the dendrite structure (Ni3P, Ni12P5 and FeNi2P), as a result of the re- phase increases with increasing the weight percentage as discussed in
moval of soft nickel matrix during their interaction with the counter- the XRD analysis. Hence the interaction of FeNi2P phase against the
face. However, dendrites did exist on the wear track, playing a vital role counterface was found more for the laser treated NiP/CSP (2.5 g/l)
on the decrease in the wear rate of laser treated NiP coating. Therefore, composite coating. As result, there was an increase in the friction
the increase in the amount of hardening phase and dendrites formation coefficient for laser treated NiP/CSP (2.5 g/l) composite coatings when
had been the primary reason for a better wear resistance for laser compared to the other heat treated and as-plated NiP/CSP composite
treated NiP coating. coatings. Despite an increase in the friction coefficient, there was a
There was a reduction in the friction coefficient and wear rate for decrease in the wear rate for laser treated NiP/CSP composite coating
as-plated NiP/CSP composite coatings after the reinforcement of CSP in when compared to the other coatings. The decrease in the wear rate was
the NiP matrix. Friction coefficient decreased considerably with in- related to the presence of hard crystalline Ni3P, Ni, FeNi2P phases and
creasing the weight dispersion of CSP from 0.5 g/l to 2.5 g/l in the NiP amorphous Ni12P5 phase. The presence of these phases caused restric-
bath and found increasing for the 3.0 g/l dispersion. The decrease in the tions on the material removal during the sliding with the counter face.
friction coefficient was due to the lubricity created by the constituent's The reduction in the growth of dendrites structure also played a major
elements of CSP (Ca, Mg, and O) and matrix elements (Ni) in the surface role in decreasing the wear rate for laser treated NiP/CSP composite
of the NiP coating. The constituent elements of CSP were dissolved in coating. No deformation in the dendrites was observed in the wear
the NiP matrix during the solid solution strengthening process, as a track of laser treated NiP/CSP (2.5 g/l) composite coating after the
result of which, lubricity is increased for the NiP/CSP coatings [17]. sliding with the counter face (Fig. 16f). This was due to the better in-
Among the various weight dispersions of CSP, NiP/CSP (2.5 g/l) com- terface strength of dendrites (Ni3P and FeNi2P) with the Ni matrix.
posite coating presented a low friction coefficient of 0.06. This was due Though cracks were seen in the morphology of laser treated NiP/CSP
to the reinforcement of more constituent elements of CSP in NiP matrix. composite coating, its influence in the wear performance is very low, as
The presence of these elements in the coatings generally leaves a way the cracks were seen overlapped with the formation of tribolayer. A
for two factors; one is the increase in the lubrication during the sliding tribolayer was also seen in the wear track strongly adhered to the
against the EN-31 counterface and other is decrease in the compatibility surface. EDS confirms the presence of Ni, P, Ca, Mg and O elements in
of the two sliding surfaces. The decrease in the compatibility of two the wear track of laser treated NiP/CSP (2.5 g/l) composite coating
surfaces certainly reduced the adhesive wear. Hence, these two factors (Fig. 17). This indicated the existence of coatings in the wear track. In
resulted in a low friction coefficient and improved wear behavior. addition to the constituent's elements of NiP matrix and CSP, presence
Tribolayer formation was seen in the wear track of as-plated NiP/CSP of O is evidenced in the wear track. The presence of O indicates the
(2.5 g/l) composite coatings (Fig. 16d). However, its distribution was occurrence of oxidation during the sliding.
only partial. The poor adhesion of the tribolayer in the wear track fa- In case of laser treated NiP coating, wear was initiated by the re-
cilitated the material removal by the counter face during the sliding. moval of soft Ni matrix. However, it was restricted in the laser treated
The poor adhesion of tribolayer was primarily due to the amorphous NiP/CSP composite coating due to the strengthening of alpha nickel
nature of the as-plated NiP/CSP composite coating. with the constituents (Ca, Mg and O) of CSP and presences of hard
Heat treated NiP/CSP composite coatings had shown a low friction FeNi2P phase. These constituents increased the strength of Ni matrix in
coefficient and wear rate compared to the as-plated NiP/CSP composite such way that it produced enough lubrication and toughness to the
coating. There was a considerable decrease in the friction coefficient coatings during the sliding with the counterface. Therefore, laser
with increasing the weight dispersion from 0.50 g/l to 2.5 g/l similar to treated NiP/CSP composite coating presented a lower wear rate than
the as-plated NiP/CSP composite coatings. Heat treated NiP/CSP the as-plated and heat treated NiP/CSP composite coatings.
(2.5 g/l) composite coating exhibited a low friction coefficient of 0.01
and a low wear rate, which was comparatively lower than the as-plated 4. Conclusions
NiP/CSP (2.5 g/l) composite coating. This was due to the sustainment
of tribolayer formation in the wear track during the sliding. The phase Electroless NiP and NiP/CSP composite coatings were prepared with
transformation of NiP/CSP composite coating from the amorphous various weight dispersions of CSP. The following conclusions have been
phase to the crystalline phase certainly improved the adhesion of tri- drawn from a comparative study of heat treatment and laser treatment
bolayer in the wear track. As a result, the formed tribolayer tend to with as-plated NiP and NiP/CSP composite coatings:
adhere more efficiently than in the as-plated NiP/CSP composite
coating, thereby reducing the friction coefficient and wear rate. The • A spherical nickel globule was formed for as-plated and heat treated
formation of tribolayer was clearly seen in the wear track of heat NiP/CSP (0.5 g/l) composite coating with the initial dispersion of
treated NiP/CSP (2.5 g/l) composite coatings (Fig. 16e), indicating the CSP (0.5 g/l) and found increasing with the increase in CSP dis-
smooth sliding of the counterface. This smooth sliding evidenced the persion. Laser treated NiP and NiP/CSP composite coatings ex-
decrease in the friction coefficient and wear rate. In addition to the hibited a morphological change with the formation of dendrite
tribolayer, the formation of Ni3P precipitates and reinforcement of CSP structure. Laser treated NiP/CSP (2.5 g/l) composite coating showed
in the NiP matrix had increased the strength of the matrix while de- a reduction in the dendrite structure with maximum porosity as a
creasing the compatibility of two sliding surfaces. These two factors result of the high weight dispersion of CSP in the NiP matrix.
could also constitute the reason for the low friction and wear rate of • Formation of Meta stable phases was seen for heat treated NiP and
heat treated NiP/CSP composite coatings. NiP/CSP composite coatings. In addition to the Meta stable phases,
There was an increase in the friction coefficient for laser treated there was a formation of FeNi2P phase for laser treated coatings.
NiP/CSP composite coatings when compared to the as-plated and heat More FeNi2P phase was formed for NiP/CSP (2.5 g/l) composite

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Fig. 17. EDS mapping of the wear track of laser treated NiP/CSP (2.5 g/l) composite coating.

coating, which was due to the low hardness of the coating prior to on their structure and abrasive resistance of autocatalytic NiP and NiP–SiC coatings,
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