J Polym Res (2016) 23:184

DOI 10.1007/s10965-016-1078-2

ORIGINAL PAPER

Preparation and characterization of poly(vinylidene fluoride)

nanocomposites containing amphiphilic ionic liquid modified
multiwalled carbon nanotubes
Ali Bahader 1,4 & Gui Haoguan 1 & Fang HaoGoa 1 & Wang Ping 1 & Wu Shaojun 3 &
Ding Yunsheng 1,2

Received: 3 August 2015 / Accepted: 2 August 2016

# Springer Science+Business Media Dordrecht 2016

Abstract We report, herein, on the structure, melting/
crystallization and mechanical properties of the PVDF nano-
composites filled with neat multiwalled carbon nanotubes,
(MWCNTs), amphiphilic ionic liquids (IL) 1-hexadecyl-3-
methylimidazolium bromide and IL-modified MWCNTs. All
samples were characterized by FESEM, FTIR-ATR, XRD,
DSC, DMA and mechanical testing. It is found that
MWCNTs become equally dispersed in nanocomposites by
wrapping them with IL molecule. The relative content of the
polar phase is higher for the nanocomposites in comparison to
neat polymer. The IL and IL-modified MWCNTs exhibited
higher nucleation efficiency for PVDF crystallization.
Besides, anion of the IL has also pronounced effect on the
properties of the nanocomposites. The nucleation efficiency
was much higher, when the anion is changed from [Br] to
[PF6]. The IL not only acts as a compatibilizer for PVDF/
MWCNTs but also helped to transform the crystal structure
Electronic supplementary material The online version of this article
(doi:10.1007/s10965-016-1078-2) contains supplementary material,
which is available to authorized users.
* Ali Bahader
alibahader@gmail.com
* Ding Yunsheng
dingys@hfut.edu.cn
1
Institute of Polymer Materials & Chemical Engineering, School of
Chemical Engineering, Hefei University of Technology,
Anhui, China
2
Provincial Key Laboratory of Advanced Functional Materials and
Devices, Hefei University of Technology, Hefei 230009, China
3
Institute of optoelectronics, Hefei University of Technology,
Hefei, Anhui, China
4
Department of Chemistry, Hazara University, Mansehra, Pakistan
of PVDF. The mechanism for different tensile properties of
nanocomposites is also discussed.
Keywords PVDF crystallization . Ionic liquid . MWCNTs .
PVDF β/γ morphology
Introduction
Over the past decade, there has been a persevere effort in
fabricating carbon nanotubes (CNT) based polymer nanocom-
posite, seen as a solution to the growing demand of the indus-
try [1]. Nanocomposites have unique mechanical and other
physical properties, owing to the presence of stiff inorganic
nanostructure within flexible polymeric material [2]. Among
various carbonaceous nanostructure, multi-walled carbon
nanotubes (MWCNTs) are regarded as forthcoming replace-
ment for nano-fortification of the polymeric matrix. Good
mechanical power of the MWCNTs arises from its high
aspect ratio and good axial strength. The Main challenge in
preparing hybrid (organic-inorganic) materials is to obtain ho-
mogeneous dispersion of nanostructure in organic matrix.
Though, great efforts have been undertaken to enhance the
dispersion and compatibility of carbonaceous MWCNTs into
polymer matrices, but it still poses significant challenges [2].
Two methods of surface modification are available in the lit-
erature to address the issue of dispersion; one is physical and
the other is chemical. The modification of nanostructure or
MWCNTs by physical method with appropriate compounds
is an elegant strategy [3, 4]. It is because physical method does
not disturb the π conjugated electronic structure of MWCNT,
which is often required for enhancing the electrical properties
of the nanocomposites [5–8]. For instance, it has been report-
ed that the ionic liquid (ILs) can establish strong interactions
with MWCNTs, when mixed [1, 7, 9, 10]. The existence of
184 Page 2 of 9
π-π interactions between MWCNTs and ILs offers new pos-
sibilities to fabricate nanocomposite materials [11, 12]. ILs
will not only finely disperse MWCNTs, but also establish
strong interfacial adhesion between the matrix and the impu-
rity. PVDF is a semi-crystalline polymer and has been exten-
sively studied due to its marvelous piezo-, ferro-, and pyro-
electric properties [13]. PVDF shows polymorphism and ex-
ists in at least four possible crystal types α, β, γ and ε [14].
