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CERAMICS
INTERNATIONAL
Ceramics International 39 (2013) 9651–9658
www.elsevier.com/locate/ceramint

Preparation and characterization of copper oxide particles incorporated

polyurethane composite nanofibers by electrospinning
R. Nirmalaa,n, Kyung Soo Jeona, Baek Ho Lima, R. Navamathavanb,
Hak Yong Kima,n
a
Department of Organic Materials and Fiber Engineering, Chonbuk National University, Jeonju 561-756, South Korea
b
School of Advanced Materials Engineering, Chonbuk National University, Jeonju 561-756, South Korea
Received 23 April 2013; received in revised form 20 May 2013; accepted 20 May 2013
Available online 30 May 2013

Abstract

In this paper, we demonstrate the preparation of copper oxide (CuO) particles incorporated polyurethane (PU) composite nanofibers by using
electrospinning. Two step processes were adopted to incorporate the CuO particles in PU nanofibers. In the first step, the cupric acetate was added
to poly(vinyl alcohol) to obtain a thin film by wet casting. Then the thin film was calcined at 500 1C and ground to prepare the CuO particles. In
the second step, these CuO particles were incorporated in the PU to obtain composite nanofibers. Different types of nanofiber mats were prepared
by varying the concentration of CuO particles. The surface morphology, structure, bonding configuration, thermal, optical and electrical
properties of the resultant nanofibers were characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier
transform infrared spectroscopy (FT-IR), UV–vis (ultraviolet visible) spectroscopy, thermogravimetric, photoluminescence and current–voltage
analysis. The electrical conductivities of the PU/CuO composite nanofibers were markedly improved than that of pristine PU nanofibers. The
improvement of electrical properties is attributed to the better carrier transport in the composite nanofibers.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Electrospinning; C. Electrical properties; D. CuO particles; D. Polyurethane

1. Introduction become highly recognized method for obtaining polymer

nanofibers with diameters down to a few nanometers and of
One-dimensional (1D) nanomaterials have attracted growing a broad range of complex architectures of nanofibers and
attention due to their unique physical traits including their nonwovens [12–15]. Polymeric nanofibers exhibit unusual
electronic, magnetic, optical, and mechanical properties [1–4]. properties due to their very small diameter, which leads to
Various strategies have been proposed for obtaining these high surface area, high aspect ratio, and better mechanical
materials. A variety of nano-scale materials with different properties. These remarkable properties underlie the substantial
morphologies have been synthesized by using various methods interests in these materials for industrial, biomedical, and
including chemical vapor deposition, arc discharge, laser electronic applications.
ablation, electrospinning and template based physical vapor In the past few years, a wide range of synthetic and natural
transport [5–11]. Among them, electrospinning is a simple and polymers in pure or blend solutions have been electrospun to
sophisticated technique for producing nanofibers. The main form nanofibers. In particular, polyurethane (PU) is a thermo-
advantage of electrospinning is the relatively quick and simple plastic resilient elastomer of significant industrial importance
way to fabricate a variety of materials into nanofibrous which possesses a wide range of desirable properties such as
structure. During last decade electrospinning of polymers has elastomeric, resistant to abrasion, and excellent hydrolytic
stability [16–18]. Numerous studies on the electrospinning of
n PU have been conducted. Electrospun PU nanofiber mats
Corresponding authors. Tel.: +82 63 270 2351; fax: +82 63 270 4249.
E-mail addresses: nirmalmathu@gmail.com (R. Nirmala), exhibit good mechanical properties and have a wide variety of
khy@jbnu.ac.kr (H.Y. Kim). potential application in high-performance air filters, protective

