Materials Letters 93 (2013) 137–140

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

A study on nanoindentation and tribological behaviour of multifunctional

ZnO/PMMA nanocomposite
Himel Chakraborty a, Arijit Sinha a, Nillohit Mukherjee b,n, Dipa Ray c, Partha Protim Chattopadhyay d
a
School of Materials Science and Engineering, Bengal Engineering and Science University, Howrah 711103, India
b
Center of Excellence for Green Energy and Sensor Systems, Bengal Engineering and Science University, Howrah 711103, India
c
Department of Polymer Science and Technology, University of Calcutta, Kolkata 700009, India
d
Department of Metallurgy and Materials Engineering, Bengal Engineering and Science University, Howrah 711103, India

a r t i c l e i n f o abstract

Article history: This work aims to compare the scratch hardness with the indentation hardness of ZnO nanoparticle
Received 22 October 2012 reinforced polymethylmethacrylate (ZnO/PMMA) composites obtained from nanoindentation measure-
Accepted 18 November 2012 ments. 50 mm thick films ZnO/PMMA nanocomposites were produced by the in-situ spin coating
Available online 27 November 2012
method. Scratch hardness was measured from the scratch width origin at low load during the course of
Keywords: the scratch measurements. A good correlation was found between the scratch hardness and the
Polymeric composites indentation hardness at low indentation depth, where a linear relationship between hardness and the
Nanocomposites reinforcement content of ZnO nanoparticles was observed. The composite was structurally established
Nanoparticles by transmission electron microscopy and furrier transform infrared spectroscopy.
FT-IR
& 2012 Elsevier B.V. All rights reserved.
Indentation and hardness
Wear and tribology

1. Introduction
The cost efficiency and property relation of the transparent
thermoplastic polymer polymethylmethacrylate (PMMA) make it
one of the most frequently employed matrices for the composite
materials with wide applications in modern science. PMMA based
materials have been utilised in many fields, like bio-medical
technologies, implants and also in microelectronics. Nanoinden-
tation (NI) has been established as a reliable tool for measuring
mechanical properties of polymer composite at the nano/micro-
scale [1–6]. An extensive study of nanoindentation on PMMA
composites has been reported by Sharan et al. [6] and Adams
et al. [7]. In nanoindentation or the depth sensing instrumented
indentation technique, hardness and elastic modulus can be
determined according to the Oliver and Pharr model [8–12]. The
scratch test is a simple and widely used method for investigating
polymer composite surface [13]. Scratch hardness (HS) can also be
measured from the scratch track made by the scratch tester. The
HS is defined as the load per unit load-bearing area during
scratching. Since it is quite difficult to measure the load-bearing
area during the course of scratch experiments, it is calculated
from the width of the scratch obtained after the completion of the
test [14,15]. An advantage of HS compared to indentation hard-
ness (HIT) measurements, is the possibility of studying the
n
Corresponding author. Tel.: þ91 33 2668 4561; fax: þ 91 33 2668 1509.
E-mail address: nilsci@yahoo.co.uk (N. Mukherjee).
variation of hardness along the length of the scratch. The hard-
ness of different constituting phases can be determined by
making a single scratch. The absolute values at specific positions
can be calculated by measuring the groove width and by applying
the appropriate hardness formula.
Here, the influence of dispersion of nano-ZnO with different
weight fraction in the PMMA matrix has been investigated in
terms of mechanical and tribological behaviour at the nano/
micro-scale.
2. Materials and method
ZnO powder ( o100 nm in size) and PMMA from Sigma-
Aldrich were used for preparing the composite. The silicon wafers
were carefully cleaned using commercial surfactant and ultra-
sonication, followed by baking at 200 1C for 120 min.
1000 ml, 100 g/L PMMA solution in trichloroethane was pre-
pared and then ZnO nanopowder with different weight per cents
(0.25, 0.50 and 1.0) was added to each 100 ml of the stock
solution. The mixtures were then sonicated for 15 min. Next,
the composites were spin coated (1000 rpm, 60 s) on pre-cleaned
silicon wafers (2  2 cm2) and finally were cured at 60 1C for
60 min, to eliminate any remaining solvent.
Nanoindentation of blank PMMA and ZnO/PMMA composites
was carried out using CSM NHTX S/N: 55-0019 nanohardness
tester with a triangular pyramidal diamond indenter (Berkovich,
B-I 93, tip radius ¼20 mm) under a constant load of 10 mN. All the

