Macromolecular Research, Vol. 24, No. 4, pp 309-313 (2016) www.springer.

com/13233
DOI 10.1007/s13233-016-4043-3 pISSN 1598-5032 eISSN 2092-7673

Structural and Electromechanical Behavior Evaluation of Polymer-Copper

Nanocomposites

Gulfam Nasar*,1, Muhammad Azhar Khan*,2, Muhammad Farooq Warsi1, Muhammad Shahid1,
Uzma Khalil3, and Muhammad Saleem Khan4
1
Department of Chemistry,The Islamia University of Bahawalpur, Bahawalpur 63100, Pakistan
2
Department of Physics, The Islamia University of Bahawalpur, Bahawalpur 63100, Pakistan
3
Jinnah College for Women, University of Peshawar, Pakistan
4
National Center of Excellence in Physical Chemistry, University of Peshawar, Pakistan

Received April 19, 2015; Revised January 3, 2016; Accepted January 24, 2016

Abstract: Copper nanoparticles were prepared by chemical reduction of copper nitrate by sodium borohydride as a
reducing agent in de-ionized water/acetonitrile mixture. The prepared nanoparticles were incorporated in poly(vinyl
alcohol) (PVA) by physical dispersion method to obtain PVA/copper nanocomposites. Various compositions of
nanocomposites were obtained by changing the w/w ratio of nanoparticles with the polymeric material. The prepared
nanocomposites cast into films of uniform thickness. The composite films were subjected to the electrical, mechan-
ical and surface morphology characterization. AC Impedance was figured out by AC Impedance analyser. The results
illustrated that copper nanoparticles impart electrical conductivity in poly(vinyl alcohol). Moreover, electrical con-
ductivity of the composites exhibited an increase with an increase of w/w% of the copper nanoparticles in poly(vinyl
alcohol). Tensile properties were studied in terms of tensile strength, elongation at break and Young’s modulus. Elon-
gation at break and Young’s modulus values demonstrated an increase while tensile strength displayed a decrease at
higher concentration of the copper nanoparticles in the composites. AFM results unfolded the surface morphology
of the composites illustrating a smooth surface with evenly distributed copper nanoparticles in the polymer matrix.
The dimensions of the uneven surface is attributed to the copper nanoparticles were estimated to be of a range less
than 100 nm. The prepared nanocomposites are suggested as potential candidates in charge storing devices.
Keywords: poly(vinyl alcohol), AFM, mechanical properties, AC impedance, copper nanocomposites, nanoparticles.

Introduction as compared to the pure constituents from which they are

Over the recent decades much attention has been paid
towards developing new materials with high energy storage
capacities. Most of such materials are polymer, or polymer
based composites and nanocomposites.1 This is due to their
enhanced properties e.g. better thermal, electrical and mechani-
cal properties that polymer nanocomposites have attained a
commendable amount of research work.2 The nanocompos-
ites have exhibited a better set of properties like fire resis-
tance,3 gas permeability4 and enhanced mechanical properties,
as compared to the immaculate polymer. These superior proper-
ties are obtained by properly dispersing the inorganic nanopar-
ticles or layered filler material particles within the polymer
matrix.
Nanocomposites, owing to their structure at nanoscale,
exhibit quite a reasonable amount of variation in the properties
*Corresponding Authors. E-mails: gulfam.nasar@iub.edu.pk or
azhar.khan@iub.edu.pk
synthesized. A nanofiller of a very little amount can vary the
properties up to a greater extend.5,6 The degree of alteration
of the properties not only depends upon the amount of the filler
material but also on its shape and size,7 extend of its disper-
sion in the matrix material and how its particles are oriented
within the matrix.8 In the domain of nanotechnology new
materials are being developed and studied extensively. The
development of new materials accomplishes the requirement
of nanotechnology with enhanced properties to meet new
demands.9
The stability of a composite depends on the10 chemical
structure of the substance;11 stability towards oxidation can
be enhanced by the addition of inhibitor. The electrical and
structural properties of nano-sized materials depend on composi-
tion and method of fabrication of the prepared material.12
Electrical and mechanical properties play an important role
in characterizing a material. The effect of inorganic/metallic
particles into a polymer system is of vital importance.13 A
composite system can be characterized by establishing a rela-

