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INDIAN INSTITUTE OF SCIENCE

POLYVINYLIDENE FLUORIDE (PVDF) :

EXPERIMENTS AND APPLICATIONS

by

KUNAL SONI

Done under the guidance of Prof. Sanjiv Sambadhan

A thesis submitted in the partial fulfillment for the

degree of Bachelor of Science (Research)

in the

IAP Department

IISc
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“The three great essentials to achieve anything worthwhile are: Hard work,
Stick-to-itiveness, and Common sense.”

- Thomas A. Edison
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ABSTRACT

Piezoelectricity is the electric charge that accumulates in certain solid materials (such

as crystals, certain ceramics, and biological matter such as bone, DNA and

various proteins) in response to applied mechanical stress. In this thesis I have tried to

explore the piezoelectric properties of PVDF and its response to various factors.

Polyvinylidene Fluoride (PVDF) is a common piezoelectric polymer. It is widely utilized

because of its advantageous mechanical, chemical, and electromechanical properties.

Because of its piezoelectricity and it being a polymer, it can be employed in a number of

applications, a few of which we will explore in this thesis.

This thesis describes the preparation of PVDF in lab using different methods, their

comparison with commercially available PVDF in terms of several of its properties as

well as devising a few applications using it.

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DEDICATION

Dedicated to the memory of my late grandmother, who always inspires me to success

and who instilled in me the value of education and hard work and to my mother who has
been a constant source of support through tough times and who showers affection on
me always.
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ACKNOWLEDGEMENTS

My heartfelt thanks are due to my advisor, Prof. Sanjiv Sambadhan who believes in me
and who has guided me to scale heights. I wish to thank him for his constant support,
guidance and encouragement. I also wish to thank him for being an example of working
relentlessly to achieve goals and for instilling self initiative in me.

This work would not be possible without the invaluable help and contributions by
Karthik Sambi, Rahul Gawande, Abhinav Ruhela. Thanks are also due to Ganapathy for
imparting knowledge during the initial stages of this project. I am also extremely
thankful to Prateek for helping me out designing and teaching me the electronics of the
pulse sensor and breath sensor. I am also thankful to Prof. Rajeev Ranjan from
Materials Department for letting me use Peizoworks apparatus for PVDF
characterization.

Thanks are due to the group members in the surface science laboratory who have been
very supportive during this work and who have helped me understand the importance of
team work.

I wish to take this opportunity to thank all my friends, old and new, for putting up with
me and for sticking with me and constantly inspiring me to achieve goals.

Finally many thanks to my parents, brother and other family members for all their love
and support and to God for making my dreams come true.
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TABLE OF CONTENTS

ABSTRACT .......................................................................................................................3

DEDICATION .....................................................................................................................4
ACKNOWLEDGEMENTS ...................................................................................................5

TABLE OF CONTENTS ......................................................................................................6

LIST OF FIGURES...............................................................................................................8

1. INTRODUCTION…………………………………………………………………………10
1.1. Outline Of Thesis…………………………………………………………………10
1.2. Historical Background……………………………………………………………11
1.3. Peizoelectricity……………………………………………………………………12
1.4. PVDF………………………………………………………………………………15
1.5. Motivation………………………………………………………………………….17

2. PREPARATION OF PVDF……………………………………………………………….19
2.1. Vacuum Coating Unit……………………………………………………………..19

2.2. Preparation of PVDF I…………………………………………………………….21

2.3. Preparation of PVDF II……………………………………………………………23

3. EXPERIMENTS WITH PVDF……………………………………………………………..27

3.1. Characterization of PVDF…………………………………………………………27

3.2. Experimental Comparison using Sinusoidal Valve……………………………..28

3.3. Response to Temperature…………………………………………………………34

3.4. Response to Sound Frequencies………………………………………………....39
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4. APPLICATIONS OF PVDF…………………………………………………………………44

4.1. Pulse Sensor………………………………………………………………………...44

4.2. Breath Sensor………………………………………………………………………..47

4.3. Concept of PVDF Weighing Scale…………………………………………………48

5. SUMMARY…………………………………………………………………………………….49

6. REFERENCES………………………………………………………………………………...50
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LIST OF FIGURES

Fig 1. Shows the chemical structure pf PVDF

Fig 2. Shows the Vacuum Coating Unit used for metal coating of PVDF

Fig 3. Shows the effect of poling on PVDF

Fig 4. Shows the poling of PVDF I in lab

Fig 5. Shows the PVDF I sheets made in lab

Fig 6. Shows the poling of PVDF II in lab

Fig 7. Shows the PVDF II sheets made in lab

Fig 8. Shows the Piezoworks apparatus used for measuring D33 coefficient of PVDF sheets