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.11.075
138 H. Chakraborty et al. / Materials Letters 93 (2013) 137–140
measurements and the load and displacement resolutions of the
instrument were 1 mN and 0.03 nm respectively. The nanohard-
ness tester was calibrated by using glass and fused silica samples
for a range of operating conditions. The HIT and instrumented
elastic modulus (EIT) were estimated from the initial gradient of
the unloading curves using the Oliver and Pharr [8] model. Five
measurements were carried out at each load on the samples.
Scratch testing was carried out on all the samples using CSM
NST: 50-133 nanoscratch tester with a diamond sphero-conical
indenter (Ref. SB-A63, R¼2 mm) inside a cantilever (serial number:
HL:126, stiffness: 6.6717 mN/mm, FNDZ coefficient at 100 mm:
11.67 mm/V) over a scratch distance of 0.5 mm with a scratch
speed of 2 mm/min. The load was increased from 0 to10 mN at a
specified loading rate. A loading rate of 100 mN/mm was used for
the scratch tests. For indenter tip of circular cross-section area, the
equation for scratch hardness is defined as [14,16].
8F N
HS ¼
pb2
where, FN is the applied normal load and b is the scratch track
width. All scratches were carried out five times in the same
direction. Images of the scratches were obtained using Hitachi
S3400N scanning electron microscope (SEM) to measure the width
of the scratch tracks.
3. Results and discussion
TEM analysis. The TEM image (Fig. 1a) clearly shows the
distribution of the spherical ZnO nanoparticles with an average
diameter of 50 nm within the PMMA matrix. The selected area
electron diffraction (SAED) pattern as inset of Fig. 1a reveals the
nanocrystalline nature of the ZnO used as reinforcement. The
lower magnification image (Fig. 2b) shows the uniform dispersion
of the 0.5 wt% ZnO NPs within the PMMA matrix.
Fig. 1. TEM micrographs (a) ZnO nanoparticles, (b) 0.5 wt% ZnO/PMMA composite and (c) FT IR spectra of (A) pristine ZnO (B) 0.5 wt% ZnO/PMMA composite.
FT-IR analysis. Fig. 1c (A and B) shows the FT-IR spectra of ZnO
particle and the 1.0 wt% ZnO/PMMA composite, respectively. In
the spectrum of ZnO particle, the peak at 3410 cm  1 (Fig. 1cA)
indicates the presence of –OH. In the FTIR spectrum of the
composite (Fig. 1cB), the transmittance bands at 1150, 1240,
1267 and 1732 cm  1 are characteristics of C–O–C and C–O
stretching vibration from PMMA [17]. The stronger transmittance
bands at 1570 and 1400 cm  1 correspond to COO– of methacry-
late moiety. The interaction between ZnO fillers and PMMA can
be deduced from the shift of carboxylic peak toward low wave
number due to electron acceptance from Zn atoms. It indicated
that ZnO particles have a strong interaction existing at the
interface of ZnO and co-polymer, the carboxylic acid groups of
methacrylate moiety possibly transformed into complex com-
pound poly(zinc methacrylate) [18].
Nanomechanical properties. In order to investigate the indenta-
tion behaviour, PMMA and ZnO/PMMA composites were sub-
ð1Þ jected to the NI measurements. The load–depth of penetration
behaviour is typical of that for soft materials with a very little
signature of an elastic recovery indicating a permanent deforma-
tion of the surface beneath the indenter.
It is clear from Fig. 2c that the HIT and elastic modulus (EIT) values
are increasing with an increase in the ZnO particle content from 0 to
0.5 wt%. But addition of 1.0 wt% ZnO particle resulted to a reduction
in HIT and EIT (0.34 and 4.91 GPa respectively).However, the H/E ratios
(Fig. 2c) of the PMMA and composites are following the same pattern.
Also the recovery index (Z) is observed a maximum recovery is
achieved with the 0.5 wt% composite (Fig. 2c) and minimum with the
PMMA. It is also seen that the elastic recovery is maximum in the
case of 0.50 wt% ZnO/PMMA composite which indicates an increase
in the hardness values. This is attributed mainly due to the effect of
higher ZnO reinforcement on the measured hardness. For the 1.0 wt%
ZnO/PMMA composite, the elastic recovery is less. This might be due
to the agglomeration of the reinforced ZnO with increase in the
content of the reinforcements. The calculated HS is found higher than
 H. Chakraborty et al. / Materials Letters 93 (2013) 137–140 139

Fig. 2. (a) Load–depth of penetration profiles for PMMA and ZnO reinforced PMMA composites at 10 mN load (b) nanoindentation impression (c) nanohardness, elastic
modulus, scratch hardness, H/E ratio and recovery index for PMMA and ZnO/PMMA composites.

Fig. 3. Variation of COF and scratch depth with scratch distance for (a) PMMA, (b) 0.25 wt%, (c) 0.50 wt% and (d) 1.0 wt% ZnO/PMMA composites.

the depth sensing instrumented hardness. A good correlation 4. Conclusion

between HS and HIT was found.
In Fig. 3a–d the relation between coefficient of friction (COF)
and the scratch depth are shown. It can be observed that the
friction coefficient reduced with reducing depth of the scratch
and with the increase in the amount of ZnO in composites, both
the depth of scratch and COF values were found to decrease than
that of the PMMA.
ZnO/PMMA composites with various amount of reinforcement
have been prepared by the in situ spin coating method. The
hardness and elastic modulus by the NI technique of the unrein-
forced PMMA and ZnO/PMMA composites were measured. The HS
was determined by single pass scratch test using scratch widths.
The measured HS values were compared with conventional HIT
140 H. Chakraborty et al. / Materials Letters 93 (2013) 137–140
and most interestingly it was observed that at lower indentation
depth there is a good correlation between the HS and the HIT.
Acknowledgements
Himel Chakraborty is indebted to CSIR-HRDG India, for financial
support through SRF (08/003(0061) 2009-EMR–I).
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