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.05.087
9652 R. Nirmala et al. / Ceramics International 39 (2013) 9651–9658

textiles, wound dressing materials and sensors [19–24]. Due to 2.2. Preparation of CuO particles
these merits, PU nanofibers have been found to be a very
promising material of interest. The properties of PU can be Initially, 0.4 g cupric acetate was added in 1 g of water and
adjusted desirably based on the requirements. Metal oxide then slowly mixed into 7.6 g of PVA aqueous solution (10 wt
containing PU nanofibers are of great interest in many %). The solution was kept under vigorous magnetic stirring
technological applications. Such kinds of composite nanofiber until to obtain a viscous gel. Then the viscous gel was gently
materials can have much improved properties in terms of poured in the Petri dish to obtain thin film by wet casting. The
thermal stability, flexibility and solubility with that of the thin film was calcined at500 1C in air ambient for 5 h to
pristine PU nanofibers. remove the organic constituents of PVA and convert the
The oxides of transition metals are of important class of precursor into pure CuO particles. The resultant product was
semiconductors, which can be utilized for variety of applications further ground to reduce the particle size.
in magnetic storage media, solar energy transformation, electro-
nics and catalysis [25–28]. Among the oxides of transition metals, 2.3. Electrospinning
copper oxide (CuO) nanoparticles are of special interest because
of their efficiency as nanofluids in heat transfer application. CuO The PU polymer solution for electrospinning was prepared
is a semiconducting compound with a narrow band gap and also by dissolving 10 wt% of PU in 85% DMF and THF solvent in
used for photoconductive and photothermal applications [29]. ratio of 1:1. Later 1, 5 and 10 wt% of the CuO particles were
Much effort has been devoted to synthesizing unique CuO mixed in the polymer solution to make the composite
nanostructures, such as, rods, wires, ribbons, cubes, spheres and nanofibers. Then the polymer solution containing the CuO
dandelions [30–32]. The gas sensing responses of oxide materials particle was loaded into a 5 ml plastic syringe equipped with a
can be improved with increasing surface-area-to-volume ratio. polystyrene micro-tip (0.3 mm inner diameter and 10 mm
Therefore, the development of oxide materials with 1D geometry length), which was connected to a high-voltage power supply
is highly desirable. (CPS-60 K02V1, Chungpa EMT, South Korea). Electrospin-
Nanofiber structures are investigated for their electrical ning was performed at a voltage of 17 kV. A grounded iron
properties and device characterizations. The electrical conduc- drum was rotated at a constant speed by a DC motor to collect
tance is a fundamental quantity encountered in every study of the developing nanofibers, which was kept at a distance of
electrical transport phenomena in nanostructured materials. 15 cm from the micro-tip. All experiments were conducted at
Polymer nanofibers can be more readily applicable if their room temperature. Later, the electrospun PU mats were
electrical conductivities were enhanced. The electrical conduc- detached from the collector and vacuum dried for 24 h. The
tivities of PU nanofibers can be significantly improved by resultant nanofiber mats were utilized for the further
adding metal oxide nanoparticles with high electric conductiv- characterizations.
ities. The electrical property is known to influence the char-
acteristics of the device and its stability under an electric field. 2.4. Characterizations
In this study, we prepared CuO nanoparticles incorporated
PU composite nanofibers by using the electrospinning process. The morphology of the electrospun PU and PU/CuO
Different types of PU/CuO composite nanofibers were electro- nanofibers were observed by using scanning electron micro-
spun by varying the concentration of CuO nanoparticles. The scopy (SEM, Hitachi S-7400, Hitachi, Japan). Elemental
prepared PU/CuO composite nanofibers were analyzed by composition analysis of the composite nanofibers was carried
scanning electron microscopy (SEM), energy dispersive X-ray out by using a SEM equipped with an energy dispersive X-ray
analysis (EDX), X-ray diffraction (XRD), Fourier transform (EDX) spectrometer. Structural characterization was carried
(FT-IR), thermogravimetric analysis (TGA) UV–vis, photolu- out by X-ray diffraction (XRD) in a Rigaku X-ray diffract-
minescence (PL) and current–voltage (I–V) measurements. ometer operated with Cu Kα radiation (λ=1.540 Å). The
bonding configurations of the samples were characterized by
2. Experimental means of Fourier transform infrared (FT-IR). Thermogravi-
metric analysis (TGA, Perkin-Elmer, USA) was carried out for
2.1. Materials the samples under nitrogen ambient with a flow rate of 20 mL/
min. The samples were heated from 30 to 800 1C at a rate of
Poly(vinyl alcohol) (PVA) solution (number averaged mole- 10 1C/min. The UV–vis spectra were measured in the range of
cular weight (Mw)=85,000–124,000 g/mol, degree of hydroly- 200–800 nm by using a UV–vis spectrometer (Lambda 900,
sis=87–89%, Aldrich Co., USA) and copper acetate (Aldrich Co., Perkin-Elmer, USA). The optical property of Pu/CuO compo-
USA) were used to prepare CuO particles. Polyurethane (PU, site nanofibers was characterized by photoluminescence (PL)
Mw=110,000) was purchased from Cardio Tech, Japan. Tetra- analysis using a 325 nm He–Cd laser. To study the electrical
hydrofuran (THF) and NN-dimethylformamide (DMF) (analytical properties, several circular silver electrodes with a diameter of
grade, Showa, Japan) were used as solvents without further about 500 mm at a distance of 0.5 mm were made on the
purification. PU solution with 10 wt% was prepared by dissolving 1
1 cm2 of composite nanofibers. Silver metal contacts were
in THF and DMF (1:1). All the above chemical reagents used made on the nanofiber mat to have good ohmic contact. Then
were of analytical grade and used without further purification. the current–voltage (I–V) characteristic was measured for the
 R. Nirmala et al. / Ceramics International 39 (2013) 9651–9658 9653

