Surfaces and Interfaces 6 (2017) 177–189

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Surfaces and Interfaces

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

Study of wear and friction of chemically deposited Ni-P-W coating

under dry and lubricated condition
Santanu Duari, Arkadeb Mukhopadhyay, Tapan Kr. Barman, Prasanta Sahoo∗
Department of Mechanical Engineering, Jadavpur University, Kolkata 700032, India

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

Article history: In the present work, ternary Ni-P-W coating is deposited on mild steel substrates from an alkaline hy-
Received 9 June 2016 pophosphite based electroless bath. The coatings are characterized in terms of their composition, phase
Revised 11 January 2017
structure and surface morphology using energy dispersive X-ray analysis, X-ray diffraction analysis and
Accepted 18 January 2017
scanning electron microscope. It is seen that the coatings exhibit a mixture of X-ray amorphous and
Available online 3 February 2017
nanocrystalline nature in their as-deposited condition due to the co-deposition of tungsten and turns
Keywords: crystalline on heat treatment at 400 °C for 1 h. A typical nodular surface morphology is observed in scan-
Electroless ning electron micrographs. Microhardness and surface roughness of the coatings are also reported. Tri-
Ni-P-W bological characterization of the coatings are carried out on a pin-on-disc configuration tribo-tester by
Wear varying the test parameters namely the applied normal load, sliding speed and sliding duration with co-
Friction efficient of friction and wear depth being the responses. The tests are carried out under lubrication as
Hardness
well as in dry condition to strike a comparison between the two environments. Wear depth is seen to
Roughness
Lubrication
increase with an increase in the applied normal load, sliding speed as well as sliding duration under lu-
bricated condition. The variation of COF under lubricated condition is seen to be quite complex due to
the synergistic effects of the tribo-testing parameters, lubrication, coating surface morphology and mi-
crostructure. A noteworthy improvement in the tribological behavior of Ni-P-W coating is achieved under
lubricated sliding condition.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction In general, EN coatings can be classified as pure nickel, nickel

Electroless nickel (EN) plating is a process of coating deposition
on a substrate without the use of electricity. It is an autocatalytic
process; where reduction of metal ions in the solution and the
coating deposition is carried out through the oxidation of a chem-
ical compound present in the solution itself i.e. a reducing agent.
An electroless bath comprises of an aqueous solution of metal ions,
reducing agent, bath stabilizer and complexing agent. The devel-
opment of this variant of coating technology can be accredited to
Brenner & Riddell in the year 1946 [1]. Though electroplating is a
more straight-forward process, electroless coatings have received
wide acceptance because of their enhanced mechanical and tribo-
logical properties [2]. Most importantly the deposition of coating is
uniform and intricate parts can be coated very easily. This process
is widely used in various industries such as electrical, aerospace,
automotive, electronics, etc [3]. EN coatings possess enhanced wear
resistance and hardness, and thus mostly find their use in applica-
tions requiring lower friction and wear of parts [1–5].
∗
Corresponding author.
E-mail addresses: psjume@gmail.com, psju_me@yahoo.com (P. Sahoo).
alloy coatings (binary, ternary or polyalloy coating) [5–10] and
electroless nickel composite coatings [3,11–13]. Hypophosphite re-
duced Ni-P coating and borohydride reduced Ni-B coating have al-
ready gained immense significance because of their enhanced tri-
bological properties such as low surface roughness, high hardness,
high resistance to wear and abrasion and good corrosion resis-
tance. They also have reduced friction properties due to their mi-
crostructure. Ni-B coating has a cauliflower like structure making it
self-lubricating in nature [7,14–16]. The hardness of both Ni-P and
Ni-B increases significantly with heat treatment as well as by vary-
ing the bath components [17,18]. But the hardness for both of them
degrades significantly with excessive heating [2,5,17]. The wear re-
sistance of electroless nickel coatings can be improved by incor-
porating hard particles such as TiO2 , SiC, Al2 O3 , diamond, etc., the
choice of which depends on the application for which it is required
[19–20]. To reduce the friction coefficient, generally solid lubri-
cants (PTFE, graphite and MoS2 ) are co-deposited along with Ni-P
[21–23].
The first instance of electroless Ni-P-W coating was presented
by Pearlstein and Weightman [24]. Since then efforts are made to
study and improve the tribological properties such as hardness,

