Engineering Failure Analysis 90 (2018) 310–323

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Engineering Failure Analysis

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

Controlling adhesive wear failure of nickel-phosphorus coating at

T
high load condition using crab shell particle as reinforcement
⁎
Arulvel S. , Elayaperumal A., Jagatheeshwaran M.S.
Department of Mechanical Engineering, Anna University, Chennai, Tamil Nadu 600025, India

A R T IC LE I N F O ABS TRA CT

Keywords: Electroless nickel phosphorus (NiP) alloy coatings have been used as a success in tribology ap-
Electroless coating plication. However, the severe adhesive wear failure at high loading condition is the dis-
Nickel advantage of NiP coating. To overcome this, crab shell particle (CSP) is used as reinforcement
Crab shell particles with nickel-phosphorus (NiP) coating. Phase structure, surface hardness, and surface features of
Adhesive wear
the coating have been studied using x-ray diffractometer (XRD), Vickers hardness tester, non-
contact-surface profilometer and scanning electron microscope (SEM).The dry sliding wear be-
haviour of NiP/ CSP composite coating against hardened en-31 steel was characterized using pin
on disc apparatus at various loads condition (4.90 N, 9.80 N and 14.70 N) in room temperature.
XRD analysis showed an intensity loss and shift in the peak for NiP/ CSP composite coating. Low
wear rate and low friction coefficient with stick slip phenomenon has been exhibited for NiP/CSP
composite coating at 14.70 N. CSP played a significant role in the reduction of adhesive wear by
minimizing the transfer of NiP layer to the en-31 steel. Various wear mechanism, such as abrasive
wear, adhesive wear, and tribolayer formation were discussed and reported.

1. Introduction

Mild steel has been the accepted material in many industrial applications such as, automobile, petrochemical, nuclear industries
and especially for making car body panels, engine parts, metal chains, nuts, and bolts considering the excellent quantities like low
cost, malleability and weld-ability. However, mild steel is still not recommended for tribology applications and, most importantly, for
components running in dry sliding condition. This is due to the abrupt transition of wear mode from mild to severe wear and vice
versa at various load condition. Generally, metals sliding in dry sliding condition could lead to three types of wear transitions: (i) T1
transition, from mild to severe wear at low loads, (ii) T2 transition, from severe back to mild wear at higher loads, and (iii) T3
transition, minor change in the wear rate above T2 transition [1]. These various wear transition regimes could lead to high material
loss and ultimately resulting in the failure of components. Many of the mechanical components usually operate under various load
condition under dry sliding condition. So, it is obvious to resist the wear transition of mild steel in various load condition, to make it
applicable for tribology applications.
Since wear is a surface deprivation property, surface engineering techniques were followed to modify the surfaces with required
characteristics [2]. Among the various techniques in practice, an extensive study has been made on the electroless deposition of NieP
alloy on metal substrate by researchers [3]. Electroless nickel-phosphorus (NiP) coating is commercially used in many industrial
applications due to its better tribology and mechanical property. Lubrication and hardness are the primary reason for sustainability of
NiP coating in friction and wear applications. However, severe adhesive wear is the predominant wear mechanism for NiP coating at

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

https://doi.org/10.1016/j.engfailanal.2018.04.004
Received 24 December 2017; Received in revised form 27 March 2018; Accepted 2 April 2018
Available online 04 April 2018
1350-6307/ © 2018 Elsevier Ltd. All rights reserved.
A. S. et al. Engineering Failure Analysis 90 (2018) 310–323