Fig 9. Shows the meter where the values measured by the Piezoworks apparatus are displayed

Fig 10. Shows the sinusoidal valve prepared in lab with PVDF clamped on the platform above
the syringe rod

Fig 11. Shows the same sinusoidal valve from a different angle

Fig 12. Shows the Analog Devices oscilloscope using which all the data in this research were
recorded

Fig 13. Shows the apparatus used for testing the pyro electric properties of PVDF

Fig 14. Shows the apparatus used for observing the response of PVDF to sound frequencies

Fig 15. Shows the PVDF patch covered in PDMS used in Pulse and Breath Sensor

Fig 16. Shows the PVDF patch covered in PDMS placed on the wrist to sense the pulse
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Fig 17. Shows the circuit diagram of amplifier used in the pulse sensor

Fig 18. Shows the pulse sensor circuit made in the lab

Fig 19. Shows the screenshot of oscilloscope when it recorded the pulse

Fig 20. Shows the screenshot of oscilloscope when it recorded the breathing pattern
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1. INTRODUCTION

Piezoelectricity to put in simple terms is the electric charge generated in a material when

mechanical pressure is applied to it. Inverse piezoelectricity is the opposite effect which leads to
change in the shape of a material when an electric charge is applied to it. The phenomenon of

piezoelectricity is found on these two effects.

Polyvinylidene Fluoride (PVDF) is a commercially available, piezoelectric polymer. It is widely

utilized due to its advantageous mechanical, chemical, and electromechanical properties.

There has been significant research and a wide range of applications of piezoelectric materials
as actuators. Nevertheless, the surface characterization, and effects of externally applied

electric fields have yet to be further investigated.

1.1. Outline of the thesis

This thesis includes five chapters.

Chapter 1 is the basic introduction of the concepts of piezoelectricity and PVDF, the research
done in the field till now and the overall objectives of the research I have undertaken.

Chapter 2 discusses the methods and theory of lab preparation of PVDF using two different
poling methods and comparing it with the commercially available PVDF.

In Chapter 3, the various experiments conducted on the PVDF made in lab as well as the

commercially available PVDF are discussed.

Chapter 4 describes the development of various applications of PVDF as well as applications

that could be employed.

Chapter 5 deals with the conclusions and future scope of the subject.
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1.2. Historical Background

Before we get into the concepts, we will try to trace back the roots of piezoelectricity and

see how it has evolved over the years.

Piezoelectricity was discovered by Curie Brothers (Jacques and Pierre) in 1880. They

had studied the conversion of mechanical energy to electrical energy and worked with

materials like quartz, tourmaline etc.. They had announced their experiments at the

session of the Académie des Sciences in Paris [1, 2]. Piezoelectricity had been quite an
unclear phenomenon at the time and wasn’t seen much as a practical application. However later

on in 1916, Paul Langevin devised the first major application by developing an ultrasonic
submarine detector. The detector consisted of a transducer, made of thin quartz crystals
carefully glued between two steel plates, and a hydrophone to detect the returned echo. By
emitting a high-frequency chirp from the transducer, and measuring the amount of time it takes
to hear an echo from the sound waves bouncing off an object, one can calculate the distance to
that object. The principle behind this was with the inverse piezoelectric effect bouncing the

sonar off the object in the water and recaptured by the quartz plate [3]. Later on, the Bell
Telephone Laboratories developed multichannel telephones using the quartz crystals as wave
filters [4]. In 1930’s and 1940’s, it entered the period when the crystal phonographs were used
in microphones.

Barium Titanate, BaTiO3, was the first synthetic substance used as piezoelectric. Its properties

are quite similar to Rochelle Salt. When pressure is applied, approximately same voltages are
developed in both and also inversely, the size change when voltage is applied is similar in both
[5]. BaTiO3 is superior to natural piezoelectric crystals as it has several advantageous

properties such as positive temperature coefficient and higher permittivity. Following years,
several other piezoelectric materials were discovered such as lead metaniobate and lead

titanate zirconate (PZT), furthering the improvements in properties and characteristics [6]. Soon,
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by 1968, synthetic quartz crystals had become quite common and started replacing natural
crystals.

