Surface & Coatings Technology 205 (2010) 766772

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Abrasive wear resistance of electroless NiP coated aluminium after post treatment
R. Rajendran a, W. Sha b,, R. Elansezhian c
a
b
c

School of Mechanical and Building Sciences, B. S. Abdur Rahman University, GST Road, Vandalur, Chennai 600 048, India
School of Planning, Architecture and Civil Engineering, Queen's University Belfast, Belfast BT7 1NN, UK
Department of Mechanical Engineering, Pondicherry Engineering College, Pondicherry 605014, India

a r t i c l e

i n f o

Article history:
Received 28 June 2010
Accepted in revised form 29 July 2010
Available online 10 August 2010
Keywords:
Amorphous materials
Coating materials
Electroless plating
Phase transitions
Scanning electron microscopy
Surface morphology

a b s t r a c t
Electroless nickel (EN) coatings are recognised for their hardness and wear resistance in automotive and
aerospace industries. In this work, electroless NiP coatings were deposited on aluminium alloy substrate
LM24 (Al9 wt.% Si alloy) and the effect of post treatment on the wear resistance was studied. The post
treatments included heat treatment and lapping with two different surface textures. Scanning electron
microscopy (SEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and micro-abrasion tester
were used to analyse morphology, structure and abrasive wear resistance of the coatings. Post heat
treatment signicantly improved the coating density and structure, giving rise to enhanced hardness and
wear resistance. Microhardness of electroless NiP coatings with thickness of about 15 m increased due to
the formation of Ni3P after heat treatment.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Surfaces produced by various processes exhibit distinct differences in
texture. These differences make it possible for honed, lapped, polished,
turned, milled, or ground surfaces to be easily identied. Variations in the
texture of a critical surface of a part inuence its ability to resist wear and
fatigue, to assist or destroy effective lubrication, to increase or decrease
its friction and abrasive action on other parts, and to resist corrosion, as
well as affect many other properties that may be critical under certain
conditions [1]. Roughness is sometimes an undesirable property, as it
may cause friction, wear, drag and fatigue, but it is sometimes benecial,
as it allows surfaces to trap lubricants and prevents them from welding
together. Hence, controlling surface roughness is important in terms of
functional and quality aspects.
The surface roughness of the coating after deposition depends on
the roughness of the surface coated, on the total coating thickness and
on the type of coating applied. In general, the surface of the coating
will have at least the same roughness as the initial coated surface; the
roughness will increase with coating thickness.
The wear resistance of a coated component is mainly determined by
the coating as long as it covers the contact area. As soon as the coating is
partly worn through, or the substrate is exposed due to adhesive failure
or cracking and spalling, the wear resistance of the substrate material
becomes important. Two main categories can be distinguished: wear
dominated by coating detachment and wear caused by gradual removal
of coating material. The latter often involves mild wear due to abrasion,

erosion, chemical dissolution, etc., and does not deviate from the
mechanisms causing wear of homogeneous materials.
Electroless nickel (EN) coating is a well established surface
engineering process widely used in automotive and aerospace industries
as it provides high hardness and excellent resistance to wear, abrasion
and corrosion [2]. The auto industry takes particular advantage of the
uniformity of the electroless nickel deposit on irregular surfaces, direct
deposition on surface activated non-conductors and the formation of less
porous, more corrosion resistant deposits [3].
AlSi alloys, with lighter weight and better heat conductivity than
cast iron, have been increasingly used in automotive engine cylinder
blocks. The eutectic AlSi alloy with high percentages of alloying
elements has better scufng resistance than the hypereutectic AlSi
alloys. Cast AlSi alloys having excellent castability are suitable for
production of large series of complex-shape components, such as engine
blocks, pistons, cylinder liners, cylinder heads, and wheels. In some
applications, however, they suffer from insufcient wear resistance.
Generally, past studies were made on heat treatment of EN
coating. Here, an attempt is made to study the effect of post treatment
(heat treatment and lapping with two different surface textures) on
the wear resistance of EN coated aluminium. In addition to the wear
performance, this work also analyses the surface morphology features
of the EN coating.
2. Experimental
2.1. Surface preparation

Corresponding author. Tel.: +44 28 90974017; fax: +44 28 90974278.

