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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


conditions can cause heart failure and life risks.
Mechanical or vibrational energy harvesting converts energy origi- Energy harvesting devices provide a ‘battery-less’ solution by ex-
nated from vibration or mechanical into electrical energy. Vibration tracting energy from ambient energy sources. The energy storage so-
sources originate from industrial machinery and transportation [1] or lutions with the development of super-capacitors are also improving
human action inside or outside the body, e.g., walking, running, chest [13,14]. This is this merging of technologies that will eventually lead to
and heart movements [2] etc. which can be utilized to power biome- successful energy harvesting devices and systems. A biomaterial based
dical implants such as pacemaker and orthopaedic implants [3,4]. Vi- powered device is the best solution for this long-standing application.
brations originated from the heavy or large industrial sector are used Collagen fibril, a biodegradable and biocompatible material which are
for large-scale power generation, e.g., wind power but energy har- abundant in nature (in animal tissues such as tendon, bone, cartilage,
vesting techniques are predominantly dedicated to small-scale power ligament and skin is the easily available biomaterials which possess
generation usable at an instant, characteristically to power small elec- piezoelectricity [15,16]. Fish scale, a bio-waste, consist of type I col-
tronic devices where mains or battery cannot deliver a practical or lagen reinforced by apatite exhibit anisotropy and piezoelectricity in
convenient solution [5]. Among existing technologies, nanogenerators meagre quantity [17]. Animal tissue is made up of Type I collagen and
based on piezoelectric method have drawn attention as a new kind of repeated triplet amino acid motif sequence of Gly(Glycine)-X-Y con-
power source due to its flexibility and adeptness in biomedical devices stituting two identical α1 (I) chains and a different α2 (I) chain in
and various portable electronics [6–9]. There are quite a few piezo- which X andY are commonly proline(Pro) and hydroxyproline (Hyp),
electric materials that have been explored to fabricate Piezoelectric respectively [18]. These α-chains spiral combine to form a unique
Nanogenerators (PNGs) based on several materials such as PZT [10], triple-helical structure leading to the formation of collagen monomers
BaTiO3 [11], ZnO [7], ZnSnO3 [9], PMN-PT [8], and synthetic polymers comprising N and C-terminal telopeptides. The quarter staggered ar-
(e.g., PVDF and its copolymers) [4,12]. The choice of material has the rangement of the collagen molecules adds to collagen fibrils with a
most concern when dealing with the self-powered devices used as an 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. Composites Communications 11 (2019) 56–61

into a collagen fibre [19,20]. Here, the piezoelectricity is shown by the room temperature. Fourier transform infrared spectroscopy is per-
hydrogen bond formation between the polypeptide chains. The intrinsic formed by reflectance mode at room temperature ranging from 500 to
presence of the polar uniaxial orientation of molecular dipoles causes 3500 cm−1 using Nicolet 5700 instrument having a resolution of
polarization and the piezoelectricity which makes the collagen to act as 4 cm−1. UV–visible spectrophotometer (Jasco V650, Japan) operating
a natural electrets or bioelectret material as well [21–26]. Up to the in the spectral range of 200 to 900 nm is used to take the spectra of the
present time, very little approach has been made to explore the pie- samples.
zoelectricity performance of the naturally occurring materials,i.e. bio- Power is calculated from the output voltage obtained by varying
materials [25–28], and this is the first attempt where the applicability resistance, and optimum resistance is obtained at which it gives the
of piezoelectric bio-waste hybrid nanogenerator,fabricated directly maximum power output with finger pressing and other modes of ap-
from the fishscale(FS) with poly(vinylidene fluoride), is demonstrated. plying load, e.g., walking, foot tapping, twisting, finger pressing, and
Biocompatibility is also discussed for the use of developed nanohybrid bending. Voltage is measured using Tektronix TBS 1072B digital sto-
as energy sources in biomedical applications. rage oscilloscope.

