DOI: 10.1002/slct.

201701780 Full Papers

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2 z Energy Technology & Environmental Science
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4
5
Induced Piezoelectricity in Poly(vinylidene fluoride) Hybrid
6 as Efficient Energy Harvester
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8 Anupama Gaur,[a] Chandan Kumar,[b] Rahul Shukla,[c] and Pralay Maiti*[a]
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11 Poly(vinylidene fluoride) (PVDF) nanohybrid with organically scopic and thermal measurements. Morphology also supports
12 modified two-dimensional nanoclay, prepared through solution the formation of b-phase in presence of nanoparticle (spher-
13 route, has been fabricated as the energy harvester. The ulite to needle like morphology). The piezoelectric coefficient
14 nanoclay induces piezoelectric phase in PVDF arising from shows a significant increase after processing due to greater
15 epitaxial crystallization over the nanoclay layers. Further piezoelectric phase and the fabrication of unimorph has been
16 enhancement of piezoelectricity has been made by stretching made using high piezoelectric coefficient material showing
17 the film at high temperature showing ~ 80% b-phase along higher peak to peak voltage generation of 2.5 V with much
18 with some g-phase in nanohybrid. Orientation of the nanofiller longer response time (6 ms) in stretched nanohybrid under an
19 along the force field creates the nanohybrid tougher and impulse load. Finally, the voltage and current output from the
20 suitable for device fabrication. Mapping of piezo-domain has devices are measured under varying load and highest power
21 been constructed through piezo force microscopy indicating density value of 25 mW/cm3 is obtained for stretched nano-
22 100 nm dimension of the electroactive phase in stretched hybrid, more than sufficient to operate a miniature self-power-
23 nanohybrid as opposed to almost zero size in pure PVDF. ing device.
24 Structural alteration has also been confirmed through spectro-
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stretching,[9] recrystallization[10,11] and molecular epitaxy on the
27 Introduction:
surface of potassium bromide.[12] g-phase was prepared by Doll
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Poly(vinylidene fluoride) exhibits various important properties, and Lando at high pressure crystallization, whose melting
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such as high mechanical strength, high temperature and temperature is 15o higher than that of a and b-phase.[13] The
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chemical resistant, nuclear radiation and UV resistance, aging addition of two-dimensional layered nanoclay in PVDF matrix
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and abrasion resistance. Its piezoelectric and pyroelectric produces bulk piezoelectric materials which enhances the
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properties have applications in various technological devices mechanical, physical and thermal properties as well.[14–17]
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like sensors and actuators.[1,2] Because of its biocompatible Two dimensional nanoclay has advantage for structural
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nature, it has also found applications in various medical improvement than zero-dimensional fillers like titania and
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devices.[3] PVDF crystallizes in five types of crystalline forms i. e. silica[18] where there is no change in structure or one dimen-
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a, b, g, d, e and available in mostly three molecular sional filler like nanorod and CNT[19] where there is very less
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conformations like TGTḠ, TTTT and T3GT3Ḡ.[4] The non-polar a- amount of b-phase due to dimensional constraints. PVDF
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phase having TGTḠ conformation is thermodynamically stable crystallizes primarily in a-phase in presence of two dimensional
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while polar b-phase having TTTT (all trans) conformation is graphene sheets with very little amount of b-phase, which can
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responsible for piezo- and pyroelectric properties and is in also be proven from distinct spherulites in nanohybrid.[20]
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metastable state.[5,6] This electroactive b-phase can be obtained Hence, better compatibility and interaction between filler and
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by high pressure melt crystallization,[7] high voltage poling,[8] polymer matrix is essential to generate electroactive phase in
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the polymer. Polar b-phase is the main reason behind the
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electronic properties whose measure is the piezoelectric
45 [a] A. Gaur, Prof. P. Maiti
coefficient. b-phase stabilization through melt intercalation in
46 School of Materials Science and Technology
Indian Institute of Technology (Banaras Hindu University) presence of organically modified nanoclay[14] shows increased
47
Varanasi, 221005, India stiffness from 1.3 to 1.8 GPa, along with the enhancement in
48 E-mail: pmaiti.mst@itbhu.ac.in elongation at break and toughness reported to be 140 and
49 [b] C. Kumar
700%, respectively, vis-a-vis pure PVDF.[16] The greater inter-
50 School of Biomedical Engineering
Indian Institute of Technology (Banaras Hindu University) action is expected between polymer and nanoclay due to large
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Varanasi, 221005, India. surface area of nanoclay which promotes the formation of b-
52 [c] Dr. R. Shukla phase arising from better dispersion. Nanohybrids of nanoclay
53 Indus Synchrotrons Utilization Division
with amorphous polymer (PMMA) and polyurethane do not
54 Raja Ramanna Centre for Advanced Technology
Indore, 452013, India. exhibit any change of structure in presence of similar nature
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Supporting information for this article is available on the WWW under and content of nanoclay.[21] Similar study on structural change
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https://doi.org/10.1002/slct.201701780
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of PVDF in presence of cloisite 30B has been reported as b has been fabricated and their piezo- responses are evaluated.