A new leap was taken in piezoelectrics, when Kawai [7] discovered the induction of
piezoelectric effect in Polyvinylidene Fluoride (PVDF) by applying an electric field. He also

found that large piezoelectric coefficient was exhibited in poled thin films. The development in

PVDF piezoelectricity started rising exponentially. Soon, Bergman et al. [8] and Wada et al. [9]
discovered that polled PVDF films also showed pyroelectricity. Also, the pyroelectricity exhibited
was at par with the crystalline pyroelectric detectors. Soon research started booming in the area

of PVDF, with several applications developing. PVDF had found itself the centre of modern day
piezoelectric applications because of the extensive properties it offered. In today’s era,
piezoelectric crystals are used as high voltage sources, sensors, actuators, motors, ultrasonic
transducers etc.

1.3. Peizoelectricity
The term piezoelectricity is derived from the greek word “piezin” meaning to squeeze or press
and ‘’electric’’ which means amber, an ancient source of electric charge. Hence piezoelectricity

is the ability of certain crystals to generate a voltage in response to applied mechanical stress.
That is, when mechanical pressure is applied to one of these materials, the crystalline structure
produces a voltage proportional to the pressure. Conversely, when an electric field is applied,

the structure changes shape producing dimensional changes in the material [1].

The naturally occurring piezoelectric crystals include Quartz, Berlinite (a

rare phosphate mineral structurally identical to quartz), Sucrose (table sugar), Rochelle salt,
Topaz, Tourmaline-group minerals, Lead titanate (PbTiO3) etc. In addition to these, Dry Bone
has also shown to exhibit some piezoelectric properties. Collagen, a connective tissue in bone,
exhibits the polar uniaxial orientation of molecular dipoles in its structure and can be considered
as bioelectric, a sort of dielectric material exhibiting quasipermanent space charge and dipolar
charge. Piezoelectricity of single individual collagen fibrils was measured using piezoresponse
force microscopy, and it was shown that collagen fibrils behave predominantly as shear
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piezoelectric materials. Other biological materials exhibiting piezoelectric properties include

Tendon, Silk, Wood, Enamel, Dentin, DNA etc.

Because of immense potential and use of piezoelectricity several synthetic piezoelectric crystals
were made such as Gallium orthophosphate (GaPO4), a quartz analogic crystal and
Langasite (La3Ga5SiO14), a quartz analogic crystal.

Also a piezoelectric potential can be created in any bulk or nanostructured semiconductor

crystal having non central symmetry, such as the Group III-V and II-VI materials, due to
polarization of ions under applied stress and strain.

A strong shear piezoelectric activity was also observed in self-assembled diphenylalanine

peptide nanotubes (PNTs), indicating electric polarization directed along the tube axis.

The nature of the piezoelectric effect is closely related to the occurrence of electric dipole
moments in solids. Polarization density or polarization is the vector field that expresses the
density of permanent or induced electric dipole moments in a dielectric material. When a
dielectric is placed in an external electric field, its molecules gain electric dipole moment and the
dielectric is said to be polarized. The electric dipole moment induced per unit volume of the
dielectric material is called the electric polarization of the dielectric. The dipole density
or polarization may easily be calculated for crystals by summing up the dipole moments per
volume of the crystallographic unit cell. As every dipole is a vector, the dipole density ‘P’ is
a vector field. Dipoles near each other tend to be aligned in regions called Weiss domains. The
domains are usually randomly oriented, but can be aligned using the process of poling, a
process by which a strong electric field is applied across the material, usually at elevated
temperatures. Not all piezoelectric materials can be poled.

Let us try and mathematically describe piezoelectricity.

Hooke’s Law 𝑆 = 𝑠 ∗ 𝑇 and electrical behavior of the material 𝐷 = 𝜀 ∗ 𝐸 combined constitutes

piezoelectricity, where where D is volumetric charge density, ε is permittivity and E is electric

field strength, S is strain, s is compliance and T is stress.
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These equations can be combined to give the coupled equations of which the strain-charge
form is:

{𝑆} = [𝑠 𝐸 ]{𝑇} + [𝑑𝑡 ]{𝐸}

{𝐷} = [𝑑]{𝑇} + [ε𝑇 ]{𝐸}

where the superscript E indicates a zero, or constant, electric field; the superscript T indicates a

zero, or constant, stress field; and the subscript t stands for transposition of a matrix.

Corresponding to these equations the four piezoelectric coefficients d, e, g and h are defined as:

𝜕𝐷 𝐸 𝜕𝑆 𝑇
𝑑= ( ) = ( )
𝜕𝑇 𝜕𝐸

𝜕𝐷 𝐸 𝜕𝑇 𝑆
𝑒= ( ) = −( )
𝜕𝑆 𝜕𝐸

𝜕𝐸 𝐷 𝜕𝑆 𝑇
𝑔 = −( ) = ( )
𝜕𝑇 𝜕𝐷

𝜕𝐸 𝐷 𝜕𝑇 𝑆
ℎ = −( ) = −( )
𝜕𝑆 𝜕𝐷

where the first set of 4 terms correspond to the direct piezoelectric effect and the second set of

4 terms correspond to the converse piezoelectric effect.