composite nanofibers by using a semiconductor parameter the pristine PU nanofibers. The pristine PU nanofibers exhib-
analyzer (4200-SCS, Keithley). ited smooth surface and bead-free nature. The diameters of the
nanofibers are in the range of 100–300 nm along their lengths.
3. Results and discussion Fig. 1(b)–(d) shows the low and high magnification SEM
image of PU/CuO composite nanofibers with CuO particles
Fig. 1 shows the morphology of the electrospun nanofibers. concentration of 1%, 5% and 10%, respectively. Significant
Fig. 1(a) shows the low and high magnification SEM image of morphological difference can be observed among pristine and

Fig. 1. SEM image of electrospun nanofibers of (a) pristine PU, (b) PU/CuO with CuO 1%, (c) PU/CuO with CuO 5%, and (d) PU/CuO with CuO 10%. The labels
1 and 2 depict the low and high magnification images.
 9654 R. Nirmala et al. / Ceramics International 39 (2013) 9651–9658

composite PU nanofibers. Due to the presence of CuO particles CuO particles, however, the PU/CuO composite nanofibers with
in PU polymer solution, the electrical conduction of the CuO content of 1% did not show any significant peaks. This may
solution can be enhanced which further increases the accel- be due to very low content of CuO particles in the composite
eration of jetting polymer solution during the electrospinning nanofibers. No significant diffraction peaks of any other phases or
process. Therefore, the highly conductive polymer solution impurities can be detected in the PU/CuO composite nanofibers,
gives faster electrospinning. As can be seen from the SEM which demonstrate the successful incorporation of CuO particles
images, the CuO particles were attached at the periphery of the in PU nanofibers. The successful incorporation of CuO particles
PU nanofibers. From the SEM data, we have estimated the in PU nanofibers was confirmed by the XRD data which is in
particles size of CuO in the composite nanofibers. The good agreement with that of SEM-EDX data.
diameters of the CuO particles are observed to be in the range The bonding configurations of the resultant composite
of 200–500 nm. At the same time, the diameters of the PU/ nanofibers were performed by using FT-IR spectroscopy.
CuO composite nanofibers were almost similar to that of Fig. 4 shows the FT-IR spectra of pristine and composite
pristine PU nanofibers. nanofibers. These FT-IR spectra illustrate of the interaction
To analyze further the elemental composition of PU/CuO between the PU nanofibers containing CuO particles. The
composite nanofibers, SEM-EDX analysis was performed. characteristic transmittance peaks of the PU films containing
Fig. 2(a)–(d) shows the SEM-EDX images of the pristine PU metal particles can be assigned as shown in Fig. 4. It can be
and PU/CuO composite nanofibers with different CuO con- seen that the characteristic peaks of PU films containing metal
centrations of 1%, 5% and 10%, respectively. The EDX
spectrum clearly confirmed that the PU composite nanofibers PU + CuO 10%