E-mail address: w.sha@qub.ac.uk (W. Sha).
0257-8972/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2010.07.124

The samples were cut into required size of 36 25 3 mm from Al

Si alloy casting by electrical discharge machining (EDM). The step-by-

R. Rajendran et al. / Surface & Coatings Technology 205 (2010) 766772

767

step cleaning procedure employed prior to plating consists of

ultrasonic degreasing in acetone, rinsing with distilled water,
deoxidizing in 10% HCl acid, rinsing with distilled water, pickling in
10% H2SO4, and rinsing in distilled water followed by a methanol
wash. It is believed that Al alloys can also be treated using NaOH and
HNO3, which is perhaps a more common option.
Usually, aluminium alloys are pre-treated by a zincate etch bath
prior to electroless nickel-plating. Zincating process was not used in
this research experimental work, potentially an advantage because
this eliminates a process, reduces the use of chemicals and thus may
have environmental advantages. However, that should be a subject of
separate studies, and is not the objective of the research shown here.
2.2. Plating bath and operating conditions
The composition of the plating bath for electroless NiP deposition
had nickel chloride as the source of nickel, sodium hypophosphite as
the reducing agent, and sodium citrate as the complexing agent. The
bath compositions and plating conditions used are given in Table 1.
Temperature of the plating bath was maintained at 85 1 C. The pH
of the bath was maintained between 9 and 10 by addition of sufcient
quantity of ammonia solution. Due to the small volume of the plating
bath and the experimental (manual operation) rather than the
commercial nature of the plating process, a stricter limit in the
variation of pH within 0.2 was not achieved in this work. This might
have resulted in variations of the amount of phosphorus in the
coatings, but this is not expected to have affected the main
conclusions from the research. The electrolyte was heated indirectly
by an electrically heated water bath. The temperature of the
electrolyte was monitored using a thermometer. The coating was
for a period of 30 min with total volume of the plating bath restricted
to 500 ml.
The heat treatment of some coating specimens was conducted in
air. Although some believe that oxidation rate of EN coating is fast as
the temperature is above 200 C, surface morphology observation and
X-ray diffraction results shown in later sections do not reveal any
oxidation product, and thus oxidation during the heat treatment in
this work is considered insignicant.
After this treatment and direct coating on Al surface without under
coating layer, the adhesion of the coated layer was found to be more
than satisfactory, as revealed by later wear testing results.
2.3. Micro-abrasion test
In conditions of mild abrasion, the coating material may determine
the wear resistance of a coating composite. Standard abrasive wear
tests are usually too coarse to be useful for measuring the intrinsic
wear resistance of thin coatings. With the crater grinder method as a
means for coating wear evaluation, it is possible to distinguish the
abrasive wear resistance of a thin coating material from that of the
substrate, also in conditions where the coating is worn through [4,5].
A Plint TE66 micro-scale abrasion tester was used to evaluate the
coating abrasive wear resistance. During the test, a directly driven ball

Fig. 1. Schematic diagram of the micro-abrasion apparatus.

is rotated against the specimen, which is mounted on a dead-weight

load lever, in the presence of slurry of SiC abrasive particles. The slurry
is drip fed onto the contact between the specimen and the ball (Fig. 1)
and the wear scar produced on the specimen surface is assumed to
reproduce the spherical geometry of the ball [6]. By making a series of
these craters and measuring the size of the scar dimensions, both
coating and substrate wear coefcients (kc and ks) can be simultaneously determined from the test [6,7]. For bulk materials, the
equation that is assumed to describe the abrasive wear is [69]
!
4
V
1 b
=
SL =
for b WW R
k
k 64R

where S is the distance slid by the ball, L is the normal force on the
sample, V is the wear volume, k is the wear coefcient, b is the
diameter of the crater, and R is the radius of the ball. Two complete
series of six tests with different durations as in Table 2 were
conducted.
Eq. (1) was extended to a model that combines the wear in the
coating and substrate, providing both coating and substrate wear
coefcients [6,7]
SL
=
b4

!


 
ks kc
t
Rt 2
1

+
4
2
k s 64R
ks kc
4b
b

where b is the outer diameter of the wear crater, ks and kc are the
substrate and the coating wear coefcients, respectively, and t is the
coating thickness. Both substrate and coating wear coefcients can be
obtained from a linear plot of SL / b4 versus t / 4b2 Rt2 / b4; the
substrate wear coefcient, ks, is obtained from the intercept of the
Table 2
Test conditions for wear tests.