The bending forces generated by converse piezoelectricity are extremely high, of the order of
meganewtons, and usually cannot be constrained. The only reason the force is usually not
noticed is because it causes a displacement of the order a few nanometers. According to the

researchers, the piezoelectric factor reduces as the grain size decreases. They solve this
problem by developing a potential function.

Pyroelectricity and ferroelectricity are subsets or derivatives of piezoelectricity. Pyroelectricity is

the ability of certain materials to generate a temporary voltage when they are heated or cooled.
Ferroelectricity is a property of certain materials that have a spontaneous electric
polarization that can be reversed by the application of an external electric field.
Ferroelectricity is a property of certain materials that have a spontaneous electric
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polarization that can be reversed by the application of an external electric field. Ferroelectricity
is generally associated with crystalline materials or semi-crystalline materials. Some pyroelectric
materials are ferroelectric, however not all ferroelectrics are pyroelectric.

Ferroelectricity exists in PVDF and the proof lies in the existence of a spontaneous polarization

coupled with polarization reversal. At high electric fields, the polarization is non linear with

electric field for PVDF.

1.4. PVDF
Polyvinylidene fluoride, or polyvinylidene difluoride (PVDF) is a highly non-reactive and pure
thermoplastic fluoropolymer produced by the polymerization of vinylidene difluoride. It has the
repeated monomer unit CH2=CF2 , is a gas at room temperature and pressure and is relatively
stable. The solubility is less than 0.02/100g of water at room temperature. It is a semicrystalline

polymer, having its glass transition temperature at -35 ºC. Commercially it is prepared by
addition polymerization or by pyrolysis reactions. Unlike other popular piezoelectric materials,

such as PZT, PVDF has a negative d33 value. Physically, this means that PVDF will compress
instead of expand or vice versa when exposed to the same electric field.

(Fig 1)
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PVDF is polymorphic and can crystallize in 5 different forms. The major crystal forms of PVDF
involve different chain conformations each of which possesses a component of a net dipole
moment perpendicular to the chain.

The polymer chains of PVDF pack the unit cell in two different ways. Either they are additive

and the crystal possesses a net dipole or they pack with dipoles in opposite directions so there

is no net dipole in the crystal. The polar conformations are piezoelectric while the antipolar ones
are not.

PVDF exists in several forms: alpha (TGTG'), beta (TTTT), and gamma (TTTGTTTG') phases,

depending on the chain conformations as trans (T) or gauche (G) linkages.

The beta phase of PVDF has a net dipole moment and the best piezoelectric coefficient after

the poling process. Hence β phase is the most important in terms applications and a lot of
research is being done on it. The polymer chains are transformed from alpha to beta phase
when the films are stretched or rolled by deformation at below 100˚ C, or under continuous high

electrical field.

The other polymorphic phases, gamma and alpha, are generally not common. These phases
usually have a net dipole moment with components parallel and perpendicular to the chain
axes.

The spatial symmetry disposition of the hydrogen and fluorine atoms in the chain of PVDF gives
rise to unique polarity effects that influence the electrical properties. Experimental investigations

have shown that deformation of textured films of PVDF after their polarization and exposure to
strong electric fields induces changes on their surface. This validates the presence of
piezoelectric activity in this polymer.

As we discussed earlier, piezoelectric properties of PVDF were first introduced by Kawai. After

that several methods to obtain the beta phase have been developed. Surface characterization

of the electro active polymers has been conducted in the past. Perez reported in using an AFM
to measure piezoelectric properties of polymers.
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PVDF has several advantageous such as high piezoelectric coefficient, flexibility,

biocompatibility, lightness, and low acoustic and mechanical impedance. These properties make
PVDF a favorable material for bio and MEMS applications and also as transducers. Their use in

piezoelectricity is boosted by the fact that they are inexpensive and easy to produce.

PVDF has found itself engrossed in a number of applications because of its properties. PVDF is

commonly used as insulation on electrical wires, because of its combination of flexibility, low
weight, low thermal conductivity, high chemical corrosion resistance, and heat resistance. The
piezoelectric properties of PVDF are used to advantage to manufacture tactile sensor arrays,

inexpensive strain gauges and lightweight audio transducers. PVDF is the standard binder
material used in the production of composite electrodes for lithium ion batteries. In the
biomedical sciences PVDF is used in immunoblotting as an artificial membrane, usually with
0.22 or 0.45 micrometers pore sizes, on which proteins are transferred using electricity. PVDF is
used for specialty monofilament fishing lines, sold as fluorocarbon replacements for nylon
monofilament. PVDF transducers have the advantage of being dynamically more suitable for

modal testing applications than semi-conductor piezoresistive transducers, and more compliant
for structural integration than piezoceramic transducers.