high load condition. This is overcome through electroless NiP composite coating, followed by co-depositing second phase particles
with NiP alloy matrix [4,5]. For the past few decade, the focus of research in electroless coating process has been on the re-
inforcement of hard particles with the NiP matrix [6,7], to enable the improvement of friction and wear property by increasing
hardness of the coating. Though wear is improved by the hardness, the other criterion for improving the wear property is increasing
lubrication between the two sliding surfaces. Metals sliding in lubricant condition uses oil as the intermediate medium for restricting
the contact of the two sliding surfaces. However, lubricant particle is necessary for dry sliding condition to improve the friction and
wear property. So, few works have reported the reinforcement of lubricant particle in the NiP matrix for improving the tribology
property [8]. However, increasing lubrication at the interface of the two sliding surfaces could lead to severe adhesive wear at high
load condition. Hence, a combination of lubricants and ceramics is preferred for minimizing the adhesive wear at high load condition.
On knowing the importance of it, few works were focused on reinforcing two compounds namely PTFE and SiO2 with the NiP matrix
for improving friction and wear property [9]. Hence, it is important to find a good combination of reinforcement (lubricant and
ceramics particles) to minimize the adhesive wear of the NiP coating. This combination is observed in the crab shell particles (CSP) to
a greater extent. Crab shell has been utilized in recent days for improving thermal property [10], mechanical property [11], ab-
sorption of heavy metals [12], synthesis of chitosan [13] etc.
In an earlier article of the author, feasibility of using proteinized and deproteinized crab shell particles for coating applications
was discussed precisely with their structural, chemical and physical properties [14]. The conclusion reached was that proteinized
crab shell particle can be utilized for coating applications without any processing. Commixture of two or more elements offers an
advantage of using CSP over the single filler reinforcement in the NiP matrix. The chelating ability of the crab shell particle is the
other added advantage of increasing nucleation during the coating process, as described in the author's previous article [15]. The use
of crab shell as a reinforcement material for coating application has not been the subject matter of any research article. Hence, the
investigation of crab shell particles for tribology application is the theme of the present work.
The study reports the friction-wear behavior of crab shell particle reinforced NiP composite coating on mild steel, fabricated using
the electroless process. Fabricated NiP and NiP/CSP composite coatings were characterized using x-ray diffractometer (XRD), Vickers
hardness tester, noncontact surface profilometer and scanning electron microscope (SEM). Friction- wear test was performed against
En-31 bearing steel in dry sliding condition at various loads using pin on disc apparatus in room temperature. Various wear me-
chanisms on the aid of wear debris, optical microscope, energy dispersive X-ray spectrometry (EDS), and SEM analysis were reported.

2. Materials and methods

2.1. Reinforcement particles

Crab shell (Carpilioidea species) wastes were collected from the Bay of Bengal, India. The collected wastes were then processed to
crab shell particles as discussed in the author previous article [14]. The particles were then made finer to a size range of 8 μm to
15 μm using a ball milling machine. The size of the particle measured using a particle analyser was not homogenous.

2.2. Specimen preparation and operating conditions for electroless coating

A spherical end mild steel pin with diameter of 6 mm and length 30 mm was used as a substrate for deposition of NiP coating and
NiP/CSP composite coating. All samples were ultrasonically cleaned with acetone for 5 min using an ultrasonicator and rinsed with
double distilled (DD) water. The specimen was then activated in dilute hydrochloric acid (HCL) for 4 min and in dilute nitric acid
(HNO3) for 2 min, followed by water rinse at room temperature. The specimen was then immersed in an alkaline electroless bath in
an electrolyte (volume: 1000 ml) containing the composition shown in Table 1. Bath pH was maintained in the range of 7 to 7.5 and
continuously monitored using pH-meter. The schematic representation of coating setup is shown in Fig. 1. After the coating process,
specimens were rinsed in DD water and dried with a stream of air. The samples were then subjected to heat treatment process at
400 °C using muffle furnace to increase the surface properties of the coating [16].

Table 1
Chemical composition and bath parameters of electroless bath.
Component Concentration

Nickel sulphate 20 g/l

Sodium hypophosphite 23 g/l
Sodium citrate 13 g/l
Lead acetate 0.001 g/l
Acetic acid 3–5 ml
Crab shell powder(CSP) 3.0 g/l
Agitation speed 350 rpm
Temperature 80 °C–90 °C

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Fig. 1. Experimental setup of electroless coating process.

2.3. Hardness test

The surface hardness of mild steel, NiP and NIP/CSP coating was measured using Vickers micro hardness tester (ECONOMET VH -
1D) at a load of 50 g for 15 s dwell time. The reported hardness value was the average of five readings measured across a distance of
5 mm on surface of the sample.

