CHAPER I - INTRODUCTION

BACKGROUND OF THE STUDY

Piezoelectric crystals are one of the small objects where we can generate electricity. This is done
by applying pressure to the crystal to the extent of deforming it. An electrical polarization is set
up in the crystal; as the result, the faces would become electrically charged. The word was
derived from the Greek term piezein meaning to squeeze or press.
Piezoelectricity has been applied to some objects of our daily use. Some people have already
manufactured piezoelectric microphones, in which this altered microphone has a better output
than our standard non-altered
microphones that we use.
Figure 1 Piezoelectric microphones has
been shown to have more noise levels than
capacitive microphones. (Littrel, 2010)
Also, piezoelectric generators has been
manufactured in shoes, therefore
making charging possible for people
walking (i.e., applying pressure) onto
the piezoelectric ceramics manufactured inside the shoe. A research about the development of a
piezoelectric shoe has been made (Baburao 2013)
When materials are brought down to the nanoscale dimension, their properties for some
performance characteristics dramatically change. One such example is with piezoelectric
materials. It is demonstrated that when materials are decreased to a particular scale, about 20
nanometres, the energy-harvesting capacity is increased by about 100 percent. (Cagin, 2008)
Not only nanoparticles can be used for effective energy harvesting, but also they can be practical
ways of energy harvesting itself. With the global energy consumption steadily increasing due to
the growing population and industrialization, it poses a threat to the fossil energy resources to its
depletion. Approaches on the usage of renewable resources have been developed (solar energy,
wind energy, wave energy, etc.) and these provide scales of power. Yet in utilizing mobile and
portable devices, a development of a different approach on energy harvesting is imminent, and
the usage of nanotechnology seems to be a viable option. (Park et al, 2012)
STATEMENT OF THE PROBLEM
Energy harvesting is making advances in portable devices due to the need for wireless, mobile
electronics with extensive life span. What we need to achieve is that manufacturing an
alternative to piezoelectric crystals/ceramics by replicating the developed nanocomposite
generator made of BatiO
3
nanoparticles and graphitic carbon, and incorporating it into footwear,
fabricating an effective energy harvesting device with the footwears capability of mechanical
pressure (with the wearers consent) , generating piezoelectric energy, and accumulating it.
OBJECTIVE
1. Obtaining previous studies about the effectuality of piezoelectric nanoparticles;
2. Fabrication of a piezoelectric generator which uses piezoelectric nanoparticles;
3. Imitate the manufacturing process of the piezoelectric-generator applied in shoes,
only changing the piezoelectric power source using nanoparticles as alternatives.
SIGNIFICANCE
People tend to have an intolerable attachment to their mobile devices. What is contributable to
these people is a way to charge their devices without them thinking that the charging process will
eventually run out of juice (so to speak). The benefit of this study is that we can have access to
quicker way of charging without faulty downsides. It is the mere act of stepping on the ground
that could generate electricity.
SCOPE, LIMITATIONS, AND DELIMITATIONS
We will create a device/prototype on shoes that uses the properties of piezoelectric crystals to
generate energy. Only, these crystals will be replaced with piezoelectric nanoparticles to ensure
the effectiveness of harvesting piezoelectricity. Yet, we will not entirely recreate the production
of the piezoelectric shoes but simply revise the piezoelectric ceramic into piezoelectric
nanoparticles. Furthermore, we will not test every piezoelectric crystal possible for the
production of the device.
CHAPTER II - REVIEW OF RELATED LITERATURE
Piezoelectricity
Piezoelectricity came from the Greek words piezo which means pressure and electric
for electricity. When a piezoelectric item is bent or deformed, this item will produce voltage.
This is known as direct piezoelectric effect. While the application of electricity in the same
material causes deformation of it, this is called indirect piezoelectric effect. The direct
piezoelectric effect is used in energy harvesting. The most commonly used piezoelectric ceramic
is the lead-zirconate-titanate (PZT). While here are also some ceramics that can be used: lead-
titanate (PbTiO
2
), lead-zirconate (PbZrO
3
), and barium-titanate (BaTiO
3
) (Nechibvute,
Chawanda and Luhanga 2012).
Applications of Piezoelectricity
Piezoelectric devices fit into four categories; it depends on the type of physical effect:
generators, sensors, actuators and transducers. Sensors and generators use direct piezoelectric
effect where the item is being deformed. Actuators use indirect piezoelectric effect where the
electricity formed in the material will cause its deformation. And last, in transducers both are
used in the same device. (Nuffer and Bein, 2006)
Table 1: Applications of piezoelectric materials and designs
Design effect
direction