1.5. Motivation
There are two major objectives in this research:

1. The first objective is to prepare PVDF is lab and compare its properties with the

commercially available PVDF. The idea is to prepare PVDF in different ways in order to
make the whole process easier, cheaper and closer to or equal in properties with the

commercially available PVDF. Two processes were used during the research and the
PVDF made during this research in lab turned out to be pretty good piezoelectric.
2. The second objective is to design some interesting and feasible applications which can

reach out to public in general. During our research we successfully designed a pulse
sensor and breath sensor, which can have quite a lot of use in the medicinal areas. We
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are trying to make it compact and more handy in order to make it useful commercially.
There are some more applications that were thought of during this research which I will
try to describe in this thesis, though we were not able to carry them out.
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2. Preparation of PVDF

As we must have understood by now, that PVDF because of its properties serves as a really
good piezoelectric. And because it is so widely used, it is available commercially. However the

commercial PVDF is quite expensive and so I tried making PVDF in lab. The poling was done in
two different ways which will be described in detail.

Before going into the preparation we will try to understand theory behind metal coating through
Vacuum Coating Unit.

2.1. Vacuum Coating Unit:

Vacuum Coating Unit is the apparatus that does the metal coating on PVDF sheet to make it
conducting in order to do the poling. For that the sheet is coated with aluminum using a Vacuum
Coating Unit. The vacuum coating unit employs the Evaporation technique to coat the PVDF

with aluminum. In this method the source material is evaporated in a vacuum. The vacuum
allows vapor particles to travel directly to the target object (substrate, which in our case is

PVDF), where they condense back to a solid state.

Evaporation involves two basic processes: a hot source material evaporates and condenses on
the substrate. However, the gaseous environment and heat source are different.

Evaporation takes place in a vacuum, i.e. vapors other than the source material are almost
entirely removed before the process begins. In high vacuum, evaporated particles can travel
directly to the deposition target without colliding with the background gas. At a typical pressure
of 10−4 Pa, an 0.4-nm particle has a mean free path of 60 m. Hot objects in the evaporation
chamber, such as heating filaments, produce unwanted vapors that limit the quality of the
vacuum.

Evaporated materials deposit non-uniformly if the substrate has a rough surface. Because the
evaporated material attacks the substrate mostly from a single direction, protruding features
block the evaporated material from some areas.
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When evaporation is performed in poor vacuum or close to atmospheric pressure, the resulting
deposition is generally non-uniform and tends not to be a continuous or smooth film. Rather, the
deposition will appear fuzzy.

The evaporation system includes a vacuum pump and an energy source that evaporates the

material to be deposited. In thermal evaporation (the one that we carried out), metal material (in
the form of wire) is fed onto heated semimetal (ceramic) evaporators known as "boats" due to

their shape. A pool of melted metal forms in the boat cavity and evaporates into a cloud above
the source. Alternatively the source material is placed in a crucible, which is radiatively heated
by an electric filament, or the source material may be hung from the filament itself (filament
evaporation).

(Fig 2)
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2.2. Preparation of PVDF I

Let us call the PVDF sheet formed by the first process as PVDF I.

Let us have a sneak at the experimental procedure of formation of PVDF I:

1. Firstly, a beaker is taken and washed thoroughly.

2. Using a measuring cylinder, 5.12 ml of 1-Methly-2-pyrrolidinone and 0.4 ml of Methyl

Ethyl Ketone is added to the beaker.

3. The beaker is then kept on the hot plate with a temperature of around 50°C.
4. Then using a sensitive weighing scale, 1 gm of PVDF powder was taken using a
spatula and added to the beaker.

5. The temperature was increased to 70°C and the magnetic stirrer was added.
6. Along with slow stirring, the solution was also mixed using a spatula because of its
high viscosity.
7. The contents were allowed to get mixed for about 20 minutes.
8. At the end, a highly viscous fluid was obtained.

9. The beaker with the fluid was then emptied on a glass pane.
10. Using a spatula the fluid was spread out evenly on the glass pane.
11. Then the glass pane with the PVDF fluid was kept in a pre heated oven for about 2-3

hours.

12. At the end of 2-3 hours, the glass pane was removed from oven and a plastic like
sheet was obtained. The sheet was then scraped off from the glass pane.