2.4. Microstructure study

Surface morphology and cross section of coated samples were observed using a scanning electron microscope. A cross section
image was taken using the following procedure: coated samples were cut across the cross section using EDM (Electrical discharge
machining) and mounted using a digital hot mounting machine (model RHM-2). The mounted samples were then polished using SiC
sand paper with various grid ranges (240, 600 and 800) followed by diamond paste finishing using a polishing machine. The average
grain size of the coated samples was measured in ASTM E112-13 using an image-j software tool.

2.5. Surface roughness measurement

Surface roughness was calculated by measuring the arithmetic mean deviation of peaks and valleys obtained in a surface area of
312 μm × 312 μm using noncontact surface profilometer (Taylor hobso). 3D surface pattern were also obtained for discussion on the
variation of peaks and valleys distributed across the surfaces.

2.6. X-ray diffraction studies

The structural characterization of coatings was done using X- ray diffractometer using CuKα radiation with a wavelength of 1.54 Å
from a diffraction angle 2theta from 5° to 80° at a step size of 0.02. The results were then matched with joint committee on powder
diffraction standards (JCPDS).

2.7. Friction-wear test

Dry sliding wear test was carried out using pin on disc apparatus (DUCOM) at various loads of 4.90 N, 9.80 N and 14.70 N in a
constant sliding velocity of 0.7 m s−1 at room temperature. Coated samples were taken as a pin and, hardened En-31 steel as a sliding
counterpart disc with a diameter of 55 mm and a thickness of 8 mm. Before the wear tests, specimens were ultrasonically cleaned
using acetone for eliminating dirt particles on the specimen surface. The mass of the samples was measured before and after wear test
using digital balancing machine with an accuracy of 0.00001 g. Average of 10 samples were taken and reported. Wear rate was
calculated using the formula shown in Eq. (1) [17]. Wear debris and wear track were characterized using an optical microscope,
noncontact surface profilometer and SEM to support the study of wear mechanism.

(Mass of the samples before wear test − Mass of the sample after wear test) (g)
Wear rate =
Total sliding distance (m) (1)

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3. Result and discussion

3.1. Formation mechanism of NiP and NiP/CSP composite coating

NiP and NiP/CSP composite coating was reported as having two mechanisms, namely electrochemical mechanism and mechanism
proposed by salvago and cavallott [18]. NiP coating generally follows an electrochemical mechanism, which is consistent with many
articles. The equation that represents electrochemical mechanism is shown in Eqs. (2)–(5).

H2PO2− + H2O → H2PO3− + 2H+ + 2e− (2)

−
Ni ++
+ 2e → Ni (3)
−
2H + 2e → H2
+
(4)
− −
H2PO2 + 2H + e → P + 2H2O
+
(5)

Generally electroless NiP composite coating is formed by the impingement and settling of particles on the surface of the substrate
[19]. Hence, there is no molecular bonding between the NiP matrix and the reinforced particles. However, this accounts for ceramic
particles, which are generally insoluble in nature. CSP is partially soluble and insoluble, which has been referred to the author
previous article [14]. Hence, the dispersion of CSP in the bath leads to two following phenomena, one is solubility of CSP giving out
carbonate (CO3), Calcium (Ca) and Magnesium (Mg) ions in the bath and the other is insoluble nature of CSP dispersed in the bath.
The surface of CSP was initially adsorbed by the Ni ions in the bath and it initiates the mechanism proposed by salvago and cavallotti
as discussed in the previous article [15]. After the particles were adsorbed with Ni, it gets direct interaction with the metal surface
surrounded by the hypophosphite ions in the electroless bath and continues the electrochemical mechanism. Then, the formed nickel
hydroxide in Eq. (6) could further react with hypophosphite ion and yields Ni on the surface of the mild steel as shown in Eq. (7). The
overall process continues repeatedly, due to which, nickel – phosphorus were simultaneously deposited on the surfaces of the mild
steel, and thereby NiP/CSP composite coating CSP is fabricated.

