Polym. Bull.
(2012) 68:253–261
DOI 10.1007/s00289-011-0628-3
ORIGINAL PAPER
Influence of nanoscale NiO on magnetic
and electrochemical behavior of PVDF-based polymer
nanocomposites
Aarti Sripathi Bhatt • Denthaje Krishna Bhat
Received: 14 July 2011 / Revised: 3 August 2011 / Accepted: 3 September 2011 /
Published online: 11 September 2011
Ó Springer-Verlag 2011
Abstract New poly(vinylidene fluoride) (PVDF)/NiO-based polymer nanocom-
posites were prepared by phase inversion method, using dimethyl formamide as
solvent and deionized water as non-solvent. The structure and porous morphology
of the membranes were studied by field emission scanning electron microscopy. The
presence of NiO resulted in overall decrease in porosity and crystallinity of the
nanocomposite membranes. Using electrochemical impedance spectroscopy, a
maximum ionic conductivity of 1.08 9 10-3 S cm-1 was obtained for PVDF
membrane with 1 wt% content of NiO. The good efficiency of conductivity
observed in the membrane was explained on the basis of decrease in crystallinity
and movement of charge carriers in NiO structure. The magnetization of nano-
composite membranes gradually increased with increase in NiO content.
Keywords PVDF NiO Porosity Crystallinity Conductivity
Magnetic measurements
Introduction
Inorganic polymer nanocomposites are promising materials for electrochemical
devices and recently also as electrolyte membranes. For more than a decade,
commercially available NafionÒ has been widely used as proton conducting
membrane due to its high conductivity. However, these membranes suffer from
major drawbacks like low thermal stability and low methanol selectivity [1]. Hence
Electronic supplementary material The online version of this article (doi:10.1007/s00289-011-0628-3)
contains supplementary material, which is available to authorized users.
A. S. Bhatt D. K. Bhat (&)
Department of Chemistry, National Institute of Technology Karnataka, Srinivasnagar,
Surathkal 575025, India
e-mail: denthajekb@[Link]
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research has been directed toward finding better alternatives. Many polymers, such
as polyethylene oxide [2], polymethylmethacrylate [3], polyacrylonitrile [4], have
been used as host polymer matrices for proton conducting membranes. Among
these, PVDF has attracted the scientific community for its versatility. Compared to
other fluoropolymers, PVDF has high purity, good strength, excellent chemical
resistance, low melt process temperature, and low cost. Moreover, it can be easily
dissolved in variety of solvents, and porous PVDF membranes can be easily
produced by phase inversion techniques [5, 6]. PVDF as such is being used for
lithium ion batteries [7–9]. However, incorporating PVDF matrix with inorganic
nanofillers improves its overall conductivity. Cao et al. [10] showed that a high ionic
conductivity can be obtained on using polyvinylpyrrolidone as additive in PVDF-
HFP polymer membrane. Additives like salt [11] and polyethylene glycol (PEG)
[12] were also used in PVDF and their various properties were studied.
Consequently, it was observed that addition of inorganic materials along with
these additives helped in improving the conductivity of PVDF. Croce et al. [1]
reported the conductivity and current–voltage studies of PVDF-CTFE copolymer
with dispersed ceramic fillers. The ionic conductivity of PVDF-HFP membranes
treated with PEG increased on adding Al2O3 particles [13].
With the advent of nanomaterials, study on the effect of nano sized particles on
PVDF matrix has gained interest. It has been suggested that transition metal oxides
with poor conductivity are capable of storing high charge when they are highly
dispersed and nanosized [14]. NiO has a wide band gap energy range from 3.6 to
4.0 eV and hence is considered as a p-type semiconductor [15]. Hence, one can
assume that incorporation of NiO nanoparticles will definitely affect the conduc-
tivity of the host polymer. Qureshi et al. [16] have employed Li- and Ti-codoped
NiO/PVDF films as electric and gas sensors.
In this study, PVDF/NiO nanocomposites were prepared by phase inversion
technique and with different contents of NiO filler. The main focus of the study is to
investigate the influence of NiO nanoparticles on conductivity and saturation
magnetization of the membrane.
Experimental
PVDF (Mw = 275,000) was purchased from Sigma Aldrich and was used in pellet
form. Dimethyl formamide (DMF) (Merck) of purity 99.5% was used as solvent.
Distilled water was used throughout the experiment.