Table 1
Composition and conditions of plating bath for electroless deposition.
Particulars

Value

Nickel chloride
Sodium hypophosphite
Sodium citrate
Ammonium chloride
Temperature
pH
Bath volume
Deposition time
Heat treatment

30 g/l
40 g/l
25 g/l
50 g/l
85 C ( 1 C)
910
500 ml
30 min
330 C/1 h

Parameters

Value

Load
Speed
Ball material
Ball diameter
Ball nish
Abrasive material SiC
Fluid carrier
Feed rate
Abrasive concentration
Test duration

0.5 N
0.1 m/s
Stainless steel AISI 440-C
25.4 mm
Conditioned using run-in procedure
3 m
Water
Keep wet
20 vol.%
400, 600, 900, 1200, 1500, 2000 ball-revolutions

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R. Rajendran et al. / Surface & Coatings Technology 205 (2010) 766772

Wear Volume, mm3

0.6
0.5

Table 3
Surface roughness value for aluminium, electroless nickel coated aluminium and heat
treated electroless nickel coated aluminium (with and without lapping).

Al
EN Al

0.4

Surface nish (m)

Specimen

HT EN Al

0.3
0.2
0.1
0
0

50

100

150

200

Al
Al S
EN Al
EN Al S
HT EN Al
HT EN Al S

Ra

Rz

4.04
1.98
4.72
1.87
4.63
1.73

24.63
11.45
26.03
11.92
23.32
10.13

S indicates lapped surface.

Sliding Distance, m
Fig. 2. Wear volume as a function of sliding distance of aluminium (Al), electroless
nickel coated aluminium (EN Al) and heat treated electroless nickel coated aluminium
(HT EN Al).

linear plot and the coating wear coefcient, kc, is calculated from the
gradient of the plot.
The wear constants kc and ks are essentially a measure of the
abrasive wear rate; the lower the wear constant, the better the
resistance to abrasive wear. After measuring the inner and outer
diameters of the wear craters, regression analyses, according to
Eqs. (1) and (2), were carried out in order to determine both kc and ks
for each sample.
A Nikon Eclipse ME600D optical microscope with a JVC digital
camera was used for measurement of the scar diameter and to check
the roundness of the scar. The analySIS Auto-version 3.0 (Soft Imaging
System GmbH) was used to digitally monitor and store the images
from the camera attached to the optical microscopy with a computer.
The morphology of wear scars and debris was observed by optical
microscopy and scanning electron microscopy (SEM).
2.4. Analysis of the deposits
Microhardness of the EN deposits was estimated using Mitutoyo
HM124 hardness testing machine, with a Vickers indenter, 50 g load,
and 10 s loading time. Surface roughness of electroless nickel deposits
was measured using a TESA Rugosurf 10G surface roughness tester,
cut-off length 0.8 mm. The surface morphology of the electroless
nickel deposits was observed using a Jeol 6400 high-resolution
scanning electron microscope. The amount of phosphorus and nickel
contents on the EN deposits were analysed using Jeol 6400 SEM EDAX
attachment. X-ray diffraction patterns were obtained from experiments using a computer controlled Philips X'Pert Pro X-ray diffractometer using Cu K radiation of wavelength 1.54060 in the scan
range of 20 to 90. X-ray diffraction is widely used to determine the

structure of materials. Diffraction patterns contain information

showing various phases of a material and residual stresses within a
coating.
3. Results and discussion
3.1. Micro-abrasion
Fig. 2 shows the wear volume of aluminium (Al), electroless nickel
coated aluminium (EN Al), and heat treated electroless nickel coated
aluminium (HT EN Al). It can be seen that the wear volume increases
with increase in the number of revolutions (sliding distance). When
the wear volume is high, the penetration is deeper. However, it is
found that in most of the samples, the penetration depth exceeds the
depth of coatings into the substrate. Therefore, the abrasion tests were
done up to 2000 revolutions in order to determine the strength of the
samples.
Fig. 3 shows the wear volume of aluminium, electroless nickel
coated aluminium, and heat treated electroless nickel coated
aluminium under lapped condition. The measured surface roughness
for the coating under different conditions is given in Table 3. The wear
volume of the lapped samples is increased when compared to the
samples without lapping. If the surface was perfectly smooth then
seizure would occur due to difculty of maintaining the lubricating oil
lm. The rates of wear are proportional to the surface areas in contact
and the load per unit area.
It should be noted that the aim of this work is not to simulate
actual cylinder liner wear, but to establish a test for evaluating the
surface characteristics of EN coated aluminium that may be related to
liner wear performance. Therefore, the ball material need not reect
the properties of the counter face in actual cylinder liners.
The kc and ks wear coefcients were obtained from the linear
regression analyses as shown in Figs. 4 and 5. It should be noted
that the x-axis in these two gures is intended to be as shown, t /
4b2 Rt2 / b4, with a unit of m 1. These diagrams show the

