Composites Communications 11 (2019) 56–61

Contents lists available at ScienceDirect

Composites Communications
journal homepage: www.elsevier.com/locate/coco

Short Communication

Bio-waste polymer hybrid as induced piezoelectric material with high T

energy harvesting efficiency
Chandan Kumara, Anupama Gaurb, Shivam Tiwarib, Arpan Biswasb, Sanjay Kumar Raia,
Pralay Maitib,
⁎

a
School of Biomedical Engineering, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005, India
b
School of Materials Science and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi 221005, India

ARTICLE INFO ABSTRACT

Keywords: Toxicity, biodegradability, biocompatibility and complex synthesis techniques are the major challenges in de-
Bio-waste velopment for self-powered piezoelectric nanogenerators for biomedical applications. Here, we report a novel
PVDF bio-waste hybrid with polymer for self-powered nanogenerator by using abundantly available natural self-
hybrid aligned collagen fibrous fish scale as an efficient energy harvester. Fish scale induces the electroactive phase over
induced piezoelectricity
its surface through synergism. Structure and morphology confirm the uniform distribution of scale particle in
energy harvesting
synergism
PVDF matrix and γ-phase formation in the presence of the filler. Energy harvesting performance of the bio-waste
based hybrid device exhibit very voltage of 22 V and high energy density of 28.5 μW/cm2, considerably higher
value than the existing waste based device. Compressive stress by the human finger is sufficient to drive the bio-
waste hybrid to generate energy along with other modes of naturally occurring vibration like twisting, bending,
walking, foot tapping etc.

1. Introduction implantable device, e.g., artificial pacemaker because toxicity in-vivo

Mechanical or vibrational energy harvesting converts energy origi-
nated from vibration or mechanical into electrical energy. Vibration
sources originate from industrial machinery and transportation [1] or
human action inside or outside the body, e.g., walking, running, chest
and heart movements [2] etc. which can be utilized to power biome-
dical implants such as pacemaker and orthopaedic implants [3,4]. Vi-
brations originated from the heavy or large industrial sector are used
for large-scale power generation, e.g., wind power but energy har-
vesting techniques are predominantly dedicated to small-scale power
generation usable at an instant, characteristically to power small elec-
tronic devices where mains or battery cannot deliver a practical or
convenient solution [5]. Among existing technologies, nanogenerators
based on piezoelectric method have drawn attention as a new kind of
power source due to its flexibility and adeptness in biomedical devices
and various portable electronics [6–9]. There are quite a few piezo-
electric materials that have been explored to fabricate Piezoelectric
Nanogenerators (PNGs) based on several materials such as PZT [10],
BaTiO3 [11], ZnO [7], ZnSnO3 [9], PMN-PT [8], and synthetic polymers
(e.g., PVDF and its copolymers) [4,12]. The choice of material has the
most concern when dealing with the self-powered devices used as an
conditions can cause heart failure and life risks.
Energy harvesting devices provide a ‘battery-less’ solution by ex-
tracting energy from ambient energy sources. The energy storage so-
lutions with the development of super-capacitors are also improving
[13,14]. This is this merging of technologies that will eventually lead to
successful energy harvesting devices and systems. A biomaterial based
powered device is the best solution for this long-standing application.
Collagen fibril, a biodegradable and biocompatible material which are
abundant in nature (in animal tissues such as tendon, bone, cartilage,
ligament and skin is the easily available biomaterials which possess
piezoelectricity [15,16]. Fish scale, a bio-waste, consist of type I col-
lagen reinforced by apatite exhibit anisotropy and piezoelectricity in
meagre quantity [17]. Animal tissue is made up of Type I collagen and
repeated triplet amino acid motif sequence of Gly(Glycine)-X-Y con-
stituting two identical α1 (I) chains and a different α2 (I) chain in
which X andY are commonly proline(Pro) and hydroxyproline (Hyp),
respectively [18]. These α-chains spiral combine to form a unique
triple-helical structure leading to the formation of collagen monomers
comprising N and C-terminal telopeptides. The quarter staggered ar-
rangement of the collagen molecules adds to collagen fibrils with a
characteristic axial periodic structure and the fibrils further assemble