Preparation of PVDF/NiO nanocomposite films
NiO nanoparticles of average diameter 10 nm were synthesized by hydrothermal
method [17]. Since the phase inversion process requires the polymer solution to
remain in a uniform and stable state, measures were taken to obtain a homogeneous
polymer solution. Desired amounts of PVDF polymer pellets were added to DMF
and were subjected to vigorous shaking to insure thorough wetting of the polymer
pellets. The dissolution was done by keeping the mixture in a sonicator maintained
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Polym. Bull. (2012) 68:253–261 255
at 60 °C. After the complete dissolution of the polymer pellets, required amount of
NiO nanoparticles were added (wherever applicable) and sonication was continued
till the nanoparticles dispersed homogeneously in the polymer solution. The
solutions were then spin coated (Spin-Coater ACE-1020 Series) on a glass substrate
at 500, 1000, and 2000 rpm for 60 s sequentially. The polymer films were
precipitated out by immersing the glass substrate in deionized water. The films were
retained in water for 24 h to insure complete removal of residual solvent. The films
were labeled as PVDF, PNH1, PNH2, PNH3, and PNH4 for NiO content of 0, 0.3,
0.5, 0.7, and 1 wt. %, respectively.
Characterization techniques
A Zeiss SUPRA 40VP Gemini field emission scanning electron microscope
(FESEM) was used for morphology and microstructure studies of the composite
films. The magnetic properties were assessed with a Vibration Sample Magnetom-
eter (ADE-DMS EV-7 VSM).
The porosity of polymer electrolyte membranes was measured by immersing the
membrane into n-butanol for 2 h after which the membrane surface was dried with a
filter paper. The membranes were weighed before and after the absorption of
n-butanol. The porosity was calculated using the following equation:
Mb =qb
P% ¼ ð1Þ
ðMp =qp Þ þ ðMb =qb Þ
where P% is porosity of the membranes, Mp is mass of membrane, Mb is mass of the
absorbed n- butanol, qp is density of the membrane, and qb is density of n-butanol.
Differential Scanning Calorimetry (DSC) data was obtained in the temperature
range of 35–250 °C (DSC-60, Shimadzu, Japan). The samples, sealed in an
aluminum pan, were heated at a rate of 10 °C per min under nitrogen atmosphere.
An empty pan was used as reference.
Electrochemical impedance measurements were carried out using an electro-
chemical work station, AUTOLAB 30. The films were placed in between two
stainless steel electrodes. The whole set up was held tightly with a plastic clamp.
1 M KOH solution was used as electrolyte. Measurements were carried out using a
small amplitude AC signal of 10 mV over a frequency range of 100 kHz to 0.01 Hz.
To avoid ambiguity, the measurements were taken thrice for each trial.
Results and discussions
Morphology
The porous morphology of the polymer is necessary to understand the transport of
ions, thereby providing information on its conductivity. The FESEM images of
PVDF/NiO films are shown in Fig. 1. In the first step of synthesis, the solvent
evaporation occurred during the spin coating process. The boiling point of DMF is
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Fig. 1 FESEM images for a PNH1, b PNH2, c PNH3, and d PNH4
153 °C, so theoretically it can remain in the membranes. However, during the high
speed spinning, the probability of DMF evaporation is also high. In the extraction
stage, the residual DMF, if any, gets exchanged with water. Since DMF has high
viscosity, the rate of exchange between DMF and water is slow. As a result, the
contraction of the membrane would be homogeneous leading to better uniformity.
Also, DMF is a low molecular weight compound. Hence, after extraction, a
homogeneous nanoporous membrane is obtained. The surface of these pores gets
occupied by the NiO additive and there are chances that the inside of the pores also
get agglomerated by these nanoparticles. It is assumed that addition of larger
content of nanoparticles leads to more aggregation which in turn affects the porosity
of films.
The impact of the presence of NiO nanoparticles on porosity of polymer matrix
was estimated by porosity measurements. The porosity values are given in Table 1.
It can be seen that with increase in the content of NiO, there is a decline in porosity
of the films. This can be possibly due to the occupation of NiO nanoparticles on
surface as well as inside of the pores.
DSC analysis
Knowledge of a polymer’s crystallinity is important as a basis for understanding its
conductivity. The DSC thermograms of PVDF/NiO nanocomposite films are
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Polym. Bull. (2012) 68:253–261 257
Table 1 Porosity, enthalpy, and % crystallinity values of PVDF/NiO films
Sample Porosity (%) Enthalpy (J g-1) Crystallinity (%)
PVDF 62.39 71.54 100.00
PNH1 56.78 58.84 56.20
PNH2 54.93 55.47 52.98
PNH3 54.12 48.12 45.96
PNH4 51.70 40.75 38.92
Fig. 2 DSC thermograms of PVDF/NiO composite films
displayed in Fig. 2. By assuming that pure PVDF is 100% crystalline, the relative
percentage of crystallinity was calculated based on the following equation
DH
% Crystallinity = 100% ð2Þ
DH 0
where DH0 is the heat of fusion of pure PVDF (104.7 J g-1) [18] and DH is the heat
of fusion of PVDF/NiO electrolyte membrane. The latter is obtained by the DSC
data. The enthalpy obtained and the calculated crystallinity of films are listed in
Table 1. The crystallinity of NiO filled PVDF membranes were lower than that of
blank PVDF film. This shows that the amorphous domain of membranes increased
after the incorporation of NiO nanoparticles. This is the reason that the porosity also
showed a gradual decrease. A possible explanation for the observed decrease in
crystallinity is that the polymer undergoes some significant structural reorganization
after the addition of NiO nanoparticles. There may be some complicated
interactions between nickel and oxygen of NiO and fluorine of PVDF which
restricts the crystal formation and promotes amorphicity.