4.5E+12

Al S

0.5

EN Al S
0.4

EN Al

4.0E+12

HT EN Al S

0.3
0.2
0.1

y = 11.1E+11x + 3.86E+11

HT EN Al

R2 = 0.987

3.5E+12

SL/b4, N/m3

Wear Volume, mm3

0.6

3.0E+12
2.5E+12
2.0E+12
1.5E+12

y = 8.62E+11x + 1.23E+11

1.0E+12

R2 = 0.996

5.0E+11

0.0
0

50

100

150

200

Sliding Distance, m

0.0E+00
0

t/4b2Rt2/b4, m-1
Fig. 3. Wear volume as a function of sliding distance of lapped aluminium (Al S),
electroless nickel coated aluminium (EN Al S) and heat treated electroless nickel coated
aluminium (HT EN Al S).

Fig. 4. Linear regression analysis of electroless nickel coated aluminium (EN Al) and
heat treated electroless nickel coated aluminium (HT EN Al).

R. Rajendran et al. / Surface & Coatings Technology 205 (2010) 766772

EN Al S

4.0E+12

HT EN Al S

SL/b4, N/m3

3.5E+12
3.0E+12
2.5E+12

y = 4.04E+11x + 9.65E+11
R2= 0.994

2.0E+12
1.5E+12
1.0E+12

y = 3.34E+11x + 6.68E+11
R2= 0.993

5.0E+11
0.0E+00

2.5

Coating Wear Resistance (kc-1)

1012 Nm/m3

4.5E+12

1.5

0.5

4
0

t/4b2Rt2/b4, m-1

EN A1

Fig. 5. Linear regression analysis of lapped electroless nickel coated aluminium (EN Al
S) and heat treated electroless nickel coated aluminium (HT EN Al S).

correlation between the y-axis function and the x-axis function. This
was explained in the paragraph below Eq. (2). The curve t
parameters are summarised in Table 4. The normal probability plots
of residuals, which were obtained for the regression in all samples,
indicated that the residuals had a normal distribution and their
variance was constant. The regression also indicated high values of
R2 and adequacy of t in all systems, conrming that the models
leading to Eqs. (1) and (2) are successful in describing the
experimental data [10].
The EN coating had the highest wear resistance to abrasion. The
1
coating wear resistance (k
c ) is shown in Fig. 6 along with the wear
resistance of the uncoated substrate for a direct comparison. As
expected, the choice of the EN coating plays an important role in
improving the micro-abrasive wear resistance. In the micro-abrasive
wear tests, SiC particles, with a mean size of 3 m, were used as
abrasives. Their sizes are smaller than the thickness of coatings. The
indentation depths of abrasive particles on surfaces depend on the
applied load, surface hardness and abrasive hardness [11]. Microhardness measurements were made on the cross-sections of the plain
electroless NiP coatings in as-plated and heat treated conditions. It is
evident from Table 5 that the hardness of the coating increased by
about 4.5 times the base hardness. The SiC hardness is expected to be
21002600 HV0.05 [12]. Habrasive was taken as 2400 HV. Therefore, it
can be seen that coatings are softer than the SiC particles.
An important parameter in abrasive wear testing is the ratio
between the hardness of the abrasive particles (Habrasive, or Ha) and
the hardness of the surface (Hs). Hard abrasion typically occurs
when the ratio Ha/Hs is higher than 1.2. In this condition, the abrasion
will lead to much greater wear rates [12].
Dependence between the kc values and the ratio Ha/Hs can be
observed for the coatings. A lower Ha/Hs ratio in general leads to
higher micro-abrasive wear resistance. The electroless nickel and the
heat treated electroless nickel coating had a lower Ha/Hs ratio than the
substrate and displayed better micro-abrasive wear resistance.
Although the hardness of the heat treated electroless nickel was
higher than that of untreated electroless nickel, its relatively low
hardness, in comparison to that of SiC particles, in combination with a
Table 4
Coating and substrate wear coefcients obtained from experimental results and linear
regression analyses.
Specimen

Model

kc
ks
Slope
(10 12 m3/Nm) (10 12 m3/Nm) (m3/Nm)

Intercept
(N/m3)

Al
EN Al
EN Al S
HT EN Al
HT EN Al S

Eq.
Eq.
Eq.
Eq.
Eq.