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promoter agent.[22] Finally, the power of the devices under mechanical stress has
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PVDF has excellent piezo-, pyro- and ferroelectric properties been measured for its applicability in the real system.
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and has great potential for energy harvesting[23] applications Morphology directed structural transformation with tougher
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along with the fields of sensors, actuators, non-volatile memory and stiffer design nanohybrid developed here can be used to
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and nanogenerators.[24–26] For the miniature electronic devices, create multifunctional devices like sensors, actuators or other
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the main concern is their working sustainability.[27–28] Powering electromechanical self-powering devices.
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these devices with conventional batteries, replacement or on-
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site charging is a very difficult task considering the small
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dimension and complicated environment.[29] Self-powering Results and discussion
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electronic devices having such integrated power generators
11 Processing and nanoclay induced piezoelectricity
can turn the surrounding thermal, mechanical or chemical
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energy into electrical energy that can be used to operate such Two synergistic approaches have been employed to induce
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devices without any external electrical input. Attempts have piezoelectricity in PVDF as pure PVDF does not exhibit any
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been made to make a self-powered piezoelectric energy piezoelectricity. All trans b-phase is known to be the reason
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harvester using inorganic nanomaterials and polymers. Piezo- behind piezoelectricity and, therefore, the particular b-phase
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electric materials like ZnO,[30] BaTiO3,[31] PZT,[32] ZnSnO3[33] and has been generated in bulk PVDF by incorporating two
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GaN[34] had been used in the literature. The first report was dimensional nanoclay in the polymer matrix followed by
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using ZnO nanowires for the electric generation showing the controlled stretching of the film at high temperature to
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ability to harvest mechanical energy into electrical energy from enhance the electroactive phase. The stress strain curve for
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body movements, ultrasonic vibrations or hydraulic forces.[34–35] pure PVDF and nanohybrid at high temperature (90 oC) is
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Although the inorganic materials show superior energy con- shown in Figure 1a indicating higher toughness and modulus
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version efficiency, they are cost intensive, toxic, brittle in nature of the nanohybrid as compared to pure PVDF. Toughness for
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and not environment friendly. Lower stability, less durable, nanohybrid increases to 101 MJ/m3 from its value of 60 MJ/m3
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packaging problem due to humidity and the high output for pure PVDF at the same temperature of measurement. It is
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voltage can damage electronic circuit, especially where important to mention that toughness values have considerably
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electronic circuit requires low power limit their practical increased at high temperature with significantly higher elonga-
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utilities.[38,39] Piezoelectric PVDF based devices are better to use tion at break as compared to room temperature measurement
28
in such situations, where its piezoelectric properties can be (Supporting information Figure S1) raising a situation of
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enhanced by adding some nanofillers. Multi wall carbon extensive uncoiling (stretching out) of PVDF chain which leads
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nanotube (CNT) has been used as filler in PVDF and is found to to the formation of all trans b-phase. Higher elongation at