The common polymorph of PVDF is α-form, with trans-
gauche–trans-gauche (TGTG′) conformation, reflecting the
monoclinic unit cell. The β-form possesses all Trans (TTT)
conformation and γ has trans-trans-trans-gauche (TTTG)
skeletal layout [13–15]. The α-form is commonly produced
by re-crystallization from the polymer melt. In terms of elec-
tronegativity the α phase is nearly neutral [14, 16], while β
and γ phases are polar [17–19]. The aligned polar β-form is
the most desirable phase for industrial application; but it dif-
ficult to directly crystallize PVDF into β phase under ordinary
conditions. The conformational energy constraints at the mo-
lecular level inhibit the crystallization of PVDF into β mor-
phology under normal processing conditions [14, 16]. For
instance, Imamura et al. [20] has uniaxially stretched, α phase
below 100 °C and obtained the β-form. The β-form can also
be produced through solution casting method below 70 °C.
But the solution casting method generates porosity in the film,
which limit its utilization in industry [16, 21]. Likewise, the
piezoelectric β-phase can also be obtained by other methods;
including electrical pooling, crystallization from polar solvent
and co-polymerization [15, 22, 23]. Nano-fillers such as
nanoclay, metallic nanoparticles (NP) and CNT have also
been utilized to produce β phase. It has been reported, that
nanoclays [24, 25] as well as CNT [26–28] can induce β-form
of PVDF. The functional groups in case of clay and curvature
in case of CNT was found responsible for the β-phase.
Despite of several claims of β-phase generation by CNT, the
quantity of crystals was not sufficient for utilization as piezo-
electric material [29]. The nanoparticles of various metals
were also cited as β-form enhancers [14, 25, 30]. Now, it
has been firmly established that the surface functionality of
the NP, is the driving force for β form formation. The NP not
only converts α crystal to β, but also facilitates the fast crys-
tallization of PVDF through heterogeneous nucleation mech-
anism. The fast crystallization and high amount of β con-
tents in the case of NP, was ascribed to the development
of specific electrostatic interaction between >CF2 of the
polymer chain and functionality exist on the surface of
nano-filler [1, 17, 31]. Manna et al., used chemically
functionalized MWCNTs for crystal transformation of
PVDF and concluded that specific interactions between
the >C═O groups and >CF2 moiety of the PVDF structure
led to β-form generation. Nevertheless, they only obtain-
ed a maximum of 50 % β polymorph, even with high
loading of the MWCNTs [31].
J Polym Res (2016) 23:184
The imidazolium based IL was recently applied to trans-
form the crystalline structure of PVDF [32]. Although, α crys-
talline morphology was significantly converted into β, but at
slow crystallization rate [33, 34]. The slow crystallization
means plasticization of polymer chain due to the presence IL
in the system. The problem of slow crystallization was solved
by combining two entities i.e., IL and MWCNTs and obtained
IL-modified MWCNTs. This strategy served two purposes: (i)
IL increased the polarity of MWCNTs surface, which is essen-
tial to obtain 100 % -β form of PVDF (ii) MWCNTs acceler-
ated the crystallization rate through its 1D templating effect.
The fast re-crystallization of PVDF into the β phase was
assigned to the development of synergistic interactions be-
tween IL and MWCNTs [1]. In other words, the MWCNTs
and IL reinforce each other by using π-π interaction and pro-
duce polar crystals. The ionic liquids are also termed as ‘de-
signer solvents’ because their properties can be tuned by ma-
nipulating their cation and anion chemistry as well as the
length of alkyl chain [35]. The structural variation of the
additives significantly changes the crystallization nature of
a polymer [36]. Our preliminary work has proved that IL hav-
ing long alkyl chain i.e., 1-hexadecyl-3-methylimidazolium
bromide ([C16mim][Br]) possesses strong dissemination
characteristics for the MWCNTs in preparing polypropylene
(PP)/MWCNTs nanocomposites with low loss tangent and
high dielectric permittivity [37]. It has been reported, that
the nanocomposite containing nano-filler wrapped by
imidazolium based IL having one C16 alkyl group, are more
thermally stable and highly compatible. The dispersion char-
acteristics of the IL with C16 alkyl group also superb as com-
pared to other compounds with chain less than C16 [8].