http://dx.doi.org/10.1016/j.surfin.2017.01.009
2468-0230/© 2017 Elsevier B.V. All rights reserved.
178 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189
wear, friction and corrosion resistance of the coatings. The incor-
poration of a transition metal like W leads to enhanced mechan-
ical and tribological properties along with high thermal stability
[25]. The hardness is seen to improve with an increase in the tung-
sten content. Wear resistance and crystallinity of the coatings in-
crease considerably with an increase in tungsten content, though,
the crystallization temperature of Ni-P coating increases with the
addition of tungsten [26]. An increase in hardness and wear resis-
tance on annealing is observed compared to the as-deposited elec-
troless Ni-P-W coating and this can be attributed to the precipita-
tion of crystalline nickel and its phosphides on heat treatment as
well as solid solution strengthening [27–29]. A higher heat treat-
ment temperature of 600 °C affects the coatings adversely. Pala-
niappa and Seshadri [30] observed that the highest hardness can
be achieved on heat treating the coatings at 500 °C for 1 h and it
decreases on heating beyond this due to softening and grain coars-
ening. In the same study it was reported that on carrying out tri-
bological tests at 40 N load on a pin – on – disc tribo-tester, the
resistance to wear increases with an increase in W content. The
COF was found to be quite high for the as-deposited coatings com-
pared to the heat treated ones and increases further on increasing
the applied normal load. Liu et al. [31] found out that microstruc-
tures and morphology of the coatings involving nanocrystallization,
phase transformation, porosity formation and grain growth could
be controlled by changing the phosphorus content of Ni–P–W ma-
trix and by performing different thermal treatments and the best
resistance to wear could be obtained by laser treatment of the
coating. Roy and Sahoo [8,32] employed Taguchi’s design of exper-
iments and grey relational analysis for the improvement of wear
and friction behavior as well as enhanced corrosion resistance of
Ni-P-W coating. Deposition of electroless Ni-P-W/ Nb2 O5 compos-
ite coatings onto NdFeB substrates results in excellent microhard-
ness, corrosion resistance and the interfacial adhesion strength can
be improved by tailoring the bath constituents [33]. Compared to
the ternary Ni-P-W alloy, a composite formed by the deposition of
Ni-P coating on tungsten particles result in more hardness, thick-
ness and deposition rate [34].
From the literature review, it is seen that there is a scarcity of
studies pertaining to the tribological behavior of EN coatings un-
der lubrication. Some investigations have been carried out for Ni-P
and its composite variants as well as Ni-B coating [35–39]. A po-
tentially hard surface coating like Ni-P-W can prove to be a suit-
able alternative for improving tribological behavior of mating parts
working under lubrication. Hence, the present study is an attempt
to analyze the tribological performance of electroless Ni-P-W coat-
ing with respect to varying combination of tribo-testing param-
eters (applied normal load, sliding speed and sliding time) on a
pin-on-disc type tribo-tester under oil lubricated condition. Tribo-
logical tests are also carried out under dry condition to strike a
comparison between the two sliding environments and observe the
improvement in wear and COF if any. Prior to that, coating charac-
terization is done using scanning electron microscopy, energy dis-
persive X-ray analysis and X-ray diffraction analysis to study and
analyze the surface morphology, composition of the coating and
microstructural characteristics. The hardness and surface roughness
of the coatings are also ascertained by using microhardness tester
and surface profilometer respectively.
2. Experimental details
2.1. Preparation of substrate and coating deposition
Cylindrical mild steel specimens (AISI 1040) of diameter 6 mm
and length 30 mm are taken as substrate material for the depo-
sition of electroless Ni-P-W coating. The percentage by weight of
different elements in AISI 1040 steel other than Fe is presented in
Table 1
Composition of AISI 1040 steel.
Composition C Si Mn S P
Percentage by weight 0.35–0.45% 0.15–0.4% 0.6–0.9% 0.04% 0.05%
Table 1. Specimens are grinded to obtain a smooth surface finish
and only the specimens corresponding to N6 grade (Ra = 0.8 μm)
is selected for coating deposition. This is particularly important
since electroless nickel coatings follow the surface profile of the
substrate. The substrate is cleaned from foreign matter, corrosion
products and oxide layers by rinsing in deionized water. Finally,
the specimens are given a pickling treatment with dilute (50%) hy-
drochloric acid. Prior to coating deposition, the substrates are im-
mersed in warm PdCl2 (55 °C) to build active sites for the deposi-
tion to initiate. This step is known as ‘activation’ and is incorpo-
rated to kick-start the deposition process. It is quite interesting to
note that though the substrate is a catalytically active one, PdCl2
activation is done such that the initiation of the deposition takes
place soon after immersion into the electroless bath. This leads to
a good deposition rate and a significant coating thickness suitable
for carrying out the tribological tests. In the mean time, the elec-
troless bath is prepared by mixing the chemicals as mentioned in
Table 2 in appropriate sequence. A bath volume of 200 ml is taken
for the electroless deposition. The coating bath formulation and
deposition condition are kept same to obtain a uniform deposition
for all the specimens. Coating deposition is carried out for 3 hrs.
After 3 hrs of deposition, the coated specimens are rinsed in deion-
ized water. They are subjected to heat treatment at 400 °C for 1hr
in a muffle furnace and allowed to cool inside the chamber itself
up to the ambient condition.
2.2. Coating characterization
The characteristics of the coatings that are mainly analyzed are
its composition, phase transformation, microstructure and surface
morphology. Composition of the coating is determined from en-
ergy dispersive X-ray (EDX) analysis (FEI, FEG Quanta 250). The
phase transformation analysis is carried out in an X-ray diffrac-
tion (XRD) analyzer (Rigaku, Miniflex) to determine the change in
phase pre and post heat treatment. Surface morphology study is
done on a scanning electron microscope (SEM) (JEOL, JSM 6360).
The microstructure of the coatings is studied by performing SEM
on the as-deposited as well as heat treated specimens. The coat-
ing thickness is obtained from the SEM micrograph of a cross cut
specimen. SEM micrographs of worn out specimens are obtained
to analyze the predominating wear mechanism under lubricated as
well as dry condition.
2.3. Measurement of microhardness and surface roughness
In the present study microhardness of Ni-P-W coating is car-
ried out in a UHL microhardness tester (VMHTMOT, Technische
Mikroskopie) with a Vickers diamond indenter. A load of 500 gf
is applied while the dwell time and indentation speed are kept at
15 s and 25 μm/s respectively. An average of 6 hardness values is
acquired from the microhardness tester.
As discussed earlier electroless nickel coatings follow the sur-
face profile of the substrate. Moreover, friction and wear are de-
pendent on the surface roughness of the mating parts. Hence,
the substrates to be coated are selected with precision. The cen-
tre line average surface roughness (Ra ) parameter is evaluated to
serve the purpose. Roughness measurements are taken prior to
coating deposition as well as after coating. Specimens with almost
same levels of surface roughness value are used in the wear and
 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189 179