0.52
0.73
0.58
0.85

6.09 1011
3.68 1011
9.65 1011
1.23 1011
6.68 1011

(1)
(2)
(2)
(2)
(2)

*S indicates lapped surface.

4.90
1.60
2.54
1.78
2.87

769

11.1 1011
4.04 1011
8.62 1011
3.34 1011

HT EN A1 HT EN A1 S

EN A1 S

A1

Coating Material
Fig. 6. Coating wear resistance of aluminium, electroless nickel coated aluminium and
heat treated electroless nickel coated aluminium (with and without lapping).

15 m lm thickness could not provide an adequate improvement in

terms of abrasive wear.
If the SiC particles deeply penetrated through the EN coating
because of its relatively low hardness, then the EN coating may have
become partly delaminated or removed through a severe ploughing or
cutting mechanism during the last stages of the test. This would
explain the high wear rates recorded for these coatings. The poor
abrasive wear resistance recorded for the EN coatings could be
attributed to the hardness being much lower than that of the SiC
abrasive particles, which caused tearing of the coating with
subsequent delamination [13].
It is sometimes reported in the literature that a reduction in
abrasive wear resistance occurs with increasing surface roughness.
This effect was not observed in this work, since the (rougher) EN
coatings exhibited higher resistance to micro-abrasion than the
lapped EN coatings. This is probably due to an increased resistance
to abrasive wear offered by the EN coating, being more important than
the supposed negative effect of the increased surface roughness.
Fig. 7 shows the optical micrographs of craters formed with
different wear durations on aluminium, electroless nickel coated
aluminium, and heat treated electroless nickel coated aluminium,
with 20% SiC and nominal 0.5 N load, after 4002000 revolutions. The
scar of the samples at shorter test duration is not spherical in shape.
It was found that the size of the crater increased as the number of
revolutions increased, but that the proportion of grooving wear that
occurred was also increasing.
Fig. 8 shows the optical micrographs of craters formed with
different wear durations on aluminium, electroless nickel coated
aluminium, and heat treated electroless nickel coated aluminium with
lapping, with 20% SiC and nominal 0.5 N load, after 4002000
revolutions. For the crater on the lapped substrate, it was not possible
to dene clearly the inner and outer crater diameter.
Most of the electroless nickel samples that are examined show the
substrate as the penetration exceeds the coatings. When viewing the
wear scars, two regions can be seen in the spherical cap. The darker
region in the middle shows the substrate whereas the region outside
the inner circle represents the coating.
It can be noticed that the wear pattern observed in the coating
region of the wear crater is the same as that seen in the substrate

Table 5
Vickers hardness of aluminium, electroless nickel coated aluminium and heat treated
electroless nickel coated aluminium.
Specimen

HV0.05

Habrasive/Hsurface

Al
EN Al
HT EN Al

90
400
650

27
6
4

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R. Rajendran et al. / Surface & Coatings Technology 205 (2010) 766772

(a)

400 Al

600 Al

900 Al

1200 Al

1500 Al

2000 Al

1200 EN Al

1500 EN Al

2000 EN Al

1500 HT EN Al

2000 HT EN Al

(b)

400 EN Al

600 EN Al

900 EN Al

(c)

400 HT EN Al

600 HT EN Al

900 HT EN Al

1200 HT EN Al

Fig. 7. Optical micrographs of craters formed with different durations on (a) aluminium, (b) electroless nickel coated aluminium and (c) heat treated electroless nickel coated
aluminium with 20% SiC and nominal 0.5 N load. The number in the micrographs is the number of revolutions. The scale bar in each micrograph is 1 mm.

region. However, the worn coating area that remains after the test is
conned to a quite thin ring outside the worn substrate area.
After a certain number of ball revolutions, the coating material is
worn through, exposing the substrate material. After this point, the

micro-abrasive wear resistance can be further increased by increasing

the substrate hardness. Although increased hardness does not
necessarily result in better abrasive wear resistance (i.e., abrasive
wear by brittle fracture), the present results indicate a strong

(a)

400 Al S

600 Al S

900 Al S

1200 Al S

1500 Al S

2000 Al S

(b)

400 EN Al S

600 EN Al S

900 EN Al S

1200 EN Al S

1500 EN Al S

2000 EN Al S

400 HT EN Al S

600 HT EN Al S

900 HT EN Al S

1200 HT EN Al S

1500 HT EN Al S

2000 HT EN Al S

(c)

Fig. 8. Optical micrographs of craters formed with different durations on lapped (a) aluminium, (b) electroless nickel coated aluminium and (c) heat treated electroless nickel coated
aluminium with 20% SiC and nominal 0.5 N load. The number in the micrographs is the number of revolutions. The scale bar in each micrograph is 1 mm.