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be b-phase nucleating agent.[40] Use of carbon black in a hybrid break (420 and 490% for P and PC, respectively) at high
32
of high density polyethylene-PVDF composite fibre has been temperature is presumably due to low viscosity while greater
33
shown for textile actuator.[41] Synthetic muscle fibre of cross elongation for nanohybrid lies in its needle like morphology in
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section 26 mm2 produces 0.5 N actuation force from 4.5 V, presence of nanoclay as discussed later.[9] Stretching has a
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sufficient to flex a human finger joint. A PVDF nanofiber, significant role to align the nanoparticle, in addition to polymer
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produced through electrospinning, generates an output volt- chain, in the direction of force field as evident from the
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age of 6.3 V under a pulse generated signal.[42] A flexible orientation of nanoclay in TEM images in the stretching
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nanogenerator with single strand DNA and PVDF has been direction as opposed to the random orientation of as prepared
39
prepared and 11 mW/cm2 power density is reported through nanohybrid (Figure 1b). However, the nanoclay platelets are
40
touch response.[43] In another study, a bilayer film has been well dispersed in PVDF matrix with greater tactoid dimension in
41
prepared with poled PVDF-TrFE and graphene oxide, where the as prepared nanohybrid while oriented and smaller dimension
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graphene oxide works as electrostatic component and its effect tactoid is noticed after stretching lead to the formation of
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with piezoelectric component (poled PVDF-TrFE) is reflected in better epitaxial crystallization of PVDF chain on top of a large
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the output voltage as 4 V as compared to 1.5 V without number of smaller tactoids in nanohybrid after stretching.
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graphene oxide layer.[44] So far, no such polymer robust film Nanoclay in hybrid nucleates piezoelectric b-phase (2q ~
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especially fluoropolymer / hybrid has been used as an energy 20.5o; 200/110 planes) in PVDF against absolute a-phase (17.6o
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harvesting material. (100), 18.3o (020) and 19.9o (110) planes) crystalline state in pure
48
In this work, nanohybrids of poly(vinylidene fluoride) with PVDF before stretching (Figure 1c).[16] Interestingly, phase
49
2D nanoclay has been prepared through solution route and the conversion occurs during stretching and considerable b-phase
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effect of elongation at moderately high temperature has been appears both in pure PVDF and its nanohybrid. Representative
51
investigated for robust energy harvester. The extent of piezo- deconvolution of stretched samples has been shown in the
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electric b-phase is enhanced by the incorporation of nanoclay inset figure from where the extent of various phases have been
53
and subsequent high temperature uniaxial controlled stretch- calculated and plotted in Figure 1d showing greater extent of
54
ing. Phase change in processed hybrid has been shown b-phase after stretching and nanohybrid exhibit as high as 80%
55
through piezo force microscopy understanding the relative of b-phase, suitable for any piezoelectric devices. The appear-
56
dimension. A unimorph for both pure PVDF and nanohybrid ance of a new peak at 2q ~ 19.2o in presence of nanoclay is due
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32 Figure 1. (a) Stress-strain curves and toughness for pure PVDF and nanohybrid at 90oC showing high elongation at break; (b) TEM images of nanohybrid before
33 and after stretching (arrow indicates the stretching direction); (c) XRD patterns for pure PVDF and nanohybrid before and after stretching (inset shows
34 deconvoluted diffractograms for stretched samples) and other deconvolution patterns have been shown in supporting information; (d) phase fraction from the
deconvoluted patterns; a, a and b represent the content of amorphous, a- and b-phase, respectively; (e) FTIR patterns of PVDF and nanohybrid before and
35
after stretching indicating the presence of different phases; and (f) DSC thermograms of PVDF and nanohybrid before and after stretching showing the change
36 in melting temperature due to phase change.