(200)
(002)
(111)
consist of copper, oxygen and carbon elements, as shown in

(113)

(220)
Fig. 2. This result confirmed the successful incorporation of
CuO particles in PU nanofibers. PU + CuO 5%

(111)
(002)
XRD is used to investigate the phase structures of the pristine
Intensity (a. u.)

and composite nanofibers. Fig. 3 shows the XRD patterns of

pristine and composite PU/CuO nanofibers. The XRD pattern of
PU + CuO 1%
pristine PU nanofibers showed a broad peak at 201 due to the
amorphous nature of the sample. The existence of the prominent
XRD patterns corresponding to the CuO particles in the PU phase
were observed for the composite nanofibers mats as indexed in PU

the Fig. 3. The intense diffraction peaks at 351, 381, 441, 481,
64.51 and 781 are corresponding to the (002), (111), (200), (202),
10 20 30 40 50 60 70 80
(113) and (2 2 0) planes of CuO, which is consistent with the
2θ (Degree)
JCPDS data (JCPDS file No. 05-661). The intensity of the
diffraction patterns were increased with increasing content of Fig. 3. XRD patterns of PU and PU/CuO composite nanofibers.

Fig. 2. SEM-EDX image of electrospun nanofibers of (a) pristine PU, (b) PU/CuO with CuO 1%, (c) PU/CuO with CuO 5%, and (d) PU/CuO with CuO 10%.
 R. Nirmala et al. / Ceramics International 39 (2013) 9651–9658 9655

particles are appeared in the range of 500–1750 cm−1. The 100

FTIR spectroscopy of electrospun composite nanofibers have 90
characteristic transmittance bands at 3240, 2960, 1740, 1530,
80
1220, 1110 and 777 cm−1, which represents υ (N–H), υ (C–H),
70
υ (C ¼ O), υ (C ¼ C), υ (C–C), υ (C–O), υ (C–H) stretching

Weight (%)
modes, respectively [33,34]. It was observed that a broad 60

transmittance band centered at 3500 cm−1 corresponding to – 50

OH stretch vibration. At the same time, the broad peak 40
between 3200 and 3600 cm−1 was increased with increasing 30
PU + CuO 10%
PU + CuO 5%
content of CuO particles in the composite nanofibers. This is
20 PU + CuO 1%
attributed to the increased amount of –OH stretching bonds in PU
the PU/CuO composite nanofibers. Moreover, compared with 10

FT-IR spectrum of pristine PU nanofibers, there was a 0

0 100 200 300 400 500 600 700 800 900
prominent transmittance peak appeared at 1600 cm−1 for the
Temperature (°C)
PU/CuO composite nanofibers due to the copper ions and
isocyanate group of CuO particles. From these results, we Fig. 5. TGA traces of PU and PU/CuO composite nanofibers.
confirm the successful incorporation of CuO particles in PU
nanofibers.
Thermal stability of the pristine and PU/CuO composite
nanofibers was evaluated using TGA in nitrogen atmosphere.
The TGA curves of the pure PU and PU/CuO composite
nanofibers are shown in Fig. 5. The onset thermal stability of
Absorbance (a. u.)