Ni + H2PO2− → P + NiOH+ + OH− (6)

− −
NiOH + H2PO2 → Ni + H2PO3 + H
+
(7)

The schematic representation of the formation mechanism of NiP coating and NiP/CSP composite coating is shown in Fig. 2. The
dissolved Ca and Mg ion tends to get located between the Ni and phosphorus atoms similar to the recent article on reinforcement of
sea shell particles in NiP matrix [20]. Hence, there could be a slight change in the property of the NiP matrix in terms of strengthening

Fig. 2. Formation mechanism of electroless NiP coating and NiP/CSP composite coating.

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Fig. 3. XRD pattern of a) CSP, b) NiP coating and c) NiP/CSP composite coating.

the dislocation. The other added advantage of CSP is adsorption phenomenon, which could enhance the role of sodium hypopho-
sphite on favouring the increased nucleation sites on the metallic surfaces, which is elaborated in the surface morphology study.

3.2. Structural characterization of CSP, NiP and NiP/CSP composite coatings

The XRD patterns of CSP, NiP, and NiP/CSP composite coatings are shown in Fig. 3. It is clear that, strong broadened peaks are
indexed to the magnesium calcite at 2theta = 26°–30° for CSP (Fig. 3a). The calcite phase of CSP is almost consistent with JCPDS
Card no. 05–0586, which has been referred to the author previous article [14].
The diffraction pattern of NiP coating matching with JCPDS card no. 65–2778 is shown in Fig. 3b. It shows the sharp diffraction
peak at 2theta = 44° of NiP coating, which evidences the existence of face center cubic Ni (111) plane. The presence of sharp peak
indicates that the structure of NiP coating is microcrystalline. Intermediate phase Ni12P5 (112) and Meta stable Ni3P (103) phase
peaks were formulated at 2theta = 37° and between 50° and 55° was assigned to the body center tetragonal plane, which is found

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Fig. 4. Schematic representation of Ni-Ni3P interfaces of a) NiP and b) NiP/CSP composite coating.

consistent with the article [16]. The existence of stable phase and an intermediate phase is related to the crystallization, which
occurred during the heat treatment process. The intensity of Ni was stronger than that of Ni3P, due to the presence of high Ni content
in the coating. Despite the intensity of Ni3P is low, the formation of Meta stable phases is primary reason for increasing the hardness
of the coating [18]. Fig. 3c shows the pattern of NiP/CSP composite coating, which almost matches with JCPDS card no. 65–2778
similar to NiP coating. It is known fact that, in electroless coating process, reinforcement of second phase particle has no effect on the
coating structure [21]. This is because the particles remain with their own phase within the NiP matrix even after the heat treatment
process. However, NiP/CSP composite coating presented an intensity loss and peak shift in contrast to the NiP coating. The loss in the
intensity of Ni is probably due to the reinforcement of second phase particles. The shift in the peak of Ni (111) to 2theta = 42° was
due to the internal stress developed by the reinforcement of CSP. The solubility of crab shell particles produced calcium and mag-
nesium solute atoms in the electroless bath [14]. These solute atoms created an internal stress in the crystalline lattice when located
between the nickel atoms during solid strengthening process and such internal stress was the primary reason for shift in the peak of
NiP/CSP composite. Among different solid solution strengthening process, the reported one of NiP/CSP composite coating is a defect
substitutional solid solution, where Ca, Mg, and Si atoms tend to occupy certain positions of the lattice and remains vacant at other
position. As a result, these atoms tend to locate between the Ni and Ni3P interfaces. Normally, NiP matrix forms with the result that,
Ni3P tends to be the convex phase on Ni–Ni3P interfaces as shown in the Fig. 4. Generally this arrangement increases the interfacial
free energy of Ni3P phases, so that the matrix possesses enough hardness and lubricity in the coating. In terms of NiP/CSP composite
coating, the inclusion of Ca and Mg atoms could decrease the interface strength of Ni and Ni3P, which could decrease the hardness as
discussed in the hardness analysis.