37
38
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to the formation of a distorted b- or g-conformation, another stretching, with the disappearance of peaks of pure PVDF at
40
electroactive phase of PVDF.[45] However, it is evident from XRD 33.0o and 37.22o (Figure 1c). Higher elongation at break or
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patterns that nanoclay induces piezoelectric phase in nano- greater draw ratio[21] augment the molecular alignment in the
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hybrid while elongation significantly enhances the electroactive direction of force field and greater alignment helps the PVDF
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phase content and predominantly the b-phase crystallizes on chains to crystallize in microfibrillar all-trans planar zigzag
44
top and bottom of silicate layers arising from good interactions conformation of b-phase. The conversion of amorphous and a-
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between nanoclay and polymer chain leading to a strong band phase into b-phase due to stretching is evident from the fact
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at 2q ~ 6.03o, appears from sandwiching the nanoclay layers that considerable reduction of amorphous and a-phase content
47
with PVDF crystals (Supporting information Figure S2).[21] The after elongation both in PVDF and nanohybrid facilitated at
48
interaction of polymer and nanoclay is revealed from UV-visible high temperature (90oC) due to greater mobility.[46,48] The
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spectroscopy from the shifting of the absorption peak at structural change over is also verified through FTIR peaks at
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247 nm of pristine nanoclay to 264 nm in nanohybrid (Support- 837, 875 and 1274 cm 1, assigned to b-peaks, after stretching
51
ing information Figure S3). This is to mention that absorption against predominant a-peaks at 762, 795, 868, 973, 1148 and
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peak of pristine nanoclay appears from the olefinic double 1210 cm 1 before stretching in pure PVDF (Figure 1e).[45,49] On
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bond present in the organic modifier of the nanoclay while the other hand, nanohybrid shows all the above b-peaks
54
pure PVDF does not show any absorption band in the energy including new b-peaks at 725, 1163 cm 1 and g-peak at
55
range studied. XRD peak in nanohybrid at 36.4o also indicates 1224 cm 1 with the disappearance of corresponding a-peaks as
56
the formation of b-phase, whose intensity enhances after commensurate from XRD studies. However, a- and amorphous
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Scheme 1. Schematic representa-
34 tion of phase transformation in
35 nanohybrid, (a) Change in struc-
36 ture of single island or domain;
(b) extent of piezo phase before
37
and after stretching; and (c) over-
38 all increment in piezophase in
39 whole matrix showing conver-
40 sion from amorphous to b-phase
leading to larger piezo phase
41
domain.
42
43
44
phases are converted into b-phase after stretching in pure erable g-phase exist in nanohybrid as observed through XRD
45
PVDF while the piezoelectric phase already exists in nanohybrid and FTIR measurements.[50,51] The increment in heat of fusion
46
and its extent increases significantly after uniaxial stretching. after stretching (39.1 to 44.9 Jg 1 for PVDF and 37.5 to 43.0 Jg 1
47
Melting endotherm of stretched PVDF exhibits peak at 169.0 oC in nanohybrid) suggests conversion from amorphous to
48
against melting point of unstretched PVDF at 175.2 oC, crystalline (b-phase) during stretching. However, there is more
49
corresponding to the b- and a-phase of PVDF after and before conversion from amorphous to b in nanohybrid after stretching
50
stretching, respectively (Figure 1f). This is to mention that while in PVDF it is predominantly a to b. Structural, spectro-
51
double melting endotherms of pure PVDF before stretching is scopic and thermal measurements strongly indicate the
52
due to melt recrystallization. On the other hand, nanohybrid induced piezoelectric phase in PVDF whose extent significantly
53
before stretching shows peak at 178.3 oC, which may be increase in the presence of nanoclay after stretching providing
54
attributed to the formation of g-phase along with b-phase good amount of electroactive phase in the material suitable for
55
while the peak position has shifted to 170.7 oC after stretching its use as piezo-device and a schematic representation of phase
56
suggesting the transformation into b-phase although consid- change during stretching is shown in Scheme 1 indicating large
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Figure 2. (a) Polarized optical microscope images of pure PVDF and its nanohybrid showing spherulite in pure PVDF and no birefringence in nanohybrid; (b)
33
SEM images of pure PVDF and nanohybrid before and after stretching indicating the direction of stretching; (c) Piezo force microscopy images of nanohybrid
34 samples before and after stretching; (d) Piezo force microscopy of P, PC, P S and PC S samples showing average profiles of magnitude; and (e) phase angle of
35 the indicated samples. Inset figure suggests the magnified view of the respective profiles.