© The Polymer Society of Korea and Springer 2016 309

 G. Nasar et al.
tion between its structural and functional properties. There has
been much work reported on the conducting nature of the
composites actually made from non-conducting polymers,
and the conductivity of the composites is reported up to 10-6 S
cm-1.14-16 Recently various types of nanoparticles17 and nanocom-
posites have been reported in dynamic applications such as
electric,18 electronical19 and biotechnological applications.20
The present study is aimed to produce nanocomposites of
PVA with copper nanoparticles that exhibit enhanced electrical
conductivity with optimized mechanical properties. With the
enhanced conductance as high as 10-5 S cm-1 and assimilated
mechanical properties the new material might be a strong candi-
date to find application in electrical and charge storing devices.
This high conductance is reported for the first time for such
polymer composite system.
Experimental
Chemicals Used. Following chemicals were used for the
present study.
Poly(vinyl alcohol) molecular mass 70,000 g/mol (BDH),
copper(II) nitrate (Uni Chem), sodium borohydride (Aplichem),
de-ionized water (Milipore), acetonitrile (Aplichem) and ethanol
(Aplichem). PVA was dried for 100 min in vacuum oven at
80 oC. Other chemicals were used as such without further
processing.
Synthesis of Copper Nanoparticles. Copper nanoparticles
were prepared by chemical reduction method using sodium
borohydride under vacuum conditions. 0.1 molar solution of
copper nitrate was prepared in a mixture of water/acetoni-
trile in the v/v ratio of 30%:70%. 25 mL of this solution was
transferred in a vacuum flask attached to a vacuum pump. A
Teflon magnetic bar was added to the flask and was corked
with a thick rubber stopper. The apparatus was fixed on a
magnetic stirrer. 0.1 molar solution of sodium borohydride
was freshly prepared and was injected drop wise through the
rubber stopper by a needled syringe along with vigorous stirring.
The process was stopped at the appearance of red wine colour.
The contents were centrifuged at 4,000 rpm and the prepared
copper nanoparticles were separated using ethanol. The nanopar-
ticles were vacuum dried for an hour and were stored in an
air-tight desiccator.
Preparation of Nanocomposite. 1, 2, 3, 4, and 5 mg nanopar-
ticles were weighed separately and were suspended in de-ion-
ized water by ultra-sonication for two hours. The contents
were added to five samples of 50 mL each of 3% w/w PVA
solutions. The contents were subjected to hotplate stirring for
12 h to synthesize composites with uniformly distributed copper
nanoparticles. The nanocomposites of PVA/copper nanoparti-
cles were cast into films using solvent evaporation method.
Films were removed from Petri dishes and were carefully cut
into appropriate sizes for characterization techniques. AC
impedance, tensile properties and Atomic Force Microscopy
were used to characterize the prepared nanocomposites.
310
Characterization of Nanocomposites. For studying the
electrical properties of Cu-PVA nanocomposite, Autolab AC
Impedance Analyzer was brought into use. The instrument
uses three probe measuring device in order to measure elec-
trical conductivity. The tests for each specimen were carried
out and the results were shown in form of Nyquist plots.
Data from the Nyquist plot was used to figure out electrical
conductivity of the various concentrations of the nanocom-
posites. Mechanical properties of dumbbell shaped specimens
were unveiled using Universal Testing Machine through
stress-strain curves, with a cross-head speed of 5 mm/min at
room temperature. The data from the stress-strain graphs were
used to find the values of tensile strength, Young’s modulus and
elongation at break. Atomic Force Microscope was employed
to reveal the surface morphology of the nanocomposites. A
specimen of one cm2 was placed under the surface analyzing
probe. The result were displayed in form of SPM (Scanning
Probe Micrograph).
Results and Discussion
AC Impedance. The impedance result of Cu-PVA nano-
composite having the greatest ratio of copper nanoparticles
is depicted in Figure 1. A semi-circular Nyquist plot was
observed for all the compositions, showing a conducting
behavior of the nanocomposite. The conductivity of the
nanocomposite is attributed to the incorporation of copper
nanoparticles due to the conducting and metallic nature of
copper. The same fact is also used to endorse the even distri-
bution of the copper nanoparticles throughout the polymer
bulk as well as on the surface. An equivalent circuit was obtained
for the Cu-PVA nanocomposite sample that is depicted by
Figure 2. Nova application software was used to add differ-
ent circuit components with the most suitable initial values.
This was done by plugging in different initial values of circuit
components in order to obtain the best fit. Warburg imped-
ances can also be added to obtain a good fit.21
Bulk resistance (Rb) was worked out from the Z' versus Z''
plot for every sample using point of intersection of the bias
and the horizontal axis. Consequently ionic conductivity (σ)
was calculated from the values of bulk resistance in each
case using Eq. (1).
σ = l/ARb (1)
‘A’ represents the area of measuring electrode while ‘l’
expresses thickness of the composite film. Average thickness
of the films was measured to be 0.001 cm and the area of
measuring electrode was 1 cm2. By incorporating these values
and the bulk resistances obtained for various composites in
the Eq. (1), ionic conductivity values were figured out for
all the developed composites. The same results are exhibited
graphically in Figure 3. The increased concentration of nanopar-
ticles in the nanocomposite is responsible for an increase in
the ionic conductivity.12 The rate gradient of ionic conduc-
Macromol. Res., Vol. 24, No. 4, 2016
 Structural and Electromechanical Behavior Evaluation Of Polymer-Copper Nanocomposites