Table 2
Bath composition and operating condition for deposition of Ni–P–W.

Bath constituents Values Operating condition Values

Nickel Sulphate (source of nickel) 20 g/l pH 7–8

Sodium Hypophosphite (reducing agent) 20 g/l Bath temperature 90 ± 2°C
Sodium Citrate (complexant) 35 g/l Duration of coating 3h
Ammonium Sulphate (accelerator) 30 g/l Bath volume 200 ml
Lactic Acid (stabilizer) 5 g/l Annealing temperature 400 °C
Sodium Tungstate (source of tungsten) 25 g/l (for 1hr in a box furnace)

Table 3 experiment. Normal load is applied by placing dead weights on

Tribological test parameter levels.
a pan attached to a loading lever (ratio 1:1). Wear is measured
Design factors Unit Levels in terms of displacement (μm) by a LVDT (Syscon) having a least
1 2 3 4 5
count of 1 μm and an accuracy of 1 ± 1% of measured wear. Fric-
tional force is acquired using a 20 kg beam type load cell (IPA) hav-
Load (L) N 10 15 20 25 30
ing a least count of 0.1 N and an accuracy of 0.1 ± 2% of measured
Speed (S) RPM 60 70 80 90 100
Time (T) Min. 3 6 9 12 15 friction force. The variation of friction force and wear depth are
recorded and displayed online via a computer attached to the tri-
botester. The friction and wear tests are carried out under dry and
lubricated condition. The lubricant used is Servo PRIDE 40 com-
friction tests. Measurements are taken using Talysurf profilome-
mercially available engine oil produced by Indian Oil. A detailed
ter (Surtronic 3 +, Taylor Hobson). It is equipped with a diamond
setup of the tribotester is depicted in Fig. 1.
stylus having a tip radius 5 μm. Measurements are taken using
0.8 mm sampling length and 4 mm traversing length. Roughness 3. Results and discussion
measurements on the coated samples have been repeated at least
four times and average of four Ra values are recorded. 3.1. Composition, phase transformation, surface morphology and
coating thickness
2.4. Tribological tests
Composition analysis of the coatings is essential because the
The friction and wear tests are carried out on a pin – on – disc percentage by weight of phosphorus deposited determines the
configuration tribotester (TR-20LE-CHM-400, DUCOM, INDIA). The crystallinity of the coatings. Incorporation of tungsten in the bi-
heat treated Ni-P-W coated specimens are held stationary using nary alloy system leads to an increase in the crystallization tem-
an attachment provided against a rotating counterface disc of EN perature of the binary Ni-P coating which in general crystallizes at
31 specification (Ø165 × 8 mm) hardened to 60 HRc and ground to 350 °C [40]. The EDX spectrums of as-deposited and heat treated
1.6 Ra surface roughness. The track diameter is kept constant at specimens are shown in Fig. 2(a) and (b) respectively. The peaks of
80 mm. The applied normal load, sliding speed and sliding time nickel, phosphorus and tungsten are quite specific confirming their
are varied as per the levels enlisted in Table 3. Accordingly, 125 presence in the coatings. The percentage by weight of nickel, phos-
experiments (53 ) are performed following full factorial design of phorus and tungsten deposited are 84%, 12% and 4% respectively in