3.3. Micro hardness analysis of NiP and NiP/CSP composite coatings

Fig. 5 shows the hardness of mild steel, NiP, and NiP/CSP samples measured using Vickers hardness tester. Hardness chart
evidences the improvement in the surface hardness of mild steel after NiP and NiP/CSP coating. Mild steel presented a low hardness
of 123 HV0.05, followed by 296 HV0.05 of NiP/CSP composite coating and 506 HV0.05 of NiP coating. As for the hardness of coating,
NiP/CSP composite coating presents a low surface hardness when compared to the NiP coating. The incorporation of crab shell
particles into the NiP matrix decreases the hardness of NiP/CSP composite coating. This is because of the inclusion of calcium and
magnesium atoms between the Ni and Ni3P interface as discussed earlier. It is a well-known fact that, in the electroless coating
process, solid solution strengthening is the basic mechanism which certainly increases the hardness of the coating [20]. This is
because the hard reinforcement impurity tends to get located between the nickel atoms and thereby, restricting the dislocation of the
material. The decrease in the hardness on the reinforcement of softer particles has also been reported in many articles [8]. As a result,

Fig. 5. Hardness of uncoated, NiP coating and NiP/CSP composite coating.

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Fig. 6. SEM image of a) NiP coating and B) NiP/CSP composite coating.

highly available calcium and magnesium atom tend to occupy between the nickel atoms, which makes NiP matrix softer and thereby,
decreasing the hardness of the coatings.

3.4. Microstructure and cross section of NiP and NiP composite coating

Fig. 6 shows the surface morphology of NiP and NiP/CSP composite coatings. NiP coating (Fig. 6a) exhibited a typical nodular
structure with an average grain size of 13 μm, which are the actual characteristics of NiP coating as discussed in many articles [22].
NiP/CSP composite coating (Fig. 6b) presented a uniform distribution of NiP matrix with an average grain size of 5 μm. As for the
grain size of nickel matrix, there is a reduction in the grain size for NiP/CSP composite coating. The reduction in the grain size is the
result of the zener pinning effect. Apart from the reduction in the grain size, more nickel matrix globules was seen on the surface of
NiP/CSP composite coating in contrast to the NiP coating. The finer and more Ni globules indicate the high rate of Ni deposition in
the composites. The high rate of deposition was due to influence of CSP. Generally, in the electroless coating process, the rate of
deposition depends upon many factors such as bath pH, level of sodium hypophosphite, catalyst and surfactants. This leads to the
tendency of the dispersed CSP to act as a catalyst, and increase the rate of deposition in the bath. The chelating ability of CSP has been
discussed in the author previous article [15]. There are no pores and voids in the morphology of composite coatings after the
reinforcement of CSP, which could basically happen in the electroless coating process when the second phase particles are reinforced
in the NiP matrix. Recent articles have shown the formation of pores and voids in the morphology of the coating when second phase
particles are reinforced [23]. However, such phenomenon is not observed for CSP when it is reinforced in the NiP matrix, which is the
added advantage of using CSP for coating applications. Cross section of NiP and NiP/CSP composite coating is shown in the inlay
image of Fig. 6. It clearly reveals the homogenous distribution of NiP matrix over the mild steel substrate. Diffusion layer has shown
the strong interaction of the coating with the mild steel substrate. The deposited coating thickness of NiP coating and NiP/CSP
composite coating is 15 μm and 21 μm. As for the coating thickness, NiP/CSP composite coating presented a high thickness when
compared to the NiP coating. The primary reason for increase in coating thickness is due to the increased nucleation site on the
substrate. The increase in nucleation site was primarily due to the dispersion of second phase particles (CSP) in the bath. These
adsorbed second phase particles on the catalytic surface tends to act as an additional nucleation site for the growth of NiP matrix. This
caused an increase in the coating thickness for NiP/CSP composite coatings.
The 3D surface topography of mild steel, NiP coating and NiP/CSP composite coating measured using non-contact surface pro-
filometer is shown in Fig. 7. Mild steel exhibited a minimum roughness of 0.50 μm with low asperities as shown in the surface texture
Fig. 7a. The surface profile of NiP coating showed low waviness (Fig. 7b) and low roughness value of 0.52 μm when compared to high
roughness value of 0.68 μm of NiP/CSP composite coating Fig. 7c. There is only a slight change in the roughness value for NiP coating
when compared to the uncoated mild steel. The distribution of peaks and valleys were homogenous for NiP coating. Homogenous
distribution of NiP matrix implies the carrying out of efficient coating process. The increased roughness and waviness of NiP/CSP
composite was due to the reinforcement of second phase particle (CSP) in the NiP matrix. The existence of CSP in NiP matrix created a
geometric perturbation over the surface, which leads to high surface roughness of NiP/CSP composite coating.
Friction and wear are the major phenomenon which occurs during the interaction of two surfaces. Hence, it is obvious to
strengthen the interface of two sliding bodies by increasing the hardness of substrate and increasing the lubrication between the
sliding surfaces, to reduce the friction and wear. Load is the prime parameter that is taken in the account for investigating the friction
and wear property of mild steel, NiP, and NiP/CSP composite coating. Fig. 8 shows the friction coefficient curve of mild steel, NiP and
NiP/CSP composite coating against hardened En-31 steel at various load condition. It is an undeniable fact that mild steel presents a
high friction coefficient on sliding against the hardened En-31 steel when compared to NiP and NiP/CSP composite coating (Fig. 8a).
Friction coefficient of mild steel increases considerably when the applied load is increased from 4.90 N to 14.70 N.
The gradual increase in the friction coefficient implies the wearing out of high material from the mild steel substrate on increasing
the load condition. Fig. 9 shows the average wear rate plotted with respect to the different loading condition. It is obvious that the