composite nanofibers was enhanced relative to that of pure PU

nanofibers. The onset of decomposition of pristine PU and
PU + CuO 10%
composite nanofibers were found to be in the range of PU + CuO 5%
200–300 1C. These results indicated that the cations of the copper PU + CuO 1%
PU
(e.g., Cu2+) might decrease the thermal stability of PU/CuO
composite nanofibers. The effect was attributed to the ability of
the cation to form complexes in which the copper atoms were
coordinately bonded to urethane group [35]. As expected, the
residual weight significantly increases with the incorporation 200 300 400 500 600 700 800
of CuO particles in PU nanofibers. It is noteworthy, to mention Wavelength (nm)
that as the amount of CuO particles is increased in the polymer
solution, the more residual amount is gained by nanofibers. It 90
was found that the residues of the PU and composite
80
nanofibers at 700 1C were about 8%, 22%, 28%, and 40%,
respectively. 70
Fig. 6 shows the UV–vis spectra of pristine PU and
60
Reflectance (%)

composite nanofibers. As shown from the absorbance spectra

50

40

30
PU + CuO 10%
20 PU + CuO 10%
Transmittance (a. u.)

PU + CuO 5%
10 PU + CuO 1%
PU
PU + CuO 5% 0
200 300 400 500 600 700 800 900
Wavelength (nm)

Fig. 6. UV–vis spectra of PU and PU/CuO composite nanofibers

PU + CuO 1%
(a) absorbance, and (b) reflectance.

PU
in Fig. 6(a), the significant increase in the absorption at a
500 1000 1500 2000 2500 3000 3500 4000
wavelength lower than 300 nm can be observed corresponding
Wavenumber (cm-1) to the composite nanofibers containing CuO nanoparticles. The
Fig. 4. FT-IR spectra of PU and PU/CuO composite nanofibers. absorbance intensity was increased with the addition of
9656 R. Nirmala et al. / Ceramics International 39 (2013) 9651–9658

CuO particles in PU nanofibers, which was attributed to the nanoparticles counterpart homogeneously present in the sur-
significant enhancement of light absorption in the visible light faces of the nanofibers. Such kind of characteristic of these
region. The respective reflectance spectra of these composite composite nanofibers are of great importance as per technolo-
nanofibers are shown in Fig. 6(b). As expected, the reflectance gical applications are concerned.
intensity was reduced with the addition of CuO particles in PU The luminescence properties of composite nanofibers are
nanofibers. It was illustrated that the incorporation of CuO useful in understanding the physics of nanostructures and their
particles in PU nanofibers could effectively block the UV potential applications in various fields. The PL spectrum of the
region (200–300 nm). The reflectance was decreased with the system is formed as a result of the competition between
addition of CuO particles in PU nanofibers which can be electron–hole separation, electron–phonon scattering, and elec-
attributed to the effective absorbance of UV emissions by the tron–hole recombination. Fig. 7 shows the room-temperature
PL spectrum of the pristine PU and PU/CuO composite
PU + CuO 10% nanofibers. As shown in the PL data, a feeble PL intensity
was observed for the pristine PU nanofibers. The PL spectra of
the PU/CuO composite nanofibers are dominated by the broad
band emission in the range of 350–600 nm. The PL intensity
PL Intensity (a. u.)

PU + CuO 5%
was drastically increased with the incorporation of CuO
particles in PU nanofibers. The broad band emission from
the PL spectrum at room temperature indicates that the
Pu + CuO 1%
PU/CuO composite nanofibers have good luminescence qual-
ity. According to the literature, the intensity of the PL peaks is
an indicator for the electrons/hole recombination rate, low
PU
intensity indicates low recombination and vice versa [36].
Fig. 8 shows the electrical properties of the composite
nanofibers. The I–V dependence is typical for a metal–
350 400 450 500 550 600 650
polymer–metal configuration, i.e., it is formed by the char-
Wavelength (nm)
acteristics of two point-to-point Schottky diodes. Fig. 8 (a) and
Fig. 7. PL spectra of PU and PU/CuO composite nanofibers. (d) shows the I–V characteristics of the pristine PU and

4
PU 60 PU + CuO 1%
3
40
2
Current (nA)

Current (nA)

20
1
0
0
-20
-1
-40
-2
-60
-3
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 -6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
Voltage (V) Voltage (V)

200
140 PU + CuO 5% PU + CuO 10%
180
120
160
100
140
80
Current (nA)
Current (nA)

120
60
100
40
80
20
60
0
40
-20
20
-40
0
-60
-20
-6 -4 -2 0 2 4 6 8 10 -6 -4 -2 0 2 4 6
Voltage (V) Voltage (V)