36
37
38
extent of polymer crystallize on top of nanoclay surface in b- and this orientation of molecules help crystallizing in b-phase
39
phase against meagre amount of b-phase in pure PVDF after during stretching. The surface morphology is also studied
40
stretching. Hence, b-phase lies like islands in the polymer through piezo force microscopy (PFM) at a bias voltage of 10 V
41
matrix and act as electroactive phase having large variation in and compared the morphology in absence of any potential
42
size and shape in pure PVDF and its nanohybrid especially after (Figure 2c). Shredded morphology is noticed in case of PC
43
stretching. (before stretching) presumably due to b-phase whose extent
44
enhances considerably after stretching (PC S) as opposed to
45
the non-shredded surface morphology of pure PVDF (Support-
46 Morphology and mapping of piezo-phase
ing information Figure S4). Average profiles for magnitude
47
The crystalline phases are revealed from polarized optical and phases are shown in Figure 2d & e. There is almost no
48
micrographs. Well defined spherulites of a-phase can be seen change in magnitude as well as phase in pure PVDF before and
49
in pure PVDF against birefringence less morphology due to tiny after applying the bias voltage in absence of any piezo phase
50
needle like crystallites of b-phase in nanohybrid (Figure 2a).[52] while there are considerable changes of magnitude and phase
51
Morphology at high magnification is observed through scan- in P S (stretched PVDF) and PC after applying the bias voltage,
52
ning electron microscope, which also supports the spherulitic as evident from the enlarge section as shown in the inset,
53
pattern in unstretched PVDF and the mesh like morphology in arising from the modest amount of b-phase (64%) there.
54
nanohybrid (Figure 2b). The oriented pattern is evident in the Interestingly, significant changes of magnitude and phase are
55
stretched samples (shown by the arrows) suggesting the noticed in PC S (stretched nanohybrid),  0.04 nA and  7.5
56
molecular reorganization due to stretching towards force field degree, after the application of bias voltage confirm the
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13 Figure 3. (a) enhancement in piezoelectric coefficient of samples after stretching; (b) schematic of unimorph made by stretched and poled film samples; and
(c) comparison of output voltage measured by impact load.
14
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16
17
presence of large extent of b-phase (80%) as compared to it is clear that higher b content samples exhibit higher d33
18
unstretched sample and pure PVDF. Further, the average size of values, which is suitable for the piezoelectric devices. As the
19
piezo-domain, as calculated from the width of individual peak piezoelectric effect originates from induced polarization and to
20
profile, is around 110 nm while the greater intensity of profile induce more polarization after stretching, the dipoles are
21
peak indicates the consolidation of the b-phase and found to oriented by electric poling with a strong electric field at an
22
be maximum in PC S. PFM images of various samples and elevated temperature. The piezoelectric properties are directly
23
corresponding phase and magnitude are shown in supporting related to the degree of polarization achieved. High temper-
24
information Figure S4 showing clear piezoelectric domains. ature helps minimizing the warping due to relaxation of
25
However, it is evident that nanoclay and stretching generate polymer and helps it to alter in a new volume. There is an
26
piezoelectric phase and the material is expected to show the optimum poling temperature which gives maximum polar-
27
piezoelectricity. Schematics of phase transformations in nano- ization, unlike the poling field where larger value will give
28
hybrid are shown in Scheme 1. Polymer molecules crystallize larger polarization.[53,54] However, we have chosen the optimum
29
on top and bottom of the layered silicates in nanohybrid. condition for better piezoelectricity.
30
Further, b-phase crystallizes just on top of nanoclay or clay A device has been fabricated as explained in the exper-
31
stacks presumably due to greater interaction followed by imental section having the unimorph of high piezoelectric
32
distorted b- or g-phase, as the interaction gradually diminish coefficient. Figure 3b shows the representative assembly of the
33
and ultimately conventional a-phase appear in the top layer. device combining the structural and electroactive layers and
34
These different phases make an island type of structure impulse load is applied in one end through cantilever. The
35
surrounded by the amorphous phase of polymer. All the phases voltage responses under impulse load are compared for
36
try to convert into b-phase after stretching and the amount of stretched PVDF and its nanohybrid samples (Figure 3c). Nano-
37
a- and amorphous phase decreases considerably (Scheme 1a). hybrid (PC S) exhibits higher output voltage (1.6 volts) as
38
The extent of piezoelectric phase is quite less before stretching compared to 1.1 volts using pure PVDF (P S). Further, the piezo
39
which increases significantly after stretching due to formation response dies out in just 3 ms in P S sample while PC S shows
40
of electroactive b-phase as shown in Scheme 1c. the response time up to 6 ms indicating superior device activity
41
using nanohybrid arising from its greater extent of piezo-
42
electricity.