R. Rajendran et al. / Surface & Coatings Technology 205 (2010) 766772

771

inuence of surface hardness on the micro-scale abrasive wear

performance, which suggests a mechanism of abrasive wear by plastic
deformation [12].
The presence of an electroless nickel deposited layer diminishes
the scratching action of the SiC abrasive particles, since the Ha/Hs ratio
is lower for an electroless nickel coated aluminium in comparison to
the base material. Therefore, for a given sort of abrasive particles, the
micro-abrasive wear resistance can be improved by increasing the
surface hardness, i.e., by depositing a harder coating than the abrasive
particles.
The micro-abrasion test can thus be seen to be a quick and
sensitive measure of the degradation of the electroless nickel coated
materials. Wear is in fact the most important property related to the
performance of these components in service. Although the mode of
wear in actual service is not the same as in the micro-abrasion test and
wear rates will differ, both cylinder liner wear and micro-abrasion
would seem to depend on the large deformation mechanical
behaviour of electroless nickel coating.

3.2. Surface morphology

Fig. 9a shows the SEM image of the aluminium substrate before
electroless plating. The image shows that the substrate has a rough,
eroded like surface, providing good adhesion of the subsequent nickel
lm on the substrate.
Fig. 9b shows the surface morphology of the electroless nickel
deposit. A smooth surface with relatively rough grains is acquired.
The round particles seen on the image are the random nickel
deposits in the solution attached to the surface of the sample. Large
amount of circular shaped grains can be seen on the images. These
grains are sized around 3 microns in diameter. The increased size of
grains may be due to the reduction of the concentration of the
chemicals in the plating solution in the last stage of plating, which
reduces the plating rate and enables the grains to grow more
extensively. The thicknesses of the coated-deposit on both sides of
the substrate were remarkably uniform. The appearance of the
deposits was homogeneous.
The heat treated (330 C/1 h) sample (Fig. 9c) does not show
signicant change in surface morphology against the as-plated one.
The spherical globules of nickel have been reduced. In the case of
electroless nickel deposit, the dispersion of nickel particles seems to
be less prominent when compared to heat treated electroless nickel
coated aluminium resulting in uniform surface nish.
It may be noted that surface morphology is not the same as
microstructure. Cross-section microscopy would be required for
identication of microstructure, but the microscopy shown in this
section is from the coating surfaces, which shows the coating
growth morphology. SEM cross-sectional micrograph [1416] and
EDX analysis [14,15,17] results are reported in previous publications for identication of coating thickness [14], elemental
composition [14,15,17], and diffusion of nickel into the substrate
[14]. These results are included in a recent book on electroless
plating [18].

Fig. 9. SEM micrographs of (a) aluminium, (b) electroless nickel coated aluminium and
(c) heat treated (330 C/1 h) electroless nickel coated aluminium.

3.3. EDX analysis

3.4. X-ray diffraction
Three different spots around the structures were analysed and
the average phosphorus content is 4.7 0.1 wt.%, balance nickel.
There is a small amount of oxygen present on the surface, which is
possibly due to very small amount of oxidation soon after the
samples were prepared. Since no signicant oxygen or other
element is found, it is reasonable to believe that the structure
seen on the deposits consists of Ni and P with no contribution from
other elements.