The sheet obtained using these step is the PVDF. Usually the PVDF sheet made using this
procedure is curved. However the bending depends on the thickness of the sheet. Less the
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thickness, more the bending. The type of PVDF obtained depends on the composition of
mixture, temperature while mixing, temperature of the oven and the spreading out of the fluid.

Even though PVDF is prepared, it won’t have any piezoelectric properties as it hasn’t been
poled yet. The PVDF prepared would have randomly oriented positive and negative groups and

hence would lack any piezoelectric properties. Poling would align the groups and generate

piezoelectricity in PVDF.

(Fig 3)

Before poling can be done the sheet need to be made conducting my metal coating which is
discussed in section 2.1. The process needs to be carried out twice, as only one side of PVDF
can be coated at one go in vacuum coating unit.

Poling:

Once the PVDF sheet is coated with metal, it is ready to be poled. As mentioned earlier, in
poling strong electric field is applied across PVDF.
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In our case, an electric field of 200 V was applied across the metal coated PVDF sheet for 4-5
hours using a high voltage generator.

The PVDF finally obtained is poled and displays piezoelectricity.

(Fig 4)

(Fig 5)

2.3. Preparation of PVDF II

Let us call the PVDF sheet prepared by the second method as PVDF II
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The second method differs from the first one primarily in terms of poling.

Let us start understanding with the experimental procedure:

1. Firstly, a beaker was taken and washed thoroughly.

2. The interior of the beaker was coated with aluminium tape.

3. Using a measuring cylinder, 5.12 ml of 1-Methly-2-pyrrolidinone and 0.4 ml of Methyl

Ethyl Ketone was added to the beaker.

4. The beaker was then kept on the hot plate with a temperature of around 50°C.
5. Then using a sensitive weighing scale, 1 gm of PVDF powder was taken using a

spatula and added to the beaker.

6. The temperature was increased to 70°C and the magnetic stirrer was added.
7. Along with slow stirring, the solution was also mixed using a spatula because of its

high viscosity.
8. The contents were allowed to get mixed for about 20 minutes.
9. At the end, a highly viscous fluid was obtained.

In this method the poling was done while PVDF was in semi solid state.

Poling:

For poling here, a metal rod was immersed in the PVDF fluid in the beaker which served as one
of the electrodes. The wall of the beaker (which is conducting because of the aluminum tape)
served as another electrode. The distance between the metal rod and the wall of beaker was

around 2 cms. Then using high voltage generator around 700V was applied across the two
electrodes for around 10-12 hours. After 10-12 hrs, the fluid was taken out. This PVDF fluid

was piezoelectric in nature now.

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(Fig 6)

Once the poling was done, the fluid was spread out on glass pane and as in the previous
method, it was made out into a sheet.

The sheet was then coated with aluminum using Vacuum Coating Unit as discussed in the
previously, and our final metal coated poled PVDF sheet was ready.

(Fig 7)
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Theoretically the sheet prepared by the first method should be a more effective piezoelectric as
the positive and negative groups (Hydrogen and Fluorine) are aligned completely. However in
the second method, the groups that are aligned because of poling become a little random again

when the fluid is made into sheet. However, the effectiveness will be tested experimentally

which will be described in the upcoming section.

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3. Experiments with PVDF

3.1. Characterization of PVDF

Before starting off with the experiments, it was important to characterize the PVDF prepared in

the lab. For characterization, the D33 of the PVDF sheets was measured using an apparatus
called D33 Piezometer from Piezotest.

(Fig 8)

(Fig 9)
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The piezotest system works by clamping the sample, and subjecting it to a low frequency force.
Processing of the electrical signals from the sample, and comparison with a built-in reference,
enables the system to give a direct reading of d33 – one of the most useful parameters in
evaluating the material. This is a material coefficient representing charge per unit force in the
direction of polarization.

The method of operation of this type of d33 meter is sometimes called the "quasi-static" or
"Berlincourt" method. A key principle is that the test frequency is low compared with any likely
system or sample resonances, yet high enough that a conclusive measurement can be made in
a few seconds and the reading is obtained on a LCD display.

For convenience we shall term the PVDF prepared using first method as PVDF I and the one
prepared using second method as PVDF II.

The apparatus showed the D33 value of the commercially available PVDF as -2 pC/N.

However, the D33 value of PVDF I and II was given as zero by the apparatus.

But the fact that the apparatus was not sensitive enough and that there were fluctuations in
value before finally settling down to zero implies that the D33 value could be between 0 and -1
of PVDF I and II.

3.2. Experimental Comparison using Sinusoidal Valve

Since one of the objectives of this research was to compare the piezoelectricity of PVDF I and II
with commercially available PVDF, I designed a sinusoidal valve to do it.