⁎
Corresponding author.
E-mail address: pmaiti.mst@itbhu.ac.in (P. Maiti).

https://doi.org/10.1016/j.coco.2018.11.004
Received 22 August 2018; Received in revised form 16 November 2018; Accepted 24 November 2018
Available online 28 November 2018
2452-2139/ © 2018 Elsevier Ltd. All rights reserved.
C. Kumar et al.
into a collagen fibre [19,20]. Here, the piezoelectricity is shown by the
hydrogen bond formation between the polypeptide chains. The intrinsic
presence of the polar uniaxial orientation of molecular dipoles causes
polarization and the piezoelectricity which makes the collagen to act as
a natural electrets or bioelectret material as well [21–26]. Up to the
present time, very little approach has been made to explore the pie-
zoelectricity performance of the naturally occurring materials,i.e. bio-
materials [25–28], and this is the first attempt where the applicability
of piezoelectric bio-waste hybrid nanogenerator,fabricated directly
from the fishscale(FS) with poly(vinylidene fluoride), is demonstrated.
Biocompatibility is also discussed for the use of developed nanohybrid
as energy sources in biomedical applications.
2. Experimental
2.1. Hybrid preparation
PVDF (Sigma Aldrich), dimethyl formamide were purchased from
Merck, Mumbai is used as received. Fish scales were brought from the
Varanasi fish market and cleaned thoroughly with distilled water. A
solvent system of 1.0 M NaCl, 20.0 mM EDTA, 0.05 M HCl and NaOH, is
used to wash the fish scales. Then the fish scales are soaked in 0.5 M
EDTA solution to get transparent fish scale. The treated fish scales then
crushed into powder and the powder obtained is collected as filler for
hybrid preparation. Hybrids of PVDF and fish scale powder were pre-
pared through solution route taking the pre requisite amount of the
components. Dimethyl formamide was used as a solvent to make a
solution of PVDF. Fish scale powder is added to the PVDF solution and
mixed on a magnetic stirrer for two hours. The prepared solution was
poured into petri-dish and dried under reduced pressure. The different
weight fraction of fish scale powder is used to prepare hybrid materials
(P-FS), and compression moulding technique is used to prepare thin
films of hybrid. The numbers after P-FS indicate the weight percentage
of fish scale in the hybrid.
3. Device fabrication
Hybrid of the dimension of 1 × 1 cm2 is taken and a conducting
layer of silver is applied on both sides to make contact between the
surface of hybrid and the respective electrodes. Effective area is of the
device 0.7 × 0.7 cm2 of sample size. Electrodes are attached to these
specimens using conductive adhesive for further measurements. Finally,
the hybrids were encapsulated by poly(dimethylsiloxane) (PDMS:
Sylgard, 184 silicone elastomer) and curing agent (10:1 wt/wt), and
dried at 55 °C for one hr. PDMS layer makes the device less vulnerable
from mechanical stress, humidity, temperature etc. and prevent it from
any further damages keeping the flexibility of the device after en-
capsulation and ensure almost equal pressure to the device.
3.1. Characterization
The surface morphology of pure PVDF, fish scale in powder form
and its hybrids are obtained through scanning electron microscopy
(Zeiss, SUPRA 40). Samples are gold coated using sputtering before
observation in SEM. Surface morphology of samples is also measured
using AFM NTEGRA Prima, NT-MDT. AFM in contact mode is used to
determine the surface roughness and height profile of pure PVDF and its
hybrid samples. The melting point of pure PVDF, fish scale hybrids are
determined using differential scanning calorimeter (Mettler Toledo
832). The peak temperature and the enthalpy of fusion are measured
from the endotherms of the peak position form its area under the curve.
DSC was calibrated using Indium before use at a scan rate of 10◦/min.
X-ray diffraction analysis is used to study the structure of pure PVDF,
fish scale and its hybrids. XRD patterns of the samples are measured