Fig. 8. I–V characteristics of nanofibers (a) pristine PU, (b) PU/CuO with CuO 1%, (c) PU/CuO with CuO 5%, and (d) PU/CuO with CuO 10%.
 R. Nirmala et al. / Ceramics International 39 (2013) 9651–9658 9657

PU/CuO composite nanofibers for the different applied bias Acknowledgments

voltage ranging between −5 and 10 V, respectively. With the
increasing voltage, current is stably increased. It was observed This research was financially supported by the Ministry of
that the pristine PU nanofibers exhibited a current value of Education, Science Technology (MEST) and National Research
3 nA corresponding to the applied voltage of 1 V. At the same Foundation of Korea (NRF) through the Human Resource Training
time, when we increased the applied bias beyond 1 V, the Project for Regional Innovation (2012H1B8A2025931). This work
current increases abruptly, we could not measure the I–V was also supported by the National Research Foundation of Korea
characteristics for the pristine PU nanofibers. The current (NRF) Grant funded by the Korea government (MEST) (No.
conduction is unstable. The unstable current characteristic for 2012R1A2A2A01046086).
the pristine PU nanofibers state can be interpreted as the poor
conduction nature of the polymer. On the other hand, the CuO References
particles incorporated composite nanofibers showed quite
stable I–V characteristics for the large range of applied bias [1] K.S. Shankar, A.K. Raychaudhuri, Fabrication of nanowires of multi-
voltages as shown in Fig. 8(b)–(d). component oxides: review of recent advances, Materials Science and
Engineering C 25 (2005) 738–751.
As shown in Fig. 8(a)–(c), the I–V characteristics of pristine [2] C.N.R. Rao, A. Govindaraj, Synthesis of inorganic nanotubes, Advanced
PU and PU composite nanofibers with CuO content of 1% and Materials 21 (2009) 4208–4233.
5%, respectively, exhibited almost similar trend of electric [3] S.V.N.T. Kuchibhatla, A.S. Karakoti, D. Bear, S. Seal, One dimensional
conduction behavior except the value of current for the specific nanostructures materials, Progress in Materials Science 52 (2007)
699–913.
applied bias voltage. However, the PU/CuO composite nano-
[4] C.C. Chen, C.C. Yeh, C.H. Chen, M.Y. Yu, H.L Li, J.J. Wu, K.H. Chen,
fibers with CuO concentration of 10% revealed quite different L.C. Chen, J.Y. Peng, Y.F. Chen, Catalytic growth and characterization
electric conduction with that of other counterparts studied here. of gallium nitride nanowires, Journal of American Chemical Society 123
This behavioral appearance of the I–V characteristics is (2001) 2791–2798.
attributed to the significant enhancement of carrier concentra- [5] Y. Wu, P. Yang, Germanium nanowire growth via simple vapor
tion in the composite nanofibers. As shown in Fig. 8(d), the transport, Chemical Materials 12 (2000) 605–607.
[6] M.H. Hunag, Y. Wu, H. Feick, N. Tran, E. Weber, P. Yang, Catalytic
measured I–V characteristics at room temperature showed a growth of zinc oxide nanowires by vapor transport, Advanced Materials
current rectification with a sharp onset voltage of 3.2 V, in the 13 (2001) 113–116.
forward bias with relatively negligible leakage currents at the [7] W. Han, P. Redlich, F. Ernst, M.R. Uhle, Synthesis of GaN carbon
reverse bias. From the I–V curve of PU/CuO composite composite nanotubes and GaN nanorods by arc discharge in nitrogen
nanofibers, the current is leniently increased with applied atmosphere, Applied Physics Letters 76 (2000) 652–654.