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Fig. 7. Non-contact optical image and surface profiles of a) mild steel, b) NiP and c) NiP/CSP composite coating Friction-wear study.

wear rate of mild steel increased considerably on increasing the load from 4.90 N to 14.70 N. The increased friction force causes mild
steel to a severe wear.
For elaborative understanding of wear mechanism, wear track has been characterized using SEM. Fig. 10 shows the wear track of
mild steel, NiP and NiP composite coating at high load condition. The presence of ploughing marks, craters, and grooves implies that
mild steel are subjected to the severe abrasive wear Fig. 10a. The existence of microchips on the wear track indicates mild steel have
undergone a severe cutting process, which leads to high material removal from the surface. Two wear scar marks with different radius
are shown in the inlay image of Fig. 10a. This scar mark indicates the wear transient stages of mild steel from mild wear to severe
wear. Wear debris collected after the wear test at load 14.70 N is shown in Fig. 11a. It is clear that, the size of the wear debris
generated for mild steel is high when compared to the debris of NiP and NiP/CSP composite coating. The larger wear debris evidences
mild steel having undergone a severe wear during the sliding test. The existence of sliding grooves and cutting marks in the wear
debris also indicates the impression of abrasive-induced delamination wear.

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Fig. 8. Friction coefficient curve at varying load condition (4.90 N, 9.80 N and 14.70 N) of a) uncoated mild steel, b) NiP coating and c) NiP/CSP composite coating.
Engineering Failure Analysis 90 (2018) 310–323
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Fig. 9. Wear rate at different loads of a) uncoated, b) NiP and c) NiP/CSP composite coating.

Fig. 10. SEM images of the wear track at load 14.70 N of a) uncoated mild steel, b) NiP coating and c) NiP/CSP composite coating.

On comparison of the friction coefficient of uncoated and coated substrates, NiP/CSP composite coated substrate presented a low
friction coefficient (Fig. 8c), followed by NiP coating (Fig. 8b) at all load condition. The friction coefficient increases with increase in
the applied load for NiP coating. At low load of 4.90 N, the heat generated during the sliding test softens the NiP film and act as a
lubricant layer to give low friction coefficient. This lubricant layer could act as a tribolayer for minimizing the friction force and wear
rate of the NiP coating. On increasing the load to 9.80 N, the enough pressure starts to delaminate the lubricant film in terms of
adhesive wear mechanism and increases the contact area between the two sliding surface. The delamination of lubricant film and
detachment of wear debris got intensified on increasing the load to 14.70 N, which was the primary cause for the high friction
coefficient for NiP coating at high load condition.
As for the wear rate is concern, wear rate of NiP coating decreases on increasing the load from 4.90 N to 9.80 N. This was due to
the smeared interface layer over the contact surface. This interface layer called tribolayer plays a vital role in reducing the friction
force and mass loss. Generally, the adhesion of tribolayer layer to the contact surface is influenced in two cases, one is the existence of
strong intermolecular force and the other is on increasing the pressure on the pin. On account of that, the enough pressure on the pin
promotes the adhesion and transfer of tribolayer in the contact interfaces and creates enough lubrication to resist the sliding. Hence,