In the present study, we incorporated IL, [C16mim](Br),
and IL-modified MWCNTs into PVDF, because it was expect-
ed that structurally different IL with C16 aliphatic chain might
achieved the objectives (i) the formation of β crystals (ii)
enhance compatibility and (iii) fast crystallization rate. This
work combines the nucleating role of the MWCNTs with the
polar nature of the IL, to achieve β phase crystals with fast
crystallization. The impact of anion on the dispersion, mor-
phology, thermal and mechanical properties was also studied.
Experimental
Material and method
PVDF pellets were obtained from Shanghai 3F New Material
Co., China. The molecular weight and PDI of the PVDF
were ~200,000 g/mol. And 2.0, respectively. MWCNTs
were purchased from Shenzhen Nanotech Port Co. Ltd.,
China, with diameter: 20–40 nm and length: <2 μm. The ionic
liquid, 1-hexadecyl-3-methylimidazolium bromide was pur-
chased from Lanzhou Greenchem ILs, China. Potassium
J Polym Res (2016) 23:184 Page 3 of 9 184

hexafluorophosphate (KPF6) was purchased from Alladin FTIR-ATR and XRD

Chemical Company; China. The hydrophobic ionic liquid,
1-hexadecyl-3-methylimidazolium hexafluorophosphate was All samples were crystallized in non-isothermal fashion in a
obtained from the anion exchange reaction of 1-hexadecyl- hot stage. The heating rate was 10 °C/min. The sample was
3-methylimidazolium bromide with KPF6. DMF and metha- first melted to 210 °C, and kept there for 10 min to erase
nol were purchased from Sinoapharm Chemical Reagent Co., thermal history. The samples were processed in the hot stage
China. All of the Chemicals were used as received. without nitrogen protection. All samples were processed in
this way, and directly used for structural characterization by
FTIR-ATR (Nicolet 6700, USA) and XRD techniques. A
Sample preparation change in the crystal structure of samples was noted by
XRD (X’Port. PRO MPD, Holland) in the 2θ = 5–30° range.
MWCNTs were dispersed in DMF through sonication for Other parameters for the XRD experiment were: scanning
30 min at room temperature. Then IL in DMF solution was speed of 2°/min, step interval 0.02°, voltage 40 kVand current
added drop-wise to MWCNTs/DMF suspension and resulting 40 mA.
mixture was sonicated for 30 min. The homogenous solution
of PVDF/DMF was prepared through sonication for 1 h at
Differential scanning calorimetry (DSC)
50 °C. The IL-modified MWCNTs dispersion was mixed with
PVDF/DMF solution and sonicated for 1 h. Finally, the IL/
The crystallization and melting behavior of all samples were
MWCNTs/PVDF/DMF mixture was concentrated using me-
recorded by differential scanning calorimeter (DSC, 821e,
chanical stirrer in a sonication bath. The concentrated semi-
Mettler Toledo). Before the sample scan, the instrument was
dried samples were dried in a conventional oven at 60 °C for
calibrated with sapphires and pure indium, respectively.
4 h, followed by vacuum drying at 60 °C for 12 h. All samples
Briefly, the sample were first heated to 210 °C and held for
were prepared following the same procedure, and labeled as
10 min to erase previous history. The sample was then cooled
PVDF (P0), PVDF/MWCNTs (P1), PVDF/IL[Br] (P2),
to 25 °C, and heated again to 210 °C. A scan rate of 10 °C/min
PVDF/IL[Br]/MWCNTs (P3) and PVDF/IL[PF6]/MWCNTs
was used for both heating re-crystallization. All experiments
(P4). The ingredients and their relative proportion in the nano-
were conducted under continuous flow of high purity nitrogen
composites are given in Table 1. The anion exchange reaction
gas. The first cooling and second heating traces were recorded
to prepare IL-2/IL with [PF6] anion was carried out according
for subsequent interpretation.
to reported method [33, 38] and the reaction is outlined in
Scheme 1 (see supplementary information).