[8] Y.C. Choi, W.S. Kim, Y.S. Park, S.M. Lee, D.J. Bae, Y.H. Lee, G.
voltages as 10 nA at 3 V, 25 nA at 4 V, and 180 nA at 5 V. S. Park, W.B. Choi, N.S. Lee, J.M. Kim, Catalytic growth of β-Ga2O3 by
The enhanced electrical conductivity of these composite arc discharge, Advanced Materials 12 (2000) 746–750.
nanofibers can readily help the carrier transport in these [9] X.F. Duan, C.M. Lieber, General synthesis of compound semiconductor
structures to perform efficient conduction which can be utilized nanowires, Advanced Materials 12 (2000) 298–302.
[10] X. Duan, C.M. Lieber, Laser-assisted catalytic growth of single crystal
for many technological applications.
GaN nanowires, Journal of American Chemical Society 122 (2000)
188–189.
[11] J.Y. Lin, B. Ding, J.Y. Yu, Y. Hsieh, Direct fabrication of highly
nanoporous polystyrene fibers via electrospinning, ACS Applied Materi-
4. Conclusions als and Interfaces 2 (2010) 521–528.
[12] R. Nirmala, J.W. Jeong, R. Navamathavan, H.Y. Kim, Synthesis and
electrical properties of TiO2 nanoparticles embedded in polyamide-6
In summary, we have successfully obtained the CuO nanofibers via electrospinning, Nano–Micro Letters 3 (2011) 56–61.
particles incorporated PU composite nanofibers by using the [13] R. Nirmala, B. Woo-il, R. Navamathavan, D. Kalpana, Y.S. Lee,
electrospinning process. The as-spun PU/CuO composite H.Y. Kim, Influence of antimicrobial additives on the formation of rosin
nanofibers were observed to be smooth with uniform diameters nanofibers via electrospinning, Colloids and Surfaces B: Biointerfaces
104 (2013) 262–267.
and randomly aligned along their lengths. The resultant
[14] R. Gopal, S. Kaur, Z. Ma, C. Chan, S. Ramakrishna, T. Matsuura,
composite nanofibers diameters were in the range of 100– Electrospun nanofibrous filtration membrane, Journal of Membrane
300 nm. The surface morphology, optical and electrical Science 281 (2006) 581–586.
characterization of the synthesized PU/CuO composite nano- [15] B. Ding, M. Wang, X. Wang, J. Yu, G. Sun, Electrospun nanomaterials
fibers were studied by means of SEM, EDX, XRD, FT-IR, for ultrasensitive sensors, Materials Today 13 (2010) 16–27.
TGA, UV–vis, PL, and I–V measurements. The current density [16] U. Ojha, P. Kulkarni, R. Faust, Syntheses and characterization on novel
biostable polyisobutylene based thermoplastic polyurethanes, Polymer 50
and conductivity of the composite PU nanofibers were (2009) 3448–3457.
significantly improved than that of the pristine PU nanofibers. [17] S. Kidoaki, I.K. Kwon, T. Matsuda, Structural features and mechanical
The measured I–V characteristics of PU/CuO composite properties of in situ bonded meshes of segmented polyurethane electro-
nanofibers with CuO content of 10% showed a current spun from mixed solvents, Journal of Biomedical Materials Research B:
rectification with a sharp onset voltage of 3.2 V, in the forward Applied Biomaterials 76 (2006) 219–229.
[18] B. Cuakmakli, B. Hazer, I.O. Tekin, F.B. Comert, Synthesis and
bias. The significant enhancement of electrical properties of characterization of polymeric soybean oil-g-methyl methacrylate (and
these PU/CuO composite nanofibers can be utilized for quite n-butyl methacrylate) graft copolymers: biocompatibility and bacterial
promising future nanotechnological applications. adhesion, Biomacromolecules 6 (2005) 1750–1758.
9658 R. Nirmala et al. / Ceramics International 39 (2013) 9651–9658