43 Piezoelectric responses
44
It is clear from the structural and morphological measurements
45 Energy harvesting using hybrid piezoelectric
that developed nanohybrid is piezoelectric in nature and the
46
piezoelectric phase has been increased through uniaxial The developed hybrid piezoelectric material has been utilized
47
stretching. The piezoelectric coefficient, d33 is an imperative for energy harvesting by measuring the power output under
48
parameter to measure the piezoelectricity of any material. the external load on to the material and compare the
49
Figure 3a shows d33 values for both unstretched and stretched efficiencies. Piezoelectric films (both unstretched and stretched)
50
samples after poling at an electric field of 600 kV/cm. The of dimension 1 3 1 cm2 are coated with silver for making
51
unstretched samples show very low d33 values of 0.2 and 1 pC/ attachment to the electrodes. An electromechanical system, as
52
N for pure PVDF and nanohybrid, respectively. The respective discussed in experimental section, is designed in which the
53
values increase considerably to 7.7 and 12.5 pC/N after sample is strike by a prefixed varying load with a particular
54
stretching indicating the significant improvement in piezo- frequency and data (voltage and current) of single and multiple
55
electricity due to induction of b-phase in presence of nanoclay strikes are recorded. Highest voltage output has been shown
56
and further enhancement due to uniaxial stretching. However, by PC S (1.26 V) with high response time of 0.13 s against
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moderate output is observed (0.85 and 0.68 V for P S and PC, more charge at higher load. This charge is transferred towards
1
respectively) with lesser response time of 0.08 s in PC under the electrodes as a result of which the electrodes experience a
2
single strike and a constant load of 500 gm indicating superior potential difference causes flow of electrons and gives output
3
piezoelectricity in stretched nanohybrid due to greater b-phase current. The power density for all the devices at different loads
4
fraction (Figure 4a). The effect of load on piezoelectricity has is measured and is presented in bar diagram shown in Figure 5.
5
been shown in Figure 4b for PC S under single strike indicating Devices using PC S exhibits the highest power (~ 25 mW/cm3)
6
higher response for elevated load due to greater strain which while PC and P S generate moderate power of 7.2 and 13.0
7
ultimately reflected in piezoelectricity. This is to mention that mW/cm3, respectively. Power density systematically increases
8
pure PVDF shows only the background for entire measurement with load for all the devices using four different types of
9
period as similar nature is observed after the response time for materials but the relative increment is significantly high in
10
PC S or P S/PC. However, to understand the reproducibility, stretched nanohybrid (PC S) presumably due to greater
11
multiple strikes has been bombarded on the sample (PC S) electroactive b-phase in presence of nanoclay and subsequent
12
and four such representative piezoelectricity are shown in stretching. However, PVDF nanohybrid with much improved
13
Figure 4C indicating very good similarity of results in every electroactive b-phase has every potential for its use as energy
14
separate strike maintaining the relative piezoelectricity as a harvester with easy processing and cost effectiveness. PVDF
15
function of load as noticed in single strike measurement. The film and nanofibre are reported for energy harvester with
16
response time is also similar to single strike studies and the voltage output of 0.32 and 2 V, respectively, without power
17
result of other samples are summarized in supporting measurement while the thin fibres have lower mechanical
18
information Figure S5. The systematic increase of output stability.[55] Another study on nanofibres prepared through near
19
voltage as a function of load for all the samples is presented in field electrospinning report 5–30 mV voltage and 0.5-3 nA
20
Figure 4d showing highest voltage output and ever increasing current.[56] Similar types of nanofibre upon application of a
21
tendency for PC S against no change in pure PVDF except compression impact of force 10 N at 5 Hz frequency results 2 V
22
initial meagre increase and level off subsequently (consider as voltage and 2 mA current.[57] Nanofibres with the addition of
23
fluctuation). This is to be noted that the output voltage does hydrated salt has been studied as compared to pure PVDF
24
not increase for PC and P S specimens after a certain load (500 nanofibres and found 0.119 mV/me for PVDF which increases to