Dynamic mechanical analysis (DMA)

Dynamic mechanical properties of the samples were studied

Characterization techniques on a compression-molded film with a (DMA Q800, TA) in a
multi-frequency strain mode. The Dynamic loss (Tanδ) was
Scanning electron microscopy (SEM) determined at a frequency of 1 Hz and heating rate of 3 °C/min
from −80 to 150 °C, in a nitrogen atmosphere.
The cross section morphology of the pristine polymer and
nanocomposites were observed using field emission scanning Tensile properties
electron microscope (FESEM, Hitachi, Japan). Samples were
immersed into liquid nitrogen for 10 min followed by sudden The prepared samples were hot pressed at 210 °C in a mold to
fracture. The fracture surface was then coated with a thin layer prepare 1 mm (thick) laminates. The samples were then cut
of gold by sputtering technique and analyzed. using a dumbbell shape die and used for the tests. Tensile tests
were carried out using an Instron universal material testing
Table 1 Compositions of the PVDF/IL/MWCNTs nanocomposites
system at 23 °C with a crosshead speed of 20 mm min−1.
Sample IL Type PVDF IL MWCNTs
(wt%) (wt%) (wt%)

P0 - 100 0 0 Results and discussion

P1 - 99 0 1
P2 [C16mim][Br] 99 1 0 Dispersion of MWCNTs
P3 [C16mim][Br] 98 1 1
P4 [C16mim][PF6] 98 1 1 Dispersion of CNTs in the polymer matrix was observed using
a field-emission scanning electron microscope (FESEM). All
184 Page 4 of 9
samples containing CNTs were fractured by immersion in
liquid nitrogen for about 5 min.
The cross sectional morphology of PVDF (P0), PVDF/
MWCNTs (P1), PVDF/IL[Br] (P2), PVDF/IL[Br]/MWCNTs
(P3) and PVDF/IL[PF6]/MWCNTs (P4) are depicted in Fig. 1.
The smooth morphology with some randomly distributed
spots can be seen in Fig. 1a, for neat PVDF. These spots
may be the polar β/γ fraction, which appears embedded in
the prevailing non-polar α phase. Similar observations have
been reported previously [13].
The electron micrograph of P1 (PVDF/MWCNTs) reflects
that most of carbon nanotubes were stretched out from the
polymer matrix (Fig. 1b). This endorses the fact that entangled
MWCNTs suffer from dispersion issue, especially in organic
polymer matrix and need some sort of functionalization.
Otherwise, they will remain inside the matrix without apparent
stretching out. It is has been recognized, that presence of
imidazolium cation onto MWCNTs surface increase the sur-
face polarity of MWCNTs. This amplified polarity leads to
greater interactions between >CF2 of the PVDF chains and
MWCNTs surface [1]. Hence, the homogeneous dispersion
of the nano-filler/MWCNTs into PVDF can be achieved
(Fig. 1c and d) [38]. This shows that IL has performed its
intended role of MWCNTs dispersion. The samples P2, P3
and P4 have shown different morphologies. A fibrillar struc-
ture of β phase was captured in the case of P2. The P3
displayed foliage type structure, which might have developed
due to the presence of amphiphilic molecule (IL[Br]) in the
Fig. 1 FE-SEM images of PVDF (P0), PVDF/MWCNTs (P1),
P V D F / I L [ B r ] ( P 2 ) , P V D F / M W C N Ts / I L [ B r ] ( P 3 ) a n d
PVDF/MWCNTs/IL [PF6] (P4). The scale bar represents 1 μm
J Polym Res (2016) 23:184
hydrophobic PVDF matrix. It is well established, that an am-
phiphilic molecule, when present in the PVDF leads to a
foliage-fibrillar structure [39]. In sharp contrast to P3, the P4
sample revealed smooth morphology. When the anion is [PF6]
instead of [Br], the incompatibility in the system due to
hydrophobic-hydrophilic imbalance is greatly minimized,
which might led to smooth texture.