[19] H. Deka, N. Karak, R.D. Kalita, A.K. Buragohain, Bio-based thermo- [29] R.V. Kumar, Y. Diamant, A. Gedanken, Sonochemical synthesis and
stable, biodegradable and biocompatible hyperbranched polyurethane/Ag characterization of nanometer-size transition metal oxides from metal
nanocomposites with antimicrobial activity, Polymer Degradation and acetates, Chemical Materials 12 (2000) 2301–2305.
Stability 95 (2010) 1509–1511. [30] X. Song, H. Yu, S.J. Sun, Single crystalline CuO nanobelts fabricated by
[20] D.K. Chattopadhaya, K.V.S.N. Raju, Structural engineering of polyur- a convenient route, Journal of Colloid Interface Science 289 (2005)
ethane coatings for high performance applications, Progress in Polymer 588–591.
Science 32 (2007) 352–418. [31] H. Hou, Y. Xie, Q. Li, Large-scale synthesis of single crystalline quasi-
[21] X. Liu, Y. Zhao, Z. Liu, D. Wang, J. Wu, D. Xu, Investigation on the aligned submicrometer CuO ribbons, Crystal Growth and Design 5
interactions between polyurethane and metal chloride, Journal of Mole- (2005) 201–205.
cular Structure 892 (2008) 200–204. [32] D. Li, Y.H. Leung, A.B. Djurisic, Z.T. Liu, M.H. Xie, J. Gao, W.K.
[22] N. Fong, A. Simmons, L.A.P. Warren, Antibacterial polyurethane J. Chan, CuO nanostructures prepared by a chemical method, Journal of
nanocomposites using chlorhexidine diacetate as an organic modifier, Crystal Growth 282 (2005) 105–111.
Acta Biomaterialia 6 (2010) 2554–2561. [33] Z. Jiang, K.J. Yuan, S.F. Li, W.K. Chow, Study of FTIR spectra and
[23] Y. Choi, R. Nirmala, J.Y. Lee, M. Rahman, S.T. Hong, H.Y. Kim, thermal analysis of polyurethane, Spectroscopy and Spectral Analysis 26
Antibacterial ciprofloxacin HCl incorporated polyurethane composite (2006) 624–628.
nanofibers via electrospinning for biomedical applications, Ceramics [34] R. Chen, C. Huang, Q. Ke, C. He, H. Wang, X. Mo, Preparation and
International 39 (2013) 4937–4944. characterization of coaxial electrospun thermoplastic polyurethane/col-
[24] R. Nirmala, K.Y. Nam, R. Navamathavan, S.J. Park, H.Y. Kim, Hydro- lagen compound nanofibers for tissue engineering applications, Colloids
xyapatite mineralization on the calcium chloride polyurethane nanofibers and Surfaces B: Biointerfaces 79 (2010) 315–325.
via biomimetic method, Nanoscale Research Letters 6 (2011) 1–8. [35] Y.B. Cai, Q.F. Wei, Q. You, F.L. Huang, L. Song, Y. Hu, Structural,
[25] A.S. Lanje, R.S. Ningthoujam, S.J. Sharma, R.K. Vatsa, R.B. Pode, thermal and antibacterial properties of polyacrylonitrile/ferric chloride
Luminescence properties of Sn1-xFexO2 nanoparticles, International nanocomposite fibers by electrospinning, International Journal of Poly-
Journal of Nanotechnology 7 (2010) 979–988. mer Analytical Characterization 15 (2010) 110–128.
[26] S. Anandan, X. Wen, S. Yang, Room temperature growth of CuO [36] J. Liu, J. Li, A. Sedhain, J. Lin, H. Jiang, Structure and photolumines-
nanorod arrays on copper and their application as a cathode in dye- cence study of TiO2 nanoneedle texture along vertically aligned carbon
sensitized solar cells, Materials Chemistry and Physics 93 (2005) 35–40. nanofiber arrays, Journal of Physical Chemistry C 112 (2008)
[27] J. Zhang, J. Liu, Q. Peng, X. Wang, Y. Li, Nearly monodisperse Cu2O 17127–17132.
and CuO nanoparticles, Chemical Materials 18 (2006) 867–871.
[28] J.B. Reitz, E.I.J. Solomon, Propylene oxidation on copper oxide surfaces:
Electronic and geometric contributions to reactivity and selectivity,
Journal of American Chemical Society 120 (1998) 11467–11478.