Fig. 1. Tribological test setup.

180 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189
(a)
(b)
Fig. 2. EDX spectrum of electroless Ni-P-W coating: (a) as deposited and (b) heat
treated.
the as-deposited coatings. This is an indication of high phosphorus
range coatings and it is expected that the coatings could be amor-
phous in nature.
To confirm the phase transformation and analyze the effect of
heat treatment on the coatings, XRD is carried out both before and
after heat treating the coatings at 400 °C for 1hr as shown in Fig. 3.
As expected from the EDX analysis, the as-deposited coatings are a
mixture of amorphous and nanocrystalline phases having a broad
peak superimposed with a sharp one of Ni. The as-deposited coat-
ings are not fully amorphous which could be due to the tungsten
deposition in the Ni-P matrix. On annealing, the coatings show
crystalline nature with high reflection from Ni peak. This happens
due to the crystallization of nickel. Short peaks of Ni3 P are ob-
served due to the precipitation of nickel and its phosphides. No
metastable phases are observed for heat treated Ni-P-W coatings
and the major peaks happen to be of Ni and Ni3 P only. The obser-
vations are seen to be in accordance with previous research works
[27,28,30].
The investigation of surface characteristics of electroless Ni-P-
W coating is done using SEM. EN coatings, as investigated by sev-
eral researchers are self lubricating in nature since they exhibit a
nodular surface morphology [2,3,5,14,15]. The microstructure has a
significant effect in reduction of friction and wear of EN coatings
under dry as well as lubricated condition [14]. Hence, it is nec-
essary to study the surface structure of electroless Ni-P-W coat-
ing such that its effect on the friction and wear behavior of the
coatings under lubricated condition can be analyzed. SEM micro-
graphs of an as-deposited and heat treated specimen are shown in
Fig. 3. XRD patterns of electroless Ni-P-W coating for as deposited and heat treated
samples.
Fig. 4(a) and (b) respectively. A nodular surface morphology similar
to that of a cauliflower can be observed for both as-deposited and
heat treated coatings. The coating deposited is quite homogenous
without any porosity. SEM micrograph at higher magnification of
800X for as-deposited and annealed coatings are shown in Fig. 4(c)
and (d) respectively. On increasing the magnification bright parti-
cles are visible to be scattered all over the coating surface. This can
be attributed to the excess growth of nickel alloy over the nod-
ules. Similar results were obtained by Selvi et al. [41] and it was
explained that this excess growth could be due to the mixed com-
plex in the electroless bath which acts as a precursor for the de-
position of the alloy. On heat treatment the nodules are seen to
become more compact and some amount of volume contraction is
observed in Fig. 4(d). The coating thickness is observed to be quite
uniform over the substrate and is around 30 μm as can be seen in
Fig. 4(e) in the SEM micrograph of a cross-cut section.
3.2. Microhardness and surface roughness
Microhardness of electroless nickel coatings are seen to have a
direct relationship with the wear resistance. Heat treated electro-
less nickel coatings present a virtually incompatible surface to the
counterface material which leads to low wear and COF. Though,
heat treatment to a very high temperature leads to deterioration
of the tribological behavior of the coatings due to grain coars-
ening and softening. A high hardness is obtained for heat treat-
ment upto 500 °C. But heat treating at 600 °C for 1 hr affects the
coating adversely [30]. In the present study, the as-deposited coat-
ings are seen to have a hardness value of 678 HV0.5 . On anneal-
ing at 400 °C for 1hr in a furnace, a significant rise in hardness is
achieved with a value of 994 HV0.5 . This can be attributed mainly
to the precipitation of hard stable phases of Ni3 P and crystalline
Ni as well as the solid solution strengthening effect which can be
inferred directly from the XRD plot (Fig. 3). The hardness values of
as-deposited and annealed coatings for all the 125 specimens are
shown in Fig. 5.
Substrate roughness plays an important role in determining the
roughness of deposited coatings, their tribological behavior, corro-
sion resistance as well as adhesion. A higher surface roughness of
 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189 181