Figure 1. AC impedance spectrum of (a) Cu-PVA nanocomposite and PVA/Copper nanoparticles; (b) 2 mg, (c) 2 mg, (d) 4 mg, and (e) 5 mg.

tivity approaches to maximum at higher concentration of size. This attributes to the fact that elongated structures have
metallic nanoparticles. This phenomenon is attributed to the very high aspect ratios as compared to non-agglomerated filler
fact that the Cu nanoparticles cause chain unfolding of the nanoparticles.24 At this amount of Cu nanoparticles, agglomerated
polymer. This makes further free volume available for ionic fillers form conducting networks in the matrix. Once the
conduction governed by high aspect ratio of nanoparticles.22 conductive network has already been made; a further addi-
In this way greater number of conducting pockets are pro- tion of the Cu NPs has no pronounced effect on the conduc-
duced due to addition of copper nanoparticles into the PVA tivity of the nanocomposite.25 This is why on further loading
matrix.23 It is noteworthy here that we are reporting the elec- of 3, 4, and 5 mg of nanoparticles, a negligible raise in the
trical conductivity of the order of 10-5 S cm-1 which is much conductivity occurs.
higher than the reported values for such a polymeric nano- Tensile Properties. The Cu-PVA nanocomposites with vari-
composite system. ous concentrations of metallic nanoparticles were subjected
The threshold of percolation for electrical properties depends to stress-strain tests. The test results were used to figure out
on the extend of dispersion, type and geometry of the con-
ducting fillers in the PVA polymer matrix. In Figure 2, ionic
conductivity increases from very low to higher value with the
incorporation of 1 mg of Cu NPs. but then increases abruptly
by addition of 2 mg Cu NPs. This is due to the fact that elec-
trical percolation threshold for Cu-PVA nanocomposites with
1 mg NP is related to the consequence that the Cu NPs were
dispersed homogeneously and evenly in the matrix. But at 2 mg
NP, due to secondary agglomeration, size as well as shape
of the particles changes and the threshold value of the con-
ductivity is attained due to larger size and elongated particle

Figure 2. Circuit diagram of Cu-PVA nanocomposite. Figure 3. Ionic conductivity of Cu-PVA nanocomposite.