25
gm) leading to an optimum load at which maximum output 0.548 mV/me for nanofibre with hydrated salt under free
26
can be obtained and further increase in load will not affect the vibration test.[58] However, our devices using stretched nano-
27
output voltage. On contrary, PC S exhibits almost continuous hybrid generates maximum power of ~ 25 mW/cm3, which is
28
increment of voltage out put up to the load of 800 gm. more than sufficient to use it as biomechanical energy harvest-
29
However, this is to mention that higher load generate greater er from human body and has vast application in health
30
strain which in turn produce more piezo-response from a monitoring systems to be used as sensors. This developed
31
particular sample while higher piezoelectricity is obtained from device can provide higher output voltage upon electric poling
32
the device with higher b-phase (PC S) as measured from as there will be more polar phase and can be used as typical
33
structural studies (Figure 1). nanogenerators.[59] The stability of nanohybrid film is also
34
On application of external force, the crystal structure of the examined for long term use as required for most devices for
35
polymer film is deformed, resulting in induction of piezo- longer durability and a video showing the output signal from
36
response by interchanging the deformed structure to a stable the novel device is presented (supporting information Fig-
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one or vice versa. b-phase PVDF molecules are self polarized ure S5 and video VS1).
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(all trans configuration) along a direction even in absence of
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any external electric field, the combined effect of stress and
40 Conclusion
surface charge induce polarization results in a self-powered
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flexible piezoelectric energy harvester. Nanohybrid layers The nanohybrid of PVDF with organically modified nanoclay
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experience appropriate strain upon impact with the load has been prepared through solution route and good dispersion
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produce deformation in its crystal structure that leads to piezo- of nanoclay in polymer matrix is confirmed through trans-
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potential across the surface and contribute to an electric mission electron microscopy. Uniaxial elongation at high
45
output signal. This creates a piezo-potential on each side of temperature shows greater breaking strain in nanohybrid
46
nanohybrid layer inducing a charge cloud and this potential where oriented pattern of nanocaly is noticed, responsible for
47
difference leads to a flow of electron in external circuit, appears its greater toughness, measured from area under the stress-
48
in observed output voltage and current. strain curve. Nanoclay induces piezoelectric b-phase and
49
Output current from the piezo devices under load (500 gm) polymer chain crystallizes on the surface of nanoclay and
50
shows very high current (~ 100 nA) in PC S as opposed to further conversion is done through uniaxial stretching at high
51
lower current in P S or PC (Figure 4e). The ‘ON’ and ‘OFF’ temperature. The piezoelectric b-phase in nanohybrid has
52
indicate the striking time over the sample for multiple hitting increased up to 80% in nanohybrid as measured from the
53
system. Moreover, current generation is also a function of load deconvoluted XRD patterns. The structural changes, either by
54
showing higher current at greater load (Figure 4f). The device nanohybrid formation or stretching, are confirmed through
55
experiences a strain upon mechanical stress on the surface XRD, FTIR, POM, SEM and DSC studies. Mapping of piezoelectric
56
which deforms the crystal structure of the hybrid generating domain is performed through piezo force microscopy, under a
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52 Figure 4. (a) voltage output of a single strike at 500 gm load for all samples; (b) single hit and (c) multiple hit voltage output at different loads for PC S; (d)
53 Voltage output as a function of load showing gradual increase of voltage with load; (e) Current measured under 500 gm of load for all the samples, ‘ON’ and
54 ‘OFF’ indicate the duration of load which generate output current; and (f) Gradual and systematic increase in current with increase in load for PC S sample.
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5 Accepted: September 6, 2017
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