Fig. 4. SEM micrograph of Ni-P-W coating (a) as-deposited at 150X (b) heat treated at 150X (c) as-deposited at 800X (d) heat treated at 800X and (e) cross-cut section.

the substrate leads to a more compact and defect free electroless
nickel coatings and enhanced corrosion resistance is achieved [2].
The average surface roughness value for the substrates is taken to
be 0.8 μm. For electroless Ni-P-W coatings obtained from chloride
based baths, the surface roughness is lower compared to the ones
obtained from sulphate based baths [42]. Ra value of Ni-P-W coat-
ings after annealing at 400 °C for 1hr is measured. The average
value of the 125 specimens is seen to be around 0.9148 μm with
very low deviation (1%) which is expected since the substrates
with similar deviation are chosen for deposition though Ra is a lit-
tle higher than the substrate roughness. The roughness profile of a
specimen is shown in Fig. 6. A constant value of Ra eliminates the
effect of roughness on tribological behavior of the coatings.
182 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189
Fig. 5. The microhardness of the 125 test specimens in their as-deposited and heat treated condition prepared to carry out the tribological tests under dry and lubricated
condition.
µm Length = 4 mm Pt = 10 µm Scale = 20 µm
8
6
4
2
0
-2
-4
-6
-8
-10
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Fig. 6. Roughness profile of a heat treated Ni-P-W coating. The abscissa denotes the traversing length of stylus in ‘mm’ while the ordinate denotes the variation of surface
profile above and below the mean line in ‘μm’.
3.3. Wear behavior and mechanism of Ni-P-W coatings
The wear behavior of electroless Ni-P-W coatings is evaluated
under lubricated sliding condition. The applied normal load, slid-
ing speed and sliding time are varied at 5 different levels. The
plots for wear depth against time at constant loads of 10 N and
30 N for varying sliding speed are shown in Fig. 7(a) and (b) re-
spectively. Similarly, the plots for varying wear depth with respect
to sliding duration at constant sliding speeds of 60 and 100 rpm
with increasing load are shown in Fig. 8(a) and (b) respectively.
Plots for lowest and highest value of applied normal load and slid-
ing speed are shown while the others are omitted for the brevity
of the paper.
At a constant load of 10 N, the wear depth is seen to increase
with an increase in the sliding speed (Fig. 7(a)). In the same plot,
the wear depth at 100 rpm at 10 N is seen to be quite high though,
the wear rate is seen to be almost constant. Initially, a high wear
is experienced due to the running in period and the slope of the
plots is seen to decrease after a sliding duration of 6 min. The plots
at a load of 30 N exhibit an increasing trend in the wear behav-
ior with respect to the sliding duration (Fig. 7(b)). The wear depth
is seen to be quite high compared to the trends obtained at 10 N
load. The wear rate is also seen to be higher at 30 N and shows
an incremental trend. Thus, wear depth increases with an increase
in sliding speed at a constant applied normal load. On increasing
the sliding speed, the sliding distance increases and higher wear
1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 mm
is observed. The wear rate exhibited in Fig. 7(a) for a load of 10 N
is quite lower compared to 30 N load as shown in Fig. 7(b). This
can be due to the breakage of the oil film at higher load and in-
adequate lubrication. Moreover, on increasing the load, the mating
surfaces advance more towards each other. The actual contact area
of the asperities increases due to inadequate lubrication film and
higher wear is encountered by the coatings.
The wear depth increases with an increase in load from 10 N to
30 N at a constant speed of 60 rpm as can be seen in Fig. 8(a). The
wear rate is quite low at 60 rpm and at all values of load. On in-
creasing the sliding speed to 100 rpm, the wear depth is seen to be
increasing with load and is quite higher than obtained at 60 rpm