Crystal structure identification
To further identify the crystal structures present in the PVDF
nanocomposites, FTIR measurements were executed on all
samples (Fig. 2). The bands correspond to the α-phase (762,
795 and 974 cm−1) can be clearly seen in the spectra of neat
PVDF [1, 32, 40]. It is worthwhile to mention that some re-
search groups have reported the peak at 835 cm−1 as an ex-
clusive band for the β crystals [1, 6]. But controversy still
exists while assigning peaks to β or γ phase, because the peak
at 835 cm−1 is sometime also assigned to the γ phase [32].
In the case of nanocomposites, the characteristic peaks re-
lated to the α-form tend to shift/decrease or even diminish.
The signal at 870 cm−1 seen in the case of P1 shifts to the value
of 872 cm−1 for P2 as well as P3. Such shift in frequency may
reflect reinforced interactions between the polymer chain and
the MWCNT’s surface [41]. It means that strong electrostatic
interactions have been developed. In the case of P4 the peak
appears at 874 cm−1 which is higher than the rest of the sam-
ples. This observation may be taken as a reason to account for
the role of the anion, which makes the IL-2/IL[PF6] more
compatible with the PVDF chain.
There is a consensus that the cation of the imidazolium
based ILs could establish interactions with the rich π-
electronic structure of the nanotubes through π-cation contact.
The stretching vibration arising from >CF2 of the PVDF was
reported to occurs at 1072 cm−1 [1]. The P1 sample shows a
Fig. 2 Room temperature FTIR-ATR spectra of PVDF (P0),
PVDF/MWCNTs (P1), PVDF/IL[Br] (P2), PVDF/MWCNTs/IL[Br]
(P3) and PVDF/MWCNTs/IL [PF6] (P4)
J Polym Res (2016) 23:184
peak centered at 1065 cm−1, which shifts to 1070 cm−1 in the
case of IL[Br], and the same band can be seen at 1072 cm−1
for IL[PF6]. This successive migration in peak position indi-
cates that, interaction between the polymer chain’s inherent
>CF2 unit and IL or IL-modified MWCNT’s surface have
been developed and strengthened [18]. It might be suggestive
of the fact that IL has performed the role of a linker, and
improved the compatibility between MWCNTs and PVDF.
The symmetrical peak at 1164 ~ 1165 cm−1 reported for
imidazolium ring confirms that IL has developed strong asso-
ciation with the polymer backbone [41]. The β and γ phases
have very similar XRD pattern and several FTIR absorptions
are obscured. The bands at 1232 cm−1 and 1274 cm−1 are
exclusively assigned to the γ and β phases, respectively.
These bands were only appeared after the addition of ILs
(Fig.2). In other words, the net polar phase is a mixture of
both phases, which coexists at the same time. The fraction of
the polar crystals in a sample can be calculated from the fol-
lowing equation, by assuming that IR absorptions follow the
Lambert − Beer law:
Fðβ=γÞ ¼ AP =ð1:26  ANP þ AP Þ
Where AP and ANP are the absorbance intensities at
764 cm−1 (representing non-polar α-phase) and 840 cm−1
(representing polar β/γ phase), respectively. The amount cal-
culated, is graphically represented in Fig. 3.
Quantitatively, the lower fraction of β phase (23 %), enun-
ciate that α and β/γ phases coexist in the neat PVDF. The
amounts of β/γ phase for all other nanocomposites are higher.