Macromol. Res., Vol. 24, No. 4, 2016 311

 G. Nasar et al.
Figure 4. Young’s modulus trend of Cu-PVA nanocomposite.
Figure 5. Tensile strength variation of Cu-PVA nanocomposite.
Young’s moduli, tensile strengths and elongation at break,
as shown in Figures 4, 5, and 6, respectively. Young’s modulus
and elongation at break show an increase with the incorpo-
ration of copper nanoparticles while tensile strength tends to
drop. This phenomenon is attributed to the increase in the
brittle nature of nanocomposite due to the interaction of Cu
nanoparticles with polymer matrix. Unlike bulk metal, cop-
per nanoparticles within the polymer matrix display a brittle
behavior.26 Network of the polymer restricts the copper nanopar-
ticles in a well dispersed morphology as depicted from the
SEM results already reported in our previous communica-
tion.27 Due to agglomeration of the metal particles within the
polymer, the resulting composite displays an overall decrease
of tensile strength. Similar results of tensile properties of nano-
composite system have been reported by Fraczek et al.28 It
is important to note that such a behavior of the composite
material prevails up to an optimized threshold value of Cu
312
Figure 6. Elongation at break trend of Cu-PVA nanocomposite.
nanoparticles for alloying with the polymer matrix. Beyond
that value due to alloying effect, there occurs a decrease in
the degree of elongation, and hence the composites would
adopt a lesser elastic behavior.29 At a further increase of Cu
nanoparticles concentration, the Cu nanoparticles tend to
interact among themselves through their electronic cloud.
This results in overall increase in elastic as well as metallic
behavior. It has been established and commonly accepted
that Young’s modulus of polymer nanocomposites depends
to a great extent on filler dispersion and interfacial interaction.
An increase in the modulus is a clear indication of a good degree
of dispersion of the nanoparticles.25,30 In this case it is signif-
icant that the elastic behavior has suggestively decreased,
resulting in imparting rigidity to the composite system and
hence Young’s modulus and elongation at break both tend
to increase. Electrical conductivity increases likewise as
already discussed.
Atomic Force Microscopy. AFM was used to characterize
the samples of the nanocomposite for their surface morphology.
This technique is used to provide a good idea of the mor-
phology of the surface and size of the nanoparticles embed-
ded on the surface depicted from the roughness of the surface.
The distribution of the nanoparticles within the polymeric
matrix is also exhibited through this technique as revealed
by Figure 7. The surface morphology of the nanocomposite
sample is evidently uniform, having completed and manifest
dispersion of the Cu particles within the bulk of the matrix.
It is notable that no nanoparticles lie outside the surface of PVA.
This fact is a positive indication to explain the even distribution
of the nanoparticles in the polymer and is attributed to a
strong interaction between the filler and the matrix.31 The
agglomerates produced due to copper nanoparticles were
characterized as less than 100 nm in three dimensions. This
provides another clue about the size of the copper nanoparticles
coated under the surface layer of PVA at the nanoscale.
Macromol. Res., Vol. 24, No. 4, 2016
 Structural and Electromechanical Behavior Evaluation Of Polymer-Copper Nanocomposites
Figure 7. AFM image depicting morphology of Cu-PVA nano-
composite.
Conclusions
Nanoparticles of copper were successfully prepared by
chemical reduction method. Various compositions of nano-
composites were prepared by incorporating copper nanoparticles