(Fig. 8(b)). The wear rate is again seen to be on the higher side for
all the plots at 100 rpm in Fig. 8(b). Thus, from Figs. 7 and 8, it can
be assimilated that wear depth increases with applied normal load,
sliding speed and sliding time. This is in accordance with Archard’s
law of wear. It can also be concluded that higher values of applied
normal load and sliding speed are detrimental to the coatings from
the view point of wear under lubricated sliding conditions.
Wear tests are carried out for Ni-P-W coatings under dry condi-
tion and compared to the ones under lubricated condition and the
plots are shown in Fig. 9. Under dry sliding condition, the wear
depth is seen to increase with sliding speed at an applied normal
load of 10 N as well as 30 N. With respect to sliding time, the wear
depth is again seen to increase. The trend of wear behavior un-
der dry condition is similar to the ones obtained under lubricated
 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189
Fig. 7. Wear vs. sliding duration with different sliding speed at constant load of (a)
10 N and (b) 30 N.
condition and corroborating well with Archard’s wear law. A sig-
nificant improvement in the wear behavior of the coatings is ob-
tained under lubricated condition as can be seen in Fig. 9. Nodu-
lated surface morphology and high hardness leads to a low wear
of electroless nickel coatings. Enhanced tribological behavior is ob-
tained under lubricated condition. Another reason for the low wear
of the coatings under lubricated condition can be due to the lu-
bricant carrying away the heat generated and lowering the flash
temperature at the contact point of the asperities. The observed
trends presented in Fig. 9(a)-(e) are almost invariant with time i.e.
the trends observed for wear depth at the end of 3 min is simi-
lar to that observed after 15 min with the applied normal load and
sliding speed. Though, a sudden decrease in the wear depth is ob-
served in Fig. 9(e) for an applied normal load of 10 N and 90 rpm
sliding speed. Moreover, at an applied normal load of 10 N, though
the wear depth is seen to increase with an increase in the slid-
ing speed, the change is not very drastic up to a sliding speed of
90 rpm as can be seen in Fig. 7(a). This may happen at a lower load
of 10 N due to a larger normal momentum transfer in the upward
direction with an increasing sliding speed [43]. This causes a sepa-
ration in the coating surface and the counterface disc and reduces
183
Fig. 8. Wear vs. sliding duration with different load at constant speed of (a) 60 rpm
and (b) 100 rpm.
the real area of contact between the asperities. Moreover, there
is a possibility of fine wear debris getting entrapped between the
mating surfaces leading to rolling effects and a reduction in wear.
Thus, a combination of these two phenomena might have resulted
in a sudden drop at 10 N and 80 rpm condition in Fig. 9(e).
To analyze the predominating wear mechanism, SEM micro-
graphs of the wear scars are taken after the tribological tests for an
applied normal load of 10 N, sliding speed of 100 rpm and sliding
duration of 15 min as shown in Fig. 10. It can be seen that some of
the nodules have undergone rubbing action. No pits or prows can
be observed. Mainly, minor scratch marks are visible at the sur-
face of the nodules in Fig. 10(a). When the worn surface is viewed
at a higher magnification of 20 0 0X (Fig. 10(b)), it can be clearly
understood that mild abrasive wear has taken place. The flowing
lubricant prevents adhesion of the coatings to the counterface ma-
terial. Moreover, on heat treatment, crystalline Ni and Ni3 P is pre-
cipitated which have low mutual solubility with iron and present
an incompatible surface to the steel counterface disc [30]. Hence,
mild abrasive wear failure of the coatings is established. The wear
behavior of electroless nickel coatings under lubricated condition is
184 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189