Fig. 10a shows the X-ray diffraction (XRD) characteristics of

aluminium. For aluminium, ve strong peaks can be observed at 2 of
around 38.5, 44.7, 65.2, 78.3 and 82.4, and for silicon, three strong
peaks can be seen at 2 of around 28.5, 47.4 and 56.3.
The widths of the diffraction peaks are related to the quality of the
crystallites. Larger and perfect crystallites have sharper diffraction
peaks. The XRD pattern of the as-deposited NiP in Fig. 10b shows a

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R. Rajendran et al. / Surface & Coatings Technology 205 (2010) 766772

4. Conclusions
In this paper, a micro-abrasive wear test was used to evaluate the
wear resistance of electroless nickel coatings after post treatment. The
experimental results indicated that:

Fig. 10. X-ray diffraction for (a) aluminium (b) electroless nickel coated aluminium and
(c) heat treated electroless nickel coated aluminium.

broad peak (around 2 = 45) and some sharp small peaks. The wide
angular range prole at the 2 position of 3555 indicates the
presence of a mixture of amorphous and microcrystalline phases in
the deposits. Though it was previously believed that phosphorus
contents of lower than 7% result in microcrystalline EN deposits [2],
some careful XRD peak separation work has shown the overlapping of
amorphous and microcrystalline diffractions [1820]. As expected,
diffraction peaks from the AlSi alloy substrate are visible, with much
reduced intensity compared to Fig. 10a, as the X-ray can penetrate
through the coating. Note that microscopy work shows that the asdeposited NiP coating having a thickness of about 15 m shows a
relatively good adherence to the substrate and uniformity.
There is one major and one weak broad-peak diffraction at the 2
positions corresponding to Ni {111} and {200} planes, respectively,
superimposed with the amorphous diffraction in the XRD proles. The
results agreed with the studies from other investigators showing that
the as-deposited low to medium phosphorus deposits consisted of an
amorphous structure [21,22].
Fig. 10c shows the XRD characteristics of heat treated electroless
nickel on aluminium. Heating to the temperature of 330 C has
caused the broad-peak reections that correspond to the 2
positions of Ni {111} and {200} planes, to develop into the relatively
broad Ni {111} and {200} diffraction peaks, respectively, with
limited height (intensity). The intensity of amorphous prole
decreased, and the Ni {220} reection was seen in the XRD prole.
In addition, the intensity of substrate peaks has reduced, because
the penetration power of X-ray through a crystalline structure is
lower than through an amorphous structure, as proved in previous
work [14,18].
Duncan indicated that the microcrystalline -phase converts to
-nickel at 250290 C, whilst the amorphous -phase converts to
Ni3P and -nickel at 310330 C [23]. In this study, the XRD
analysis conrms the above results by conrming the transformation from an amorphous structure to crystalline nickel. According to
the low temperature phase diagram of NiP, the structure of asdeposited NiP coating consists of microcrystalline -phase and
amorphous -phase for a phosphorus content between 4.5 and
11 wt.% [23].
This study was carried out to understand the changes in the XRD
patterns of electroless nickel deposits with annealing temperature.
In general, the heat treatment process transforms the NiP phase to
a mixture of hard nickel phosphides (Ni3P) and nickel. As expected,
the as-deposited coating and coating heat treated at low temperatures show a broad peak of NiP phase and sharp peaks of
crystalline aluminium and silicon from the substrate. The phase
composition of NiP coatings was analysed by X-ray diffraction.
Further investigation will be required to quantitatively explain
micro-abrasive wear resistance change by phase transitions of EN
coatings.

(1) The microhardness of electroless NiP coating heat treated at

330 C for 1 h was higher than that of NiP alloy coating, due to
the presence of Ni3P particles.
(2) The wear volume of the lapped samples is increased when
compared to the samples without lapping. The wear abrasion was
found to be dependent on the ratio between the hardness of the
SiC abrasive particles and the hardness of the surface (coating) or
subsurface. By decreasing this ratio, the ability of the SiC abrasive
particles to scratch the coated surface was reduced.
(3) Electroless nickel coatings showed higher micro-abrasive wear
resistance than the base material. Electroless nickel coatings
were effective in improving the micro-abrasive wear resistance
of the substrate, since their wear coefcients were lower than
the substrate wear coefcients. The hardness of the electroless
nickel coating was found to be much lower than the hardness of
the SiC abrasive particles. Consequently, these coatings seem to
have partly delaminated during the test due to the presence of
harder SiC abrasives, which caused tearing of the coating with
subsequent delamination.
(4) The deposition of thicker electroless nickel coatings may be
expected to yield an improvement in the abrasive wear
resistance, since the SiC particles would not be able to
penetrate heavily into the electroless nickel lm and coating
delamination would be inhibited.
Acknowledgement
We hereby express our sincere thanks to the UK Royal Society for
providing the support for this project and Queen's University Belfast,
in the form of an International Travel Grant, 2009R2 Travel for
Collaboration.
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