For the P1 sample, the polar crystal content was calculated to
be 30 %, which is higher than that for neat PVDF, representing
slight enrichment of polar crystals by the neat MWCNTs. In
the case of P2, P3 and P4 systems, where the ionic liquid was
used, the fraction of β/γ reached up to 74 %, 68 % and 69 %,
Fig. 3 Fraction (%) of β/γ contents of the PVDF (P0), PVDF/MWCNTs
(P1), PVDF/IL[Br] (P2), PVDF/MWCNTs/IL[Br] (P3) and
PVDF/MWCNTs/IL [PF6] (P4)
Page 5 of 9 184
respectively. The nearly equal amount of β/γ phase in P3 and
P4 is not surprising, because the generation of the β/γ phase
depends on the presence of positive charge in the system [38].
To augment the results from FTIR data, and to decipher the
structure, x-ray crystallography was carried out for all samples
(Fig. 4). Four distinctive diffraction peaks were observed at
17.6°, 18.3°, 19.9° and 26.5° for neat PVDF, which are attrib-
uted to (100), (020), (110), and (021) reflections of α-phase
crystal, demonstrating the very high α-crystals in the melt
crystallized PVDF [1, 42, 43].
The polar β/γ form gives signal at value higher than 20.2°
[1, 43]. The peaks in our system are shifted relatively to the
high values, which reveal that β/γ phases have been generat-
ed. The shape of the peak is also one of the properties to take
into account for structural elucidation. It is also reported, that
shape (height) of the peak at 17.6°, may reduce or even dis-
appear for the crystal labeled as β or γ. Apart from this,
movement of the peak centered at 19.9° to the higher value
is also supportive of the fact that β or γ crystals are predom-
inantly generated. In the present scenario, change in peak
height and position is quite discernable and sufficient to draw
the conclusion, that addition of IL or IL-modified MWCNTs
induces the formation of polar crystals. The change of anion
(From Br to PF6) also has profound effect on the physical
properties of nanocomposites. Being amorphous, the IL when
inserted into the galleries of PVDF tends to broaden the XRD
profile of the nanocomposites. The decrease sharpness sup-
ports the fact that addition of IL, which is an amorphous com-
pound, minimizes the rigidity and increases the flexibility of
the polymer chain. Likewise, the IL[PF6] is hydrophobic but
the anion [PF6] is a labile non-coordinating anion and permits
the imidazolium cation to be in close contact with >CF2 unit of
the PVDF. The dynamic interaction between the imidazolium
cation and >CF2 are strengthen and the PVDF chains are
Fig. 4 XRD profile of PVDF (P0), PVDF/MWCNTs (P1), PVDF/IL[Br]
(P2), PVDF/MWCNTs/IL[Br] (P3) and PVDF/MWCNTs/IL [PF6] (P4)
184 Page 6 of 9
forced to adjust to the new molecular orientation in the β/γ
phase. Both XRD and FTIR results are in good agreement.
Thermal properties
The DSC cooling traces of the melt crystallized neat polymer
and its nanocomposites during non-isothermal process are
displayed in Fig. 5. The melt crystallization temperature (Tc)
of PVDF (P0), PVDF/MWCNTs (P1), PVDF/IL (P2),
PVDF/IL[Br]/MWCNTs (P3) and PVDF/IL[PF6]/MWCNTs
(P4) are 135.8 °C, 139.0 °C, 136.7 °C, 139.2 °C, and
145.0 °C, respectively. These results indicate that both, pris-
tine MWCNTs and IL act as nucleating agent, and accelerate
the crystallization of PVDF [1, 44]. Interestingly, the Tc of the
PVDF/IL (P2) blend is higher than the neat polymer by a digit
of 0.9. Commonly, the 1D templating effect of MWCNTs is
knows for it nuclei formation role in the polymer melt, but
ionic liquids are recognized for their plasticization effect on
the polymer system. Plasticization means low crystallization
temperature. For P3 and P4 samples where IL-MWCNTs were
used, the melt crystallization temperatures (Tc) were 139.2 °C
and 145 °C, respectively. These values are even higher than
the ones recorded for the P1. This means that the IL-
MWCNTs blended in a ratio of 1:1 are more efficient as a
nucleation agent for the PVDF than pristine MWCNTs.