(a) (b)

(c) (d)

(e)
Fig. 9. Comparative analysis of wear behavior of Ni-P-W coating after (a) 3 min, (b) 6 min, (c) 9 min, (d) 12 min and (e) 15 min under lubricated and dry condition.
 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189 185

(a) (b)
Fig. 10. SEM micrograph of wear track under lubricated condition at (a) 800X and (b) 20 0 0X magnification for an applied load of 10 N, sliding speed of 100 rpm and sliding
duration 15 min.

(a) (b)
Fig. 11. SEM micrograph of wear track under lubricated condition at 30 N load and 15 min sliding time and sliding velocity (a) 60 rpm (b) 100 rpm.

governed by another important factor which is surface smoothen-
ing effect and formation of protective tribo films on the coating
tips [14,35]. Tribo layers prevent the coating to directly come in
contact with the counterface disc. This leads to low wear of the
coatings. But, this effect seems to absent when the coatings are
tested at 10 N normal load (Fig. 10). But when the coatings are
tested at 30 N normal load and 15 min sliding duration, the sur-
face smoothening effect can be observed in Fig. 11(a) and (b). Wear
mechanism is again abrasive in the present case. The SEM mi-
crographs in Fig. 11 mainly represent the change in wear behav-
ior on increasing the sliding speed at 30 N load. As discussed ear-
lier, higher values of tribo-testing parameters lead to higher wear
of the coatings under lubricated condition. The same can be con-
firmed from Figs. 10 and 11. The wear of the coatings is also seen
to increase on increasing the sliding speed from 60 rpm to 100 rpm
at a constant load of 30 N (Fig. 11). Thus wear mechanisms repre-
sented in Figs. 10 and 11 are seen to be in accordance with the
trends of wear behavior obtained in Figs. 7 and 8.
The wear mechanism under dry sliding condition is established
from SEM micrograph of the wear tracks as shown in Fig. 12(a) and
(b) at a magnification of 80 0X and 40 0 0X respectively correspond-
ing to an applied normal load of 30 N, sliding speed of 100 rpm and
15 min sliding duration. No detachment of the coating from the
substrate is observed. Parallel grooves along the direction of sliding
with high degree of plasticity can be seen in Fig. 12(a) which is the
indication of ductile failure of the coatings and wear debris get-
ting displaced to the sides of the wear track is visible in Fig. 12(b).
From the results, it can be assimilated that highly abrasive wear
mechanism is predominant. The ranges of test parameters selected
to evaluate the tribological performance of Ni-P-W coating might
have resulted in abrasive wear. On comparing the SEM micrographs
under lubricated condition (Fig. 11(b)) with dry condition (Fig. 12),
it can be clearly understood that the coatings undergo higher wear
under dry condition compared to lubricated condition. In Fig. 9, it
can be seen that at 30 N load, 100 rpm speed and 15 min sliding
duration, the wear encountered under lubricated condition is quite
lower than at dry condition and conforms with the SEM micro-
graphs in Figs. 11(b) and 12. Thus it can be assimilated that even
though higher parametric combinations of the tribo-testing param-
eters is detrimental to the coatings under lubricated condition, still
lower wear is encountered compared to dry sliding condition. This
can be attributed to the surface smoothening effect along with
186 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189
(a)
Fig. 12. SEM micrograph of wear track under dry condition at (a) 800X and (b) 4000X magnification for 10 N applied normal load, 100 rpm sliding speed and 15 min sliding
duration.
surface oxide layers which may have formed for the tribological
test under lubricated condition at higher level of the test parame-
ters.
Finally, it can be concluded from the analysis of wear trends
and the wear mechanism that electroless Ni-P-W coating is suit-
able for reduction of wear of tribological contact applications
working under lubrication. At this point, it is interesting to note
that the wear depth of the coatings obtained for both dry and
lubricated sliding condition is lower than the coating thickness.
Moreover the hardness of the coatings is lower than that of the
hardened counterface disc. This indicates that wear of only the
coatings has taken place and the measurement of wear in terms
of displacement adequately represents the wear of the coatings.
3.4. Friction behavior of Ni-P-W coatings
The variation of coefficient of friction with the tribological test
parameters under lubricated sliding condition is analyzed for elec-
troless Ni-P-W coatings. Plots for COF vs. sliding time with varying
sliding speed and applied normal loads of 10 N and 30 N are shown
in Fig. 13(a) and (b) respectively.
In Fig. 13(a) it can be observed that at a constant load of 10 N,
the COF decreases with an increase in sliding speed. This is due
to an increased adsorbed oil film at higher sliding speeds. Though,
at 70 rpm, the COF is seen to be a little higher than at 60 rpm. It
decreases progressively again from 80 rpm onwards to 100 rpm. An
unstable oil film and tribo oxide layers causes an increase in the
value of COF. But the sudden rise in COF at 10 N and 70 rpm in
Fig. 13(a) could be due to an irregular shaped micron size debris
particle getting trapped in the lubricant along the wear track. At
a normal load of 30 N (Fig. 13(b)) the COF is seen to be almost
same at all the sliding speeds and is seen to be insensitive to the
rise in same. In fact, the COF is even lower compared to the val-
ues obtained at 10 N (Fig. 13(a)). Plots for the variation of COF at
other levels of applied normal load are omitted for the brevity of
the paper. The variation of COF with sliding duration is seen to be
almost constant in Fig. 13.
The trend in variation of COF vs. sliding duration with varying
normal load and constant speed of 60 rpm is shown in Fig. 14(a).
A decrease in COF is observed as the load is increased progres-