using a Rigaku Miniflex 600 ×-rd operated at a voltage of 40 kV and a
current of 15 mA using Cu Kα Radiation at the scan rate of 3◦/min at
57
Composites Communications 11 (2019) 56–61
room temperature. Fourier transform infrared spectroscopy is per-
formed by reflectance mode at room temperature ranging from 500 to
3500 cm−1 using Nicolet 5700 instrument having a resolution of
4 cm−1. UV–visible spectrophotometer (Jasco V650, Japan) operating
in the spectral range of 200 to 900 nm is used to take the spectra of the
samples.
Power is calculated from the output voltage obtained by varying
resistance, and optimum resistance is obtained at which it gives the
maximum power output with finger pressing and other modes of ap-
plying load, e.g., walking, foot tapping, twisting, finger pressing, and
bending. Voltage is measured using Tektronix TBS 1072B digital sto-
rage oscilloscope.
4. Biocompatibility study
4.1. Cell culture
Hela cells were cultured in a sterilized flask keeping Dulbecco’s
Modified Eagle Medium (DMEM), 10% heat inactivated fetal bovine
serum (Himedia) and 100 U/ml penicillin and 100 mg/ml strepto-
mycin. After that, the culture flask was incubated in a 5% CO2 in-
cubator maintaining the temperature at 37 °C.
4.2. MTT Assay
Cytotoxicity of the developed materials was cheeked using cell
viability measurement. MTT (3-(4,5- dimethylthiazol-2-yl)-2,5-diphe-
nyltetrazolium bromide) assay was used to quantify the viable cells in
presence of samples at different time intervals, as described elsewhere
[29]. In brief, on 70–90% confluence cells were trypsinized to detach
from the surface of the flask. After centrifuging, suspension of cells in
DMEM were spreaded on the wells of the 96-well culture plate and
incubated for 24 hr in 5% CO2 incubator at 37 °C. After incubation,
media was replaced with sample containing fresh media and incubated
in CO2 incubator for 24, 48 and 72 h. After predetermined time, media
was replaced with 100 μl MMT solution and keep it in CO2 incubator for
the formation of formazan. Then, formazan crystals were dissolved in
DMSO and the absorbance was taken at 570 nm using a microplate
reader. The relative cell viability of the samples is expressed with re-
spect to control using the following equation.
OD of Sample
%of Cell viability = × 100
OD of Control
where, OD is optical density.
4.3. Cell adhesion
For studying the adhesion efficiency of the cells on the developed
samples, thin coating of the samples were done on the wells of the 96-wells
culture plate and treated with DMEM media and incubated for 24 hr in
CO2 incubator. After incubation, cells were seeded on the surface of the
samples and incubated for 24 hours in 5% CO2 incubator at 37 °C. On next
day, cells were fixed with 5% paraformaldehyde solution and phase con-
trast images of the cells were taken using inverted microscope.
4.4. Fluorescence imaging
To understand the effect of developed materials on cells, fluores-
cence imaging was done. 1 × 104 cells were seeded on the wells of the
96-well culture plate and were incubated for 24 h at 37 °C in 5% CO2
incubator. After incubation, the samples were added and further in-
cubated at 37 °C in CO2 incubator for 24, 48 and 72 hours. After the
predetermined time, cells were strained using 100 mg/mL-1 acridine
orange and ethidium bromide and images were taken using fluores-
cence microscope.
C. Kumar et al. Composites Communications 11 (2019) 56–61

Fig. 1. (a) Scanning electron microscopic images of fish scale and its hybrids (P-FS20 and P-FS50) showing good dispersion of fiber like morphology; (b) AFM image
of hybrid (P-FS50); (c) XRD patterns of PVDF, fish scale and its indicated hybrids; (d) FTIR spectrum of fish scale and their hybrids showing different peak positions of
various crystalline forms; (e) DSC thermograms of PVDF, and its hybrids; and (f) schematic of epitaxial crystallization in hybrid systems showing different phases.