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Fig. 11. Wear debris collected at load 14.70 N of a) uncoated mild steel, b) NiP coating and c) NiP/CSP composite coating.

there was a decrease in the wear rate for NiP coating from load 4.90 N to 9.80 N. The increased wear rate of NiP coating at 14.70 N
were presumably related to the distortion of tribolayer occurred during the sliding. The formation of tribolayer for NiP coating was
not seen on the wear track at 14.70 N loading conditions (Fig. 10b), which evidences its distortion from the wear track. The high load
on the pin increases the pressure on the tribolayer. Hence on sliding, it was easy for the counter face to plough a formed tribolayer on
the NiP coating. So, NiP coating failed to sustain at higher load conditions. Along with the smooth surface, there was a mark of
ploughing furrows and slight scratches on the wear track of NiP coating, which is the characteristic of abrasive wear and adhesive
wear. These furrows and scratches are generally created on the wear track due to the third body particles commonly called wear
debris (Fig. 11b). The smooth worn out surface pattern of NiP coating indicates the existence of an adhesive wear as the counterface
slides over the NiP coating. NiP coatings are susceptible to severe adhesive wear and material transfer, when sliding against the
carbon steel. Hence, to discuss the wear mechanism in the counterface, optical image and EDS pattern of the wear track is shown in
Fig. 12. Fig. 12b shows the wear track of NiP coating, where the black patches was seen distributed along with the grooves. These
black patches were the material transferred from the NiP coating surface. The elemental composition of the black patches had shown
the presence of Ni and P in counterface, which evidences the transfer phenomenon. In addition to the existence of Ni and P, elements
like Fe, O and Si were also depicted, representing the chemical composition of the counterface. Adhesive wear was due to the
combination of low interfacial and high surface energies of the sliding materials, which produces highly compatible surfaces.
However, surface treatment of the coatings reduces adhesive wear by inducing crystallization of NiP. As an alternate to the surface
treatments, recent improvements on minimizing the adhesive wear of NiP coating by reinforcing suitable ceramic particles and
lubricant were followed. However, besides controlling adhesive wear, the reinforcement of ceramic particles could lead to high
friction force. Hence, it is important to find the reinforcement particles which present low friction coefficient and better wear
resistance.
In the case of NiP/CSP composite coating, there was a reduction in friction coefficient in respect of an increase in the load
condition (Fig. 8c). The decrease in friction coefficient for NiP/CSP composite coating is primarily due to the reinforcement of CSP in
the NiP matrix. Surface of NiP/CSP composite coating is a face centre cubic structure composed of Ni, P, Ca and Mg, which generally
has a strong intermolecular force. As a result, the formed tribolayer during the sliding tend to adhere more efficiently then the NiP
coating and hence, reducing the friction coefficient. The smearing of tribolayer in the wear track is increased on increasing the
pressure on the pin. Hence, on increasing the load condition from 4.90 N to 14.70 N, there was a considerable decrease in the friction
coefficient for the NiP/CSP composite coating. In addition to the presence of CSP on surface of NiP matrix, CSP present in subsurface
layer also come in contact with the surface during sliding and decreases the friction coefficient. Low negative friction coefficient was
observed for 14.70 N. The negative friction coefficient revealed the stick slip phenomenon during the sliding. Stick slip is generally
caused due to the existing of strong adhesive layer between the two sliding surfaces. The effect of roughness has no effect on the
friction property of the coatings, due to the exhibition of the low friction coefficient with increased roughness value. NiP/CSP
composite coating presented a low wear rate when compared to NiP coating and uncoated mild steel (Fig. 9c), which shows the
improvement in wear resistance after the reinforcement of CSP in the NiP matrix. In these conditions, the excellent lubrication and
anti-sticking properties of CSP disperse in the NiP matrix minimize the material removal from the surface. The reinforcement of CSP