2. Experimental 4. Biocompatibility study

2.1. Hybrid preparation 4.1. Cell culture

PVDF (Sigma Aldrich), dimethyl formamide were purchased from Hela cells were cultured in a sterilized flask keeping Dulbecco’s
Merck, Mumbai is used as received. Fish scales were brought from the Modified Eagle Medium (DMEM), 10% heat inactivated fetal bovine
Varanasi fish market and cleaned thoroughly with distilled water. A serum (Himedia) and 100 U/ml penicillin and 100 mg/ml strepto-
solvent system of 1.0 M NaCl, 20.0 mM EDTA, 0.05 M HCl and NaOH, is mycin. After that, the culture flask was incubated in a 5% CO2 in-
used to wash the fish scales. Then the fish scales are soaked in 0.5 M cubator maintaining the temperature at 37 °C.
EDTA solution to get transparent fish scale. The treated fish scales then
crushed into powder and the powder obtained is collected as filler for
4.2. MTT Assay
hybrid preparation. Hybrids of PVDF and fish scale powder were pre-
pared through solution route taking the pre requisite amount of the
Cytotoxicity of the developed materials was cheeked using cell
components. Dimethyl formamide was used as a solvent to make a
viability measurement. MTT (3-(4,5- dimethylthiazol-2-yl)-2,5-diphe-
solution of PVDF. Fish scale powder is added to the PVDF solution and
nyltetrazolium bromide) assay was used to quantify the viable cells in
mixed on a magnetic stirrer for two hours. The prepared solution was
presence of samples at different time intervals, as described elsewhere
poured into petri-dish and dried under reduced pressure. The different
[29]. In brief, on 70–90% confluence cells were trypsinized to detach
weight fraction of fish scale powder is used to prepare hybrid materials
from the surface of the flask. After centrifuging, suspension of cells in
(P-FS), and compression moulding technique is used to prepare thin
DMEM were spreaded on the wells of the 96-well culture plate and
films of hybrid. The numbers after P-FS indicate the weight percentage
incubated for 24 hr in 5% CO2 incubator at 37 °C. After incubation,
of fish scale in the hybrid.
media was replaced with sample containing fresh media and incubated
in CO2 incubator for 24, 48 and 72 h. After predetermined time, media
3. Device fabrication
was replaced with 100 μl MMT solution and keep it in CO2 incubator for
the formation of formazan. Then, formazan crystals were dissolved in
Hybrid of the dimension of 1 × 1 cm2 is taken and a conducting
DMSO and the absorbance was taken at 570 nm using a microplate
layer of silver is applied on both sides to make contact between the
reader. The relative cell viability of the samples is expressed with re-
surface of hybrid and the respective electrodes. Effective area is of the
spect to control using the following equation.
device 0.7 × 0.7 cm2 of sample size. Electrodes are attached to these
specimens using conductive adhesive for further measurements. Finally, OD of Sample
%of Cell viability = × 100
the hybrids were encapsulated by poly(dimethylsiloxane) (PDMS: OD of Control

Sylgard, 184 silicone elastomer) and curing agent (10:1 wt/wt), and
where, OD is optical density.
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- 4.3. Cell adhesion
capsulation and ensure almost equal pressure to the device.
For studying the adhesion efficiency of the cells on the developed
3.1. Characterization 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
The surface morphology of pure PVDF, fish scale in powder form CO2 incubator. After incubation, cells were seeded on the surface of the
and its hybrids are obtained through scanning electron microscopy samples and incubated for 24 hours in 5% CO2 incubator at 37 °C. On next
(Zeiss, SUPRA 40). Samples are gold coated using sputtering before day, cells were fixed with 5% paraformaldehyde solution and phase con-
observation in SEM. Surface morphology of samples is also measured trast images of the cells were taken using inverted microscope.
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 4.4. Fluorescence imaging
hybrid samples. The melting point of pure PVDF, fish scale hybrids are
determined using differential scanning calorimeter (Mettler Toledo To understand the effect of developed materials on cells, fluores-
832). The peak temperature and the enthalpy of fusion are measured cence imaging was done. 1 × 104 cells were seeded on the wells of the
from the endotherms of the peak position form its area under the curve. 96-well culture plate and were incubated for 24 h at 37 °C in 5% CO2
DSC was calibrated using Indium before use at a scan rate of 10◦/min. incubator. After incubation, the samples were added and further in-
X-ray diffraction analysis is used to study the structure of pure PVDF, cubated at 37 °C in CO2 incubator for 24, 48 and 72 hours. After the
fish scale and its hybrids. XRD patterns of the samples are measured predetermined time, cells were strained using 100 mg/mL-1 acridine
using a Rigaku Miniflex 600 ×-rd operated at a voltage of 40 kV and a orange and ethidium bromide and images were taken using fluores-
current of 15 mA using Cu Kα Radiation at the scan rate of 3◦/min at cence microscope.

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

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C. Kumar et al. Composites Communications 11 (2019) 56–61

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

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C. Kumar et al. Composites Communications 11 (2019) 56–61

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

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C. Kumar et al. Composites Communications 11 (2019) 56–61

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