5. Results and discussion
Hybrids of fish scale and PVDF have been prepared through solution
route to create a homogenized system. Fish scale is known to be pie-
zoelectric, and its fibre-like pattern is evident from the SEM image
(Fig. 1a). The dispersion of crushed scale in PVDF matrix is homo-
geneous, and particle-like morphology is clear at the lower content of
scale, and the hybrid becomes fibrous with increasing the scale content
of 50 wt.%. The good dispersion of scale is also evident from the AFM
image of the hybrid, P-FS50 with a particulate diameter of 350 nm
(Fig. 1b). The surface roughness of the hybrid increases (average
roughness value increases from 9 in pure PVDF to 30 nm in P-FS50)
with increasing scale amount in the hybrid. The structural change in
hybrid due to the presence of scale has been confirmed through XRD
and FTIR measurements. Pure PVDF showspeaks at 20.0° (110), 18.4°
(020) and 17.7° (100), which corresponds to α-phase (TGTG ) [30–33]
while the peak positions shift to 20.54°, 18.9° and 18.3° in P-FS 50
(Fig. 1c) suggest a possible change of structure to γ-phase (T3 GT3 G ) in
presence of scale which is further confirmed from the appearance of a
new FTIR peak at 839 cm-1, assigned for β/γ-electroactive phase, in all
the hybrids against the peaks at 762 and 976 cm-1, corresponds to
conventional α-phase in pure PVDF (Fig. 1d) [34,35]. The melting
temperature of P-FS20 and P-FS50 hybrids increases to 159.2 and
160.1 °C, respectively, as compared to the melting point of 156.9 °C of
α-crystalline phase of pure PVDF as measured through differential
scanning calorimetry (Fig. 1e). This is to mention that γ-phase in PVDF
has higher melting temperature than that of α-phase and higher melting
temperature further endorse the nucleation of electroactive γ-phase in
PVDF matrix in presence of fish scale in the hybrids. Moreover, the
melting temperature increases gradually with increasing content of fish
scale in the hybrid indicating larger quantity of electroactive phase
greater amount of fish scale. This is to be noted that fish scale exhibit a
broad endothermic peak ~100 °C, primarily due to water evaporation
(supplementary Fig. S1) and it does not influence the melting behavior,