Principle of Sinusoidal Valve:

The idea and principle behind creating a sinusoidal valve is to keep providing a constant force to
the PVDF sheets to measure the piezoelectricity generated.

Design of Sinusoidal Valve:

The materials used in designing this valve were:

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1. A small speaker
2. A metallic board with holes and its components
3. A syringe rod

The syringe rod was glued to the speaker using feviquick. Using metallic board and its
components, a base was made to place the speaker and a platform for the PVDF sheet. The
components were so adjusted such that when the PVDF sheet was placed on the platform, it
just touched the syringe rod tip underneath.

Experiment:

The PVDF sheets were placed on the platform above the speaker just touching the syringe rod
tip. Then using MATLAB, a 200Hz sine wave was fed into the speaker, such that the rod
vibrated at with the speaker, providing a constant force to the PVDF sheet from underneath.
The piezoelectric voltage generated was measured using Analog Devices oscilloscope.

(Fig 10)
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(Fig 11)

(Fig 12)

Observations and Analysis:

The Voltage vs Time graph for PVDF I, PVDF II and Commercial PVDF are summarized below
(the bigger band in middle of the graph corresponds to the time when the PVDF was receiving
vibration from the rod):
 31

Commercial PVDF

0.4
Sample 1
0.3
0.2
0.1
Voltage

0
-0.1 0 5000 10000 15000 20000

-0.2
-0.3
-0.4
-0.5
Time

Sample 2
0.25

0.2

0.15

0.1

0.05
Voltage

0
0 5000 10000 15000 20000
-0.05

-0.1

-0.15

-0.2

-0.25
Time
 32

Sample 3
0.25
0.2
0.15
0.1
0.05
Voltage

0
0 5000 10000 15000 20000 25000
-0.05
-0.1
-0.15
-0.2
-0.25
Time

PVDF I

0.004

0.003

0.002
Voltage

0.001

0
0 200 400 600 800 1000 1200
-0.001

-0.002

-0.003
Time

Below is the screenshot from Analog Devices Oscilloscope Software for PVDF II
 33

PVDF II

0.005

0.004

0.003

0.002
Voltage

0.001

0
0 200 400 600 800 1000 1200
-0.001

-0.002
Time

Below is the screenshot from Analog Devices Oscilloscope Software for PVDF II
 34

As we can see both PVDF I and II posses piezoelectricity and PVDF I is supposedly more
effective piezoelectric than PVDF II as it generates a higher voltage on being subjected to the
same force. Both PVDF sheets are however less piezoelectric in comparison to the commercial
PVDF.

3.3. Response To Temperature

Normally materials that are piezoelectric are also pyroelectric. Pyroelectricity is the ability of
certain materials to generate a temporary voltage when they are heated or cooled. The change
in temperature modifies the positions of the atoms slightly within the crystal structure, such that
the polarization of the material changes. This polarization change gives rise to a voltage across
the crystal.

Pyroelectricity is different from thermoelectricity as in pyroelectricity the whole crystal is

changed from one temperature to another, and the result is a temporary voltage across the
crystal while in thermoelectricity one part of the device is kept at one temperature and the other
 35

part at a different temperature, and the result is a permanent voltage across the device as long
as there is a temperature difference.

Since we knew the PVDF prepared in the lab were decent piezoelectrics, they could also be
tested for their pyroelectric properties.
The following experiment was performed to analyse the pyroelectric properties of PVDF I, II and
commercially available PVDF.

Experimental Procedure:

1. A hot plate was taken and kept at room temperature.

2. A small beaker was filled with water and kept aside the hot plate.
3. The PVDF samples were taken and stuck to the hot plate using aluminum
tape.
4. The water containing beaker was then placed on the PVDF sheet.
5. The temperature was increased in steps of 5°C up to 85°C at intervals of
around 1 min. This is termed as forward case.
6. The voltage generated vs time graph was recorded using the Analog
Devices oscilloscope.
7. Then temperature was decreased gradually from 85℃ to room
temperature and the voltage vs time graph was recorded. This is termed
as reverse case.