Direct piezoelectric effect Indirect piezoelectric
effect
Both effects
Sensor Generator Actuator Transducer
Bulk material
(d33 effect)
Accelerometers
Knock sensors
Pressure/Force
sensor
High voltage
igniters
- Ultrasonic sonar
devices
Distance meters
Ultrasonic materials
characterization
Multilayer
(d33 effect)
- Energy
harvesting
Active Vibration
Reduction
Nano Positioning
High force
actuation
-
Patch
(monolithic)
Dynamic strain
sensor
Energy
harvesting
Active Vibration
Reduction
-
(d31 effect)
Patch (fiber
composites)
(d31 and d33
effect)
Dynamic strain
sensor
Energy
harvesting
Active Vibration
Reduction
-
Bi-trimorph
d31 +
bimorph effect
- - Textile machine Fans -
Special
designs
- Cymbal
transducers
for Energy
harvesting
Ultrasonic Motors Transformers
Taken from: Jrgen Nuffer, Thilo Bein 2006. Application of piezoelectric materials in
Transportation industry; 2.

Piezoelectric shoes
Energy harvesting is a way to power sensors and locator. But the energy harvesting technology is
quite low in terms of power output. Some generators might give only small amount or power that
can only support low power sensors.
Piezoelectric transducers generate electricity when deformed. This makes the
piezoelectric materials to be used in energy harvesting because it doesnt require bias voltage for
operation. In general, a piezoelectric transducer with two diodes is enough to generate dc output
voltage.
The piezoelectric generator is based on a low cost polymer that has metal surface so
electricity can pass. Unlike the other ceramic transducer which are plastic based generator that
is soft and strong like the properties of regular shoe fillings. The transducer can replace the
regular shock absorber with nothing to lose.
The hard part in harvesting piezoelectricity energy is that piezoelectric materials are best
for generating high voltage but provide only a low current output. The polymer used in the shoe
transducer provides over 5J of energy per step but the voltage is too large (>50 V) that can be
used in low power sensors. An advance feature in piezoelectricity is the new voltage regulation
circuits. A conversion circuit converts the charge into a usable voltage (Kaajakari 2010).
The study of Nanotechnology
If a nanometre (0.000000001 m) is to a meter then what the diameter of a hazelnut is to the
diameter of the Earth. When working on nanotechnology, you basically produce, analyze, or
utilize structures in an order of magnitudes of less than 100 nanometres. In this world of
nanotechnology, some of the classic principles of both physics and chemistry are necessarily
followed. Some properties of materials often change in a way when the size is reduced due to the
technology of nanomaterials. For example, when a gold coin is observed, it is seen as precious,
beautiful, and shiny, not to mention it has a low chemical reactivity. But a particle of gold
decreased to a few nanometres displays a rather red colour. It can also accelerate chemical
reactions as a catalyst. (Frick et al. 2007)

Though not all, some nanoparticles also have another interesting property called the Lotus
effect, is only seen in surfaces with peculiar nanoarchitectures. Through this principle,
nanostructured substances do not allow any dirt to gather. This eventually led to the creation of
self-cleaning bathtubs and roofing tiles. (Frick et al. 2007)

Piezoelectric materials brought to the nanoscale
Figure 2 - Normalized effective piezoelectric
constant of tetragonal piezoelectric BaTiO
3

beam. An enhancement of 20% of its bulk
value at 8 nm and a 500% increase at 5 nm are
observed. (Majdoub et. al. 2008)

As said that when materials are brought
into a significant change in scale, they
react differently. Some performance
characteristics also change. In
piezoelectricity, for example, when you
go to a scale of 20 nanometres, these materials exhibit energy-harvesting capacity improvements
by 100%. This is observed through the flexoelectric effect having exhibiting a size effect and
thus, having ramifications through the piezoelectric properties of nanomaterials. Materials are
more susceptible to change and are more affected in response to the environment that surrounds
it when its structure is ridiculously small (in scales of nanometres, to be precise).

In a recent study on the topic, piezoelectric phases of BaTiO
3
(BT) nanoscale cantilever
beams are used to carry out calculations under deformation of the material. Increases in the
piezoelectric responses from the BT are occurring differently on (also) different scales. The
effective piezoelectric response from the BT is increased by 20% on 8 nm, while a great increase
of 500% is observed under 5 nm. (Majdoub et al. 2008)

In another study, researchers have successfully manufactured a nanocomposite-based
nanogenerator and have developed new forms of large-area nanogenerator technology using
piezoelectric ceramic nanoparticles. It was made by using BaTiO
3
nanoparticles and graphitic
carbon nanotubes, successfully creating a nanocomposite generator (NCG). Mechanical
deformation and even slight biomechanical movements are converted to electrical energy by the
developed device. Piezoelectric energy generated by the NCG managed to light up a commercial
red LED through a circuit connected by four capacitors in a serial without any external power
source. (Park et al. 2012)
Figure 3 (a) A red LED is placed to the
circuit, bottom inset shows the measured
voltage ( 2 .37 V) when the four capacitors
are aligned in a serial. (b) the red LED is
shown to be lit up by the piezoelectricity
generated by the NCG.