58
C. Kumar et al.
Fig. 2. (a) Digital photograph of bio-waste based hybrid as energy harvestor showing different components; (b) open-circuit voltage from the devices using fish scale
and its hybrid with PVDF at indicated compositions; (c) The variation of output voltage and current as a function of applied resistance; (d) effective output power
density of indicated devices as a function of variable external resistances ranging from 0.5–200 MΩ; (e) generation of output voltage under different types of load
onto the devices as mentioned; and (f) 3D representation of power density obtained from different modes of human motion i.e. walking, foot tapping, bending and
twisting.
rather it helps inducing the electroactive phase. The nucleation phe-
nomena has been revealed in the scheme (Fig. 1f) where γ-phase nu-
cleate over the scale surface to a certain extent up to which interaction
between the two phase matters. Beyond a certain limit, the polymer
chain crystallizes in conventional α-phase and the scheme illustrates
the typical epitaxial crystallization of electroactive phase over another
weak electroactive material (fish scale) enhancing the total quantity of
piezo-phases. The intimate interactions between the phases are re-
sponsible for the nucleation in γ-electroactive phase as suggested from
the considerable shifts in peak position (281 →285 nm) in UV–vis
spectra (Supplementary Fig. S2). However, fish scale powder increases
the electroactive phase of the polymer significantly, in addition to its
own value, and makes the hybrid useful for the energy harvesting
material.
With sufficient amount of electroactive phases, PVDF-fish scale
hybrid material has enough potential to be used for energy harvesting
purpose. Devices are fabricated to measure the energy harvesting cap-
ability of the material using its piezoelectricity and are shown in Fig. 2a
with the miniaturized device, electrical connections and conventional
load applying system like finger pressing. The generated open circuit
voltages (Voc) from the devices made of different materials are shown in
Fig. 2b. Device made using only fish scale show the meager voltage of
~4.8 V and higher output voltages are obtained with increasing fish
scale content in the hybrid. The maximum peak-to-peak open circuit
voltage generated is 22 V by adding 50 wt. % of fish scale. Finger
pressing method is used as mechanical input, the mechanism of voltage
generation under finger pressing and release is shown in Supplementary
Fig. S3. It can be construed from the figure that voltage increases with
the increase in the percentage of fish scale in the hybrid. To confirm the
viability of the bio-waste nanogenerators, voltage and current and
power densities are measured at different external load resistors as
shown in Fig. 2c indicating higher output voltage but lower short-
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Composites Communications 11 (2019) 56–61
circuit current with the increase in load resistance. The power gen-
eration capability of bio-waste nanogenerators is calculated by mea-
suring the voltage across the external resistance, i.e. from 0.5 to 200 MΩ
and the power density is calculated by the equation:-
V2
P = A × R , where, Ae is the effective area, V is the voltage drop
e L
across the load RL. The maximum power density is obtained from P-
FS50 is 28.5 μW/cm2 at 5 MΩ resistance (Fig. 2d). The achieved power
~28.5 μW/cm2 is by far superior to the reported bio-based nanogen-
erators (Supplementary Table S1). At later stage, the power starts de-
creasing with the increase of further resistance as the voltage starts to
saturate [35,36]. The power density of device using fish scale alone is
~2 μW/cm2 which is comparable to the previously reported literature
[17]. This is to mention that pure PVDF does not generate any power in
a similar condition of measurement, but synergism plays an important
role in hybrid to generate power 14 times to that of pure fish scale
arising from the nucleation of electroactive phase over the fish scale as
depicted in the scheme (Fig. 1f). Moreover, it is clear that power gen-
eration increase with an increase in filler content (Fig. 2d) with the
highest value of 50 wt. % of fish scale. Further increase in fish scale
content deteriorates the voltage/power output presumably due to poor
dispersion at high fish scale content hybrids (supplementary Fig. S4).
However, this hybrid device can generate 22 V/28.5 μW/cm2 energy
against device made of pure fish scale (4 V/ 1.14 μW/cm2 power den-
sity) [17].
Herein, the practicability of this hybrid device has been shown for
energy harvesting using various other vibrational energies originated
from day-to-day activities like walking, foot tapping, twisting, bending
and finger pressing with their comparison in terms of the output voltage
(Fig. 2e). The devices are sensitive to bending (2 V) and twisting (3.5 V)
as well. The corresponding power generation is shown in Fig. 2f by
utilizing different modes of vibration / pressing to show the range of
C. Kumar et al. Composites Communications 11 (2019) 56–61