Furthermore, the more compatible [PF6] anion as in P4
might be the reason for high (Tc) among all samples. For P4
sample the DSC peak is a little wide, which represents the
high compatibility of the system. Such increase in compatibil-
ity might lead to velocity gradient and affect the speed of
polymer chain to reach at the crystallization front. The move-
ment of polymer chains at the surface of polymer film may be
faster than in the bulk, which appears in the form of stretched/
wide DSC curve with a slight tailing. To further clarify,
Fig. 5 DSC cooling traces for crystallization of PVDF (P0),
PVDF/MWCNTs (P1), PVDF/IL[Br] (P2), PVDF/MWCNTs/IL[Br]
(P3) and PVDF/MWCNTs/IL [PF6] (P4)
J Polym Res (2016) 23:184
another term used to portray the heterogeneous nucleation is
the nucleation efficiency (NE) of the fillers. The (NE) can be
expressed as: [45]
T c;NA −T c;neat
NE ¼ *100
T c;max −T c;neat
Where Tc,NA is the maximum crystallization temperature of
the nanocomposites, Tc,neat is the maximum crystallization tem-
perature of pure polymer, and Tc,max. (148.1 °C) is the maximum
crystallization temperature of polymer after it has been self-
nucleated and annealed [46]. The results shows that P1, P2,
P3 and P4 have NE of 26.02 %, 7.32 %, 27.64 % and
74.80 % respectively. It is apparent that NE of IL-modified
MWCNTs is higher than the rest of the samples. But the
IL[PF6]-modified MWCNTs indicates much higher heteroge-
neous nucleation capability in comparison to its other counter-
parts. Such an increase in nucleation efficiency can be explained
by keeping in view the difference between [Br] and [PF6] ions.
The volume of the non-coordinating hexafluorophosphate anion
is 73 A°, which is much bigger than the volume of bromide
anion [47]. The small symmetrical [Br] anion with volume of
1.8 A°, tend to occupy the crystal lattice of the ILs more tightly
without any noticeable crystal disruption. On the other hand, the
asymmetrical big sized non-coordinating [PF6] anion tends to
dissociate easily from the cation thus exposing the positive
charge center (imidazolium cation) to interact more strongly
with the polymer backbone and cause accelerated crystallization
of PVDF [1, 32, 41].
It has been reported that the melting temperature of polar β-
and γ-phases are higher than that of α phase. Figure 6 exhibits
the second DSC heating curves of neat PVDF and its nanocom-
posites with MWCNTs, ILs, and IL-modified MWCNTs. The
presence of single melting peak for neat PVDF confirms the
occurrence of α phase, while the melting endotherms at higher
Fig. 6 Melting endotherms for PVDF (P0), PVDF/MWCNTs (P1),
P V D F / I L [ B r ] ( P 2 ) , P V D F / M W C N Ts / I L [ B r ] ( P 3 ) a n d
PVDF/MWCNTs/IL [PF6] (P4)
J Polym Res (2016) 23:184
temperature may be easily ascribed to the β/γ phase [20, 21,
40]. The melting temperature of pure IL[Br] is 77 °C and that of
IL[PF 6 ] is 65 and 72 °C. (Figure S1, Supplementary
Information). In the mixed state with PVDF, both ILs (whether
IL/[Br] or IL/[PF6]) are molecularly dissolved into the PVDF
and have no opportunity to crystallize, independently.
Furthermore, the shifting of the melting peaks to the higher
temperature in the case of P2, P3 and P4 can be ascribed to
the disruption of IL, accompanying the promoting effect on
PVDF crystallization as reported elsewhere [48]. However, it
is pertinent to mention that wideness in the band came from
the melting contribution of both nonpolar α and polar crystals
in the sample, as evident in FTIR and XRD measurements.