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Electrochemical impedance spectroscopy measurements
Electrochemical impedance spectroscopy is a well-established technique to deduce
number of material properties like conductivity, dielectric constant, relaxation
frequency, and other interfacial properties. The Nyquist plots for the blank PVDF
film and the sample PNH4 is given in Fig. 3. It is obvious from the plots that the
resistance of the polymer film decreased after the incorporation of NiO nanopar-
ticles. By fitting the curves, the charge transfer resistance value for PNH4 was found
to be 2.3713 9 102 ohms. This value is comparatively lower than that obtained for
PVDF film (3.154 9 103 ohms). From the impedance plots, the ionic conductivity
of the polymer electrolytes was estimated by the equation r = L/RA, where L,
A, and R are thickness, area, and bulk resistance of the composite films,
respectively. The bulk resistance was calculated from the high frequency intercept
on the real impedance axis of the Nyquist plot [19]. The conductivity of the blank
PVDF film is 4.77 9 10-4 S cm-1. The value increased to 1.08 9 10-3 S cm-1
with the presence of 1 wt% NiO. On careful observation it can be seen that the
impedance of blank PVDF is a quasi-vertical line whereas after the incorporation of
NiO, the impedance curve tends to be semi-circular in shape. A pure NiO generally
gives a semi-circular curve [20] which implies that the conduction is mainly under
charge transfer control. It is known that ionic conductivity is governed by
the content of carrier ions and their mobility. Also, the semi-circle nature of the
impedance plot suggests that there is a major contribution of NiO to the
conductivity of the membrane. Conductivity in NiO is attributed to the large
number of Ni2? vacancies [21]. A single Ni2? vacancy leads to the transformation
of two adjacent Ni2? ions into Ni3? to attain charge neutrality [22]. The size of NiO
here being nano, the density of Ni2? vacancies is expected to be high. Thus, the
presence of NiO nanoparticles increases the conductivity of PVDF membrane.
Moreover, as discussed in previous sections, NiO also restricts the crystallinity of
the polymer segment. This further enhances the conductivity.
Fig. 3 Nyquist plots for PVDF and PNH4
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Polym. Bull. (2012) 68:253–261 259
Magnetic measurements
It is known that bulk NiO is antiferromagnetic. However, with the reduction in size,
the uncompensated magnetic spins associated with the surface atoms remain no
more negligible and they add up to give rise to a net magnetization. In the present
case, NiO of average particle size of 10 nm, exhibited a ferromagnetic behavior
[17].
Figure 4 shows the room temperature magnetization curves for PVDF films
incorporated with different wt% of NiO nanoparticles. PVDF being diamagnetic
[refer online resource 1], any kind of magnetization inferred to the composite films
is entirely contributed by NiO. Although a slight increase in magnetization along
with NiO content is observed, PVDF/NiO nanocomposite films retain diamagnetism
for NiO content less than 1 wt%. However, the impact of the magnetic nanoparticles
can be clearly observed for PNH4 with 1 wt% of NiO. Here, the transition from
diamagnetic to ferromagnetic behavior is clearly demarcated.
Conclusion
In summary, PVDF/NiO nanocomposite membranes were successfully prepared by
phase inversion method. It has been found that, mainly by porosity and crystallinity
studies, NiO nanoparticles can influence the PVDF structure. Due to the presence of
NiO nanoparticles, there is a possibility of some kind of structural reorganization in
the polymer chain which leads to a decrease in crystallinity of the polymer. It was
observed from impedance measurements that NiO also influences the conductivity
to a large extent, the diameter of the Nyquist plot decreased on addition of NiO
nanoparticles. Conductivity value obtained for polymer with 1 wt% NiO was
1.08 9 10-3 S cm-1. This is much smaller than that obtained for blank PVDF film.
Fig. 4 Magnetization curves for PVDF/NiO composite films
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The PVDF/NiO nanocomposite with 1 wt% NiO exhibited ferromagnetism. These
nanocomposites can be employed as proton conducting membranes, sensors or as
electrochemical devices.
Acknowledgments Financial assistance in the form of an R&D project grant from DST, Govt. of India
is gratefully acknowledged. ASB is thankful to NITK Surathkal for the award of a research Fellowship.
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