output using this hybrid material which can able to deliver power
generation demonstrating its wider acceptability. Voltage/power gen-
erated from walking and foot tapping is higher as compared to twisting
and bending (Supplementary information Video VS1& Fig. S5, S6).
However, the maximum power output achieved from the hybrid device
(P-FS50) is 28.5 μW/cm2 suitable for most applications in miniaturized
devices including in bio-implants.
Supplementary material related to this article can be found online at
doi:10.1016/j.coco.2018.11.004.
Mechanical and durability of the bio-waste hybrid have been
checked through hand pressing and releasing cycle test for long times
up to two months. The device works well over 20,000 cycles (1000 s),
as shown in Supplementary Fig. S7 and evidence of lighting LED is
presented in supplementary video VS2. The generated output voltage
remains almost unchanged even after long cycles, indicating good
mechanical and chemical stability for realistic applications in bio-
medical applications.
Supplementary material related to this article can be found online at
doi:10.1016/j.coco.2018.11.004.
For any biomedical application of material, it should be
biocompatible in nature. MTT assay quantifies the viable cells in pre-
sence of any material and the viability of the cells is related with the
biocompatibility of that material. In MTT assay, mitochondria of viable
cells reduces the yellow coloured tetrazolium salts to intense coloured
formazan derivatives. Fig. 3a shows almost 100% cell viability for pure
PVDF, fish scale and their composite. Further, no significant changes in
cell viability with increasing time take place in cell viability for all
samples. This is to mention that the viability of the cells cultured onto
the surface of 96 wall culture plate is taken as control whereas cell
viability of pure PVDF, fish scale and their composite are expressed
with respect to control. The cells adhesion study (Fig. 3b) shows
spreaded morphology of the cells on the surface of the developed
samples which indicates better adhesion of the cells with the materials.
This good adhering property helps the cells to proliferate in a better
way and greater viable cells are observed [37]. The relative cell via-
bility in presence of PVDF, fish scale and their composite is further
confirmed through fluorescence imaging of Hela cells after 24, 48 and
72 h after staining with acridine orange and ethidium bromide (Fig. 3c).
Acridine orange and ethidium bromide differentiate the normal cells
from apoptotic cells depending on the permeability through cell

Fig. 3. : Cell culture of different materials using Hela cell line: (a) MTT assay measures the cytocompatibility of pure PVDF, fish scale and their composite in terms of
cell viability at day-1, day-2 and day-3. The results show almost 100% cells viability for all the materials; (b) The cell adhesion study shows spreaded morphologies of
cells over different developed materials which indicates cells adhere nicely over the samples; (c) The fluorescence imaging of the Hela cells after staining with AO/
EtBr dyes showing almost equal number density of cells in presence of different materials.

60
C. Kumar et al.
membrane. In healthy cells, ethidium bromide can penetrate the
membrane while in dead cells both can penetrate resulting different
coloured images of the healthy and dead cells. The fluorescence ima-
ging shows number density of the healthy cells in presence of developed
materials is almost equal to the control which has a good agreement
with MMT assay. Further, the number density of live cells increases
with increasing time for the all the materials which indicate that the
materials helps the cells to proliferate on them. Therefore, the devel-
oped materials are biocompatible in nature and suitable for its biome-
dical applications.
6. Conclusion
Robust bio-waste based piezoelectric hybrid materials have been
investigated for energy harvester. The weak piezoelectric fish scale has
been used to prepare hybrid with poly(vinylidene fluoride). Uniform
dispersion of fish scale particle has been achieved through solution
route. Fish scale nucleates the piezoelectric γ-phase in matrix PVDF as
evident from the appearance of new peaks in FTIR, higher melting peak
in DSC and XRD studies. A plausible mechanism has been proposed to
understand the nucleation of electroactive phase over the fish scale
surface through epitaxial crystallization. The device has been fabricated
using bio-waste hybrid material for energy harvesting. The overall
power generation using bio-waste hybrid material is 28.5 μW/cm2,
considerably higher than literature reported value of any bio-waste
material. This device is mechanically stable and can generate energy
over a wide range of load application e.g. twisting, bending, walking,
foot tapping and finger pressing and thereby demonstrate its versatility
for generating energy from various mechanical sources for the appli-
cations in miniaturized equipment including bio-implants. The device
shows very good mechanical stability and durability over 20,000 cycles.
In brief, a stable, sensitive power generator over a wide range of fre-
quencies and an efficient energy harvesting material which can lead a
world of possibilities open for biomedical applications using bio-waste
hybrid with the polymer. The biocompatibility results of the developed
composite shows that the biohybrid helps the cells to proliferate
showing its biocompatible nature.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.coco.2018.11.004.
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