in poly(vinyl alcohol). Smooth films of the nanocomposites
were obtained. Electrical conductivity was enhanced to the
order of 10-5 S cm-1. Mechanical properties were found to
improve by incorporating copper nanoparticles in PVA. Young’s
modulus and elongation at break indicated an increase while
tensile strength decreased at higher concentration of copper
nanoparticles. AFM studies revealed a uniform and smooth
morphology of the prepared films with agglomerates of less
than 100 nm due to the copper nanoparticles beneath the poly-
mer surface. Due to its enhanced electrical properties, the
prepared composite can be used effectively in electrical and
charge storing devices.
Acknowledgment. Authors are thankful to The Higher
Education Commission of Pakistan for funding and provid-
ing facilities for the present research work.
References
(1) S. Liu, S. Xue, W. Zhang, and J. Zhai, Ceram. Int., 40, 15633
(2014).
(2) E. P. Giannelis, Adv. Mater., 8, 29 (1996).
(3) B. H. Liu, P.-J. Su, C.-H. Lee, and J.-L. Huang, Ceram. Int.,
39, 4205 (2013).
(4) F. Alberto, B. Sergio, and C. Giovanni, American Chemical
Society 2009, pp 10-24.
(5) H. Ismail, S. Z. Salleh, and Z. Ahmad, Polymer-Plastics Technol.
Macromol. Res., Vol. 24, No. 4, 2016
Eng., 50, 681 (2011).
(6) M. Khan, A. Shakoor, and J. Nisar, Ionics, 16, 539 (2010).
(7) J. P. G. Villaluenga, M. Khayet, M. A. López-Manchado, J. L.
Valentin, B. Seoane, and J. I. Mengual, Eur. Polym. J., 43,
1132 (2007).
(8) G. Nasar, M. S. Khan, and U. Khalil, Macromol. Symp., 298,
124 (2010).
(9) M. A. Khan, S. Riaz, I. Ali, M. N. Akhtar, G. Murtaza, M.
Ahmad, I. Shakir, and M. F. Warsi, Ceram. Int., 41, 651
(2015).
(10) A. Sobhani and M. Salavati-Niasari, Ceram. Int., 40, 8173
(2014).
(11) F. Hamid, S. Akhbar, and K. H. K. Halim, Procedia Eng., 68,
418 (2013).
(12) R. Ali, M. A. Khan, A. Mahmood, A. H. Chughtai, A. Sultan,
M. Shahid, M. Ishaq, and M. F. Warsi, Ceram. Int., 40, 3841
(2014).
(13) Y. Zhong, D. Janes, Y. Zheng, M. Hetzer, and D. D. Kee,
Polym. Eng. Sci., 47, 1101 (2007).
(14) X. Qian, N. Gu, Z. Cheng, X. Yang, E. Wang, and S. Dong,
Electrochim. Acta, 46, 1829 (2001).
(15) M. N. Ashiq, S. Shakoor, M. Najam-ul-Haq, M. F. Warsi, I. Ali,
and I. Shakir, J. Magn. Magn. Mater., 374, 173 (2015).
(16) A. K. Nath and A. Kumar, J. Membr. Sci., 485, 30 (2015).
(17) Q. Choudhry, M. A. Khan, G. Nasar, A. Mahmood, M. Sha-
hid, I. Shakir, and M. F. Warsi, J. Magn. Magn. Mater., 393,
67 (2015).
(18) S. Yoon, S. Lee, I. Choi, Y. Do, and S. Park, Macromol. Res.,
23, 713 (2015).
(19) G. Salimbeygi, K. Nasouri, A. Shoushtari, R. Malek, and F.
Mazaheri, Macromol. Res., 23, 741 (2015).
(20) N. Ahn, T.-H. Kim, S. Song, J.-M. Moon, T. Ha, and J. Choi,
Macromol. Res., 23, 726 (2015).
(21) A. Palit and S. O. Pehkonen, Corros. Sci., 42, 1801 (2000).
(22) A. K. Nath and A. Kumar, Electrochim. Acta, 129, 177 (2014).
(23) W. M. Daoush, B. K. Lim, C. B. Mo, D. H. Nam, and S. H.
Hong, Mater. Sci. Eng. A, 513-514, 247 (2009).
(24) X. Yang, Y. Zhan, R. Zhao, and X. Liu, J. Appl. Polym. Sci.,
125, 828 (2012).
(25) Y. Zhan, Y. Lei, F. Meng, J. Zhong, R. Zhao, and X. Liu, J.
Mater. Sci., 46, 824 (2011).
(26) J. Hwang, T. Yoon, S.H. Jin, J. Lee, T.-S. Kim, S. H. Hong,
and S. Jeon, Adv. Mater., 25, 6724 (2013).
(27) G. Nasar, U. Khalil, and M. S. Khan, J. Sci. Technol., 35, 1
(2013).
(28) A. Fraczek-Szczypta and S. Blazewicz, J. Mater. Sci., 46, 5680
(2011).
(29) B. Lin, G. A. Gelves, J. A. Haber, and U. Sundararaj, Ind.
Eng. Chem. Res., 46, 2481 (2007).
(30) Y. Srithep, L.-S. Turng, R. Sabo, and C. Clemons, Cellulose,
19, 1209 (2012).
(31) Y.-J. Choi, H.-H. Park, S. Golledge, and D. C. Johnson,
Ceram. Int., 38, S525 (2012).
313