III. Proposed Methodology
Part 1 Fabrication of Nanocomposite Generator made of BaTiO
3
Nanoparticles and
Graphine Carbon
The fabrication method used for the NCG has been drafted by Park et al. (Park et al, 2012) and
will be replicated.
Synthesis of BaTiO
3
nanoparticles
Ti precursors are prepared by hydrolysis reaction of Ti-butoxide (Ti[O(CH
2
)
3
CH-]
4
, reagent
grade 97%, Aldrich Chemical Co.). The Ti-butoxide (0.025 mol) is diluted with 5mL ethanol
and 5 mL of deionized water. Then ammonia is added to the mixture. For the BaTiO
3
powders,
the solutions are dispersed with magnetic stirring at 80 C. After this, add a 10 mL solution of
37.5 M barium hydroxide monohydrate. The created suspension will be added to a 100 mL
Teflon-lines stainless-steel autoclave with a parameter of 60 %. The autoclave is heated to 200
C for 24 hours and then cooled down to a room temperature. The result will be filtered and
washed 5 times with distilled water and ethanol and will be dried at 80 C for 24 hours.
Preparation of reduced graphine oxide (RGO)
Graphene oxide (GO) is created using the modified methods from the commercially available
graphite sources. Then the graphite will be oxygenated in 40 mL sulfuric acid. Then a 3.5
potassium permanganate is slowly added at 35 C. The reaction mixture is stirred for 24 hours
with nitrogen for proper oxygenation. After the completion of the oxygenation, the excess water
and 35 % of H
2
O
2
are added to the mixture. The 2 g of GO powder is filtered and washed 5 times
with 1M of an HCI solution and deionized water; the dispersed again in 1 L of deionized water.
Then GO is put in a water bath ultrasonicator for 30 minutes for monolayer exfoliation. The GO
dispersion that is sealed in a membrane is submerged in deionized water and stirred for 3 days.
When the supernatant and unexfoliated are removed by centrifugal separation, the fully
exfoliated GO dispersion is gained. The final step in RGO is annealing the GO solution in a tube
furnace at 700 C for 1 hour
Fabrication of the Nanocomposite Generator
Radio frequency magnetron sputtering is used to deposit layers of Cr (10 nm) and Au (100 nm)
onto exible substrates (Kapton lm, 25 m and 125 m in thickness) for the top and bottom
electrodes. A layer of PDMS is spin-casted onto the Au/Cr plastic substrates to form a dielectric
layer and then cured at 85 C for 10 min in an oven
The nanomaterials (BaTio
3
nanoparticles and graphene oxide) are dispersed in
polydimethylsiloxane (PDMS) by mechanical agitation to produce a piezoelectric nanocomposite
(p-NC). The mixture is poured into a petri dish and is cured in room temperature for a day.
The final p-NC product is spin-casted onto the PDMS/Au/Cr plastic substrates and cured in 85
degree oven for 5 min.
A PDMS/metal coated plastic substrate is placed uniformly with the p-NC/PDMS/metal-coated
substrate and is cured in room temperature for a day. Copper wires are attached to metal pads
through silver paste for the output voltage.
Almost 100% sure that you plagiarized (like direct copying of the methodology). Text in red are
those which I found to be exactly the same with the source article. Those in blue are those which
seems like taken directly from the article (hence, poorly paraphrased)
Part 2 Development of the Energy Accumulating Device
The method used for harvesting the piezoelectric energy developed by the NCG will be outlined
by the research of Rocha et al (Rocha et al; 2009) and/or of Baburao (Baburao, 2013)

Figure 4 A schematic of a power harvesting circuit (Baburao, 2013)
A circuit may be adapted from a circuit designed for a self-powered RF tag (Baburao, 2013) and
the resulting may be connected to a thin-film rechargeable lithium battery, which will be used to
store the energy generated.

Part 3 Testing the NCG Device
1 Measuring the Output Voltage and Current Signals from the NCG Device
Following the test methods conducted by Rocha et al, (Rocha et al 2009), an
experimental set-up similar to the aforementioned research will be conducted: the NCG device
will be placed in the midsection of the (shoe) soles, tests will be administered by (1) steps (2)
sprints (3) jumps, which will then be measured by a known voltage measuring device (i.e.
voltmeter,).

Please include partial bibliography
1) Your methodology seems half-baked. If you can, polish it more.
2) For the paper, change the plagiarized parts (not just the ones I saw). We will be using Turnitin
to check your papers so well know how well you copied and pasted.
a. Well definitely prefer a substandard paper that you yourselves wrote than a
high-grade paper that is copied directly from the source.
i. Quotes placed to mean differently from its denotation
3) Minor grammar errors siguro
4) Minor writing inconsistencies