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Fig. 12. Optical image and EDS pattern of the counterface used at 14.70 N of a) uncoated mild steel, b) NiP coating and c) NiP/CSP composite coating.
A. S. et al. Engineering Failure Analysis 90 (2018) 310–323

into the NiP matrix shows a direct correlation on decreasing the wear rate of the NiP/CSP composite coating. When a load of 4.90 N
was applied, the wear life of NiP/CSP composite coating was longer than that of NiP coated specimen. On increasing the load from
4.90 N to 14.70 N, the wear rate is decreased considerably for NiP/CSP composite coating. NiP matrix generally smears as a tribolayer
to resists the wear of the component as discussed earlier for the wear mechanism of NiP coating. Such tribolayer is seen in the wear
track of NiP/CSP composite coating even at 14.90 N along with the tearing marks (Fig. 10c). This is due to the strengthening of NiP
matrix by the CSP in two ways; one is particles sticking to the matrix and other is solid solution strengthening of the matrix. Both
conditions favour the delay in adhesive wear and removal of tribolayer formed during the sliding. When compared to the NiP coating,
no furrows and scratches were observed on the wear track of NiP/CSP composite coating. However, tearing marks were seen on the
wear track. This was due to the effect of second phase particles. Some of the CSP removed on the wear track was further pressed into
the soft NiP matrix during the sliding, which causes the tearing features on the worn surface. The second phase particles were seen
clearly embedded on the wear track of composite coating, which suggests the effective interaction of particles with the NiP matrix
even after the sliding. Fig. 12c shows the wear track and elemental composition of the counter face used for the NiP/CSP composite
coating, where it evidences the limited amount of material transfer from the coating surface. The reduction in the material transfer of
NiP/CSP composite coating indicates the control over adhesive wear after reinforcing CSP in the NiP matrix. Also, when the load is
increased, the fracture toughness could be the important factor for the wear life of the coating. This could results in the introduction
of fatigue wear. However, such phenomenon is not observed for NiP/CSP composite coating, which suggests the advantage of using
CSP as reinforcement with NiP matrix.

4. Conclusion

Electroless NiP/CSP composite coating was successfully fabricated using alkaline electroless nickel- phosphorus bath. Friction and
wear properties of NiP coating were modified by reinforcing crab shell particles into the NiP matrix. The following conclusions have
been drawn from the experimental characterization:

• The results confirm that, the incorporation of crab shell particles does not have any influence on the structure of the coating, as
there is a similar existence of peaks NiP and Ni P for both NiP and NiP/CSP composite coating.
3

• Grain size of NiP/CSP composite coatings reduced 62% after reinforcing crab shell particles with NiP matrix and also, solubility of
CSP decreased the hardness of NiP/CSP composite coatings.
• Surface roughness of NiP/CSP composite coating is increased after reinforcing second phase CSP in the NiP matrix. However, it
does not have any influence on the friction coefficient at any load condition.
• NiP/CSP composite coating exhibited a low friction coefficient with stick slip phenomenon due to the smearing of NiP layer and
presence of CSP.
• wear mechanism of electroless NiP and NiP/CSP at varying load conditions presented a various combination, such as abrasive
The
wear, adhesive wear and tribolayer formation.
• The overall conclusion is that, crab shell particles can be effectively used as a second phase particle for minimizing friction
coefficient and adhesive wear in dry sliding condition.

Acknowledgement

The author thanks the UGC (NFST scheme) for providing stipend for doing research and also to the Engineering Design Division,
(Grant No: 201516-NFST-2015-17-ST-TAM-2123) Anna University, Chennai, Tamilnadu, India, for providing the facilities needed for
this research.

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