Dynamic mechanical properties
The dynamic mechanical analysis (DMA) has been carried out
for neat PVDF and its nanocomposites. In Fig.7 the loss tan-
gent (tan δ) vs temperature plot of the melt blended nanocom-
posites are given. Usually, the tan δ vs temperature plot of
PVDF shows three relaxation peaks at lower, intermediate
and higher temperature. The peak at lower temperature may
be related to the mobility of the polymer chains in the amor-
phous region, which is denoted by glass transition (Tg) of the
PVDF, while the intermediate signal stand for crystal − amor-
phous interface, and the last peak at high temperature is des-
ignated as crystalline zone or the imperfection present in the
crystal [31, 32, 49, 50]. The nature of relaxations depends on
the functionality present on the surface of MWCNTs. The
miscibility of ingredients gives birth to single amorphous peak
as recorded in our case, at −35 °C and cited earlier [31, 32, 49,
50]. The intermediate relaxation bands were recorded at 14 °C
for the sample P0, P1 and P2, respectively. Accordingly, the
sample P3 and P4 show different relaxation signals, anchored
Fig. 7 The loss tangent as a function of temperature with a frequency of
1 Hz for PVDF (P0), PVDF/MWCNTs (P1), PVDF/IL[Br] (P2),
PVDF/MWCNTs/IL[Br] (P3) and PVDF/MWCNTs/IL [PF6] (P4)
Page 7 of 9 184
at 19.5 °C and 16 °C. It is probable that the hydrophilic-
hydrophobic balance generates such behavior.
In fact, the polymer crystals are by no means perfectly
crystalline like its solid counterparts. All samples for the
DMA test were prepared by melt blending method, followed
by hot pressing at 200 °C. It means that sufficient fraction of
β/γ phase has already been generated during sample prepara-
tion. Therefore, prior to conducting DMA test, samples com-
posed of β/γ phase or mixture of both phases. The β and γ
phases are directionally different from one another. The simul-
taneous presence of different crystalline polymeric phases in
the film leads to generation of micro-stresses and might be
responsible for observation recorded in the crystalline region.
Mechanical properties
In Fig. 8, the stress − strain curves of the melt-blended nano-
composites are presented. From the curves, it is evident that
tensile strength of the P1 (PVDF/MWCNTs) is high, which in
turn means high toughness.
The MWCNTs, proved very effective in enhancing the me-
chanical properties of the polymeric materials. There might be
two reasons; the orientation of MWCNTs and inhibition of
cracks due to crack deflection and bridging mechanism. The
high concentration (>0.1 %) of chemically modified IL/
MWCNTs/PVDF was cited to change orientation from
aligned to random [42]. The modified crystal structure of
PVDF might also have played the role and resulted in en-
hanced toughness. In the sample P2, micro-stresses may be
present due to the coexistence of β and γ phases. Because of
the presence of micro-stress, the P2 sample needs less force
for deformation and hence exhibit low tensile strength
(Fig. 8). Another reason is the presence of water of hydration,
which exists as a complementary unit of IL structure and
Fig. 8 Stress-strain curves of PVDF (P0), PVDF/MWCNTs (P1),
P V D F / I L [ B r ] ( P 2 ) , P V D F / M W C N Ts / I L [ B r ] ( P 3 ) a n d
PVDF/MWCNTs/IL [PF6] (P4)
184 Page 8 of 9 J Polym Res (2016) 23:184

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Acknowledgments This work was financially supported by the 31. Manna S, Batabyal SK, Nandi AK (2006) J Phys Chem B 110:
National Natural Science Foundation of China (Grant No. 51373045). 12318–12326
The author thanks to acknowledge the help extended by Wang XH and 32. Xing C, Zhao M, Zhao L, You J, Cao X, Li Y (2013) Polym Chem
Qiu LZ of the academy of Optoelectronic Technology, Hefei University 4:5726–5734
of Technology as well as Prof. Wang ZG of the University of Science and 33. Chen B-K, Wu T-Y, Chang Y-M, Chen AF (2013) Chem Eng J215–
Technology for assisting in the testing/analysis of the samples and sub- 216:886–893
sequent discussion, which helps in the preparation of this manuscript. 34. Zhao L, Li Y, Cao X, You J, Dong W (2012) Nanotech 25:255702
35. Ranke J, Mölter K, Stock F, Bottin-Weber U, Poczobutt J,
Hoffmann J (2004) Ecotoxicol Environ Saf 58:396–404
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