sively in steps of 5 N. Since at very low sliding speeds, the ad-
sorbed oil film thickness is not adequate, the decrease in COF can
be attributed primarily to the surface morphology i.e. nodulated
(b)
structure similar to that of a cauliflower (Fig. 4(a)-(d)). In fact, the
COF is very low at 30 N and 20 N applied load conditions. The rise
in frictional force is almost negligible due to the self lubricating
nature of the coatings which leads to a decrease in the COF. The
variation of COF is observed at 100 rpm and a sliding duration of
15 min with varying applied normal loads in Fig. 14(b). It can be
seen that the COF increases with an increase in load from 10 N
to 20 N in steps of 5 N. It has already been established that wear
depth increases with an increase in load at 100 rpm in Fig. 8(b).
This results in more fragments of the coatings being detached and
getting entrapped in the wear track. Moreover at very high sliding
speeds, breakage of the oil film is observed. Thus, a correspond-
ing rise in the COF takes place. The COF again decreases at 25 N
and 30 N applied normal loads and sliding speed of 100 rpm (Fig.
14(b)). This decrease is due to the profound surface smoothening
effect that takes place at higher parametric combinations as can
be observed in Fig. 11(b). Thick tribo layers also may have formed
due to which a decrease in COF is observed. The trends obtained
in Fig. 13(b) can be justified from the same reason. Similar plots at
70, 80 and 90 rpm are omitted for the brevity of the paper.
The variation of COF with the test parameters under dry sliding
condition is shown in Fig. 15. The plots for lubricated condition are
also illustrated in Fig. 15 to strike a comparison between the two.
The COF is seen to be higher under dry condition compared to lu-
bricated condition. Under dry condition at a constant load of 10 N
or 30 N, the COF is seen to decrease with an increase in sliding
speed as well as sliding duration. Also, with an increase in normal
load from 10 to 30 N, the COF is seen to decrease under dry sliding
condition. The COF under lubricated condition is significantly lower
under lubricated condition even at higher parametric settings of
the test parameters. It may be seen that the friction and wear be-
havior of the coatings under lubricated condition depends on the
tribological test parameters as well as the coating microstructure.
The COF decreases under lubricated condition due to its high hard-
ness and nodular surface morphology which effectively reduces the
real area of contact. The surface smoothening effect also leads to
an effective improvement in the COF. Moreover, the flowing lu-
bricant carries away the heat generated during the sliding wear.
A higher sliding velocity may also lead to a lower COF as dis-
cussed previously. Thus, it can be assimilated that the COF is con-
trolled by the combination of all these effects leading to enhanced
performance under lubricated condition compared to dry condi-
tion. Thus, electroless Ni-P-W coating is found to be quite effec-
 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189
(a)
(b)
Fig. 13. COF vs. sliding duration with different sliding speed at constant load of (a)
10 N and (b) 30 N.
tive in reduction of COF of mating parts under lubrication though
optimum COF can be obtained at higher values of applied normal
load and sliding speed under lubricated condition.
4. Conclusion
The investigation attempts to study and analyze the friction and
wear behavior of electroless Ni-P-W coating under lubricated and
dry condition and also correlate the effect of coating microstruc-
ture on the same. The following conclusions can be drawn from
the study:
(a) The deposited coatings are seen to be a mixture of amorphous
and nanocrystalline phase in the as-deposited state. On anneal-
ing at 400 °C for 1 hr, precipitation of crystalline nickel and its
phosphides take place and an improvement in the microhard-
ness of the coatings is achieved due to precipitation harden-
ing as well as by solid solution strengthening phenomenon. On
observing the coated specimens under SEM, nodulated surface
morphology is seen for both as-plated as well as for the an-
nealed coatings.
187
(a)
(b)
Fig. 14. COF vs. sliding duration with different load at constant speed of (a) 60 rpm
and (b) 100 rpm.
(b) The wear depth is seen to increase with tribological test param-
eters under dry as well as lubricated sliding condition. Though,
the wear depth under lubricated condition is significantly lower
compared to dry sliding. The wear mechanism under lubri-
cated condition is investigated to be mild abrasive for the coat-
ings tested at lower level of the parameters with minor scratch
marks on some of the nodules. On increasing the normal load
and sliding speed the abrasion is seen to be higher accompa-
nied by a surface smoothening effect. Under dry condition, se-
vere ploughing with parallel grooves in the sliding direction is
observed with high degree of plasticity at higher levels of test
parameters.
(c) Superior COF is obtained under lubricated condition rather than
in dry condition even at higher levels of the test parameters.
These lower wear and COF values obtained in the case of oil
lubrication are accredited to the nodulated morphology, high
hardness, lubricant carrying away the heat generated and the
surface smoothening effect along with expected formation of
protective tribolayers.
188 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189

(a) (b)

(c) (d)

(e)
Fig. 15. Comparative analysis of COF of Ni-P-W coating after (a) 3 min, (b) 6 min, (c) 9 min, (d) 12 min and (e) 15 min under lubricated and dry condition.
 S. Duari et al. / Surfaces and Interfaces 6 (2017) 177–189
Acknowledgement
The authors gratefully acknowledge the financial support of
University Grants Commission (UGC), Govt. of India through Ma-
jor Research Project vide Ref. No. F No. 41-984/2012 (SR) dated
25.07.2012.
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