(Fig 13)
 36

Observations:

Commercial PVDF

Forward

0.05
0.04
0.03
0.02
0.01
Voltage

0
0 20000 40000 60000 80000 100000
-0.01
-0.02
-0.03
-0.04
-0.05
Time

Reverse
 37

PVDF I

Forward

0.05
0.04
0.03
0.02
Voltage

0.01
0
0 10000 20000 30000 40000 50000 60000 70000
-0.01
-0.02
-0.03
-0.04
-0.05
Time

Forward

0.3

0.2

0.1
Voltage

0
0 10000 20000 30000 40000 50000 60000 70000

-0.1

-0.2

-0.3
Time
 38

Reverse

0.04

0.03

0.02

0.01
Voltage

0
0 5000 10000 15000 20000 25000 30000
-0.01

-0.02

-0.03

-0.04
Time

PVDF II

Forward

0.2

0.15

0.1

0.05
Voltage

0
0 10000 20000 30000 40000 50000 60000
-0.05

-0.1

-0.15

-0.2
Time
 39

Reverse

0.06

0.04

0.02
Voltage

0
0 5000 10000 15000 20000 25000 30000

-0.02

-0.04

-0.06
Time

Analysis:

In all three cases (Commercial PVDF, PVDF I and PVDF II), the forward case graph is diverging
implying greater voltage generated for greater temperature (as temperature is increasing with
time) and the reverse case graph is converging implying decreasing generated voltage with
decreasing temperature. Hence all three PVDF sheets are pyro electric in nature.

3.4. Experiments with Sound

Once, just while seeing what all things PVDF could do, I placed the PVDF sheet (covered in thin
PDMS) on my throat near the vibrating vocal chords. And I saw patterns in the oscilloscope in
correspondence to what I spoke. This property of PVDF could be potentially used for making
microphones.
 40

But if one were to make a microphone out of PVDF, it had to be checked what frequencies does
PVDF respond to best. So I performed an experiment to find out the response of PVDF to
different sound frequencies.

Since I was trying to make an application out if it, I used commercial PVDF for the experiment
as it gave the most profound response.

Experimental Procedure:

1. A metallic board with holes and its components were taken to make and
apparatus as shown in the figure below:

(Fig 14)

2. A speaker was kept on the metallic board, which took the audio input from
the laptop.
3. The PVDF sample (connected to Ananlog Devices oscilloscope) were
placed on the platform just above the speaker.
4. Sound of frequencies from 50 Hz to 6000Hz was provided to the speaker
through MATLAB, and the voltage vs time graph was recorded for each
frequency through Ananlog Devices oscilloscope.
 41

Observations:

A few of the graphs between 50 Hz and 6000Hz that were recorded for Commercial PVDF are
shown below:

50Hz 200Hz
0.2 2
0.15
1.5
0.1
0.05 1
0 0.5
-0.05 0 5000 10000 15000
-0.1 0
0 5000 10000 15000
-0.15 -0.5
-0.2
-1
-0.25
-0.3 -1.5

400 Hz 600Hz
0.4 0.3
0.3
0.2
0.2
0.1 0.1

0 0
-0.1 0 5000 10000 15000 0 5000 10000 15000
-0.1
-0.2
-0.3 -0.2

800 Hz 1000Hz
0.15 0.15
0.1 0.1
0.05 0.05
0 0
0 5000 10000 15000
-0.05 -0.05 0 5000 10000 15000

-0.1 -0.1
-0.15 -0.15
 42

2000 Hz 3000Hz
0.15 0.15
0.1 0.1
0.05 0.05
0 0
0 5000 10000 15000 0 5000 10000 15000
-0.05 -0.05
-0.1 -0.1
-0.15 -0.15

4000 Hz 5000 Hz
0.15 0.2
0.1 0.15
0.1
0.05
0.05
0
0 5000 10000 15000 0
-0.05
-0.05 0 5000 10000 15000
-0.1 -0.1
-0.15 -0.15
-0.2 -0.2

6000Hz 7000 Hz
0.2 0.2

0.1 0.1

0 0
0 5000 10000 15000 0 5000 10000 15000
-0.1 -0.1

-0.2 -0.2

8000 Hz 9000Hz
0.2 0.2

0.1
0.1
0
0 5000 10000 15000 0
-0.1 0 5000 10000 15000
-0.1
-0.2

-0.3 -0.2
 43

Analysis:

In order to understand the response of PVDF to different sound frequencies, a single frequency
spectrum was made using all the frequency vs time graphs of the sample.

For this, the root mean square voltage was calculated by finding out the peak to peak voltage of
the plot corresponding to each frequency. Then the RMS voltage was plotted against the
corresponding frequency to obtain the frequency spectrum of PVDF.

The frequency spectrum of the PVDF is shown below:

1.6

1.4

1.2
RMS Voltage

0.8

0.6

0.4

0.2

0
0 200 400 600 800 1000 1200
Frequency

As we can see from the spectrum, PVDF is most responsive to frequencies between 50Hz and
300Hz and the RMS voltage falls to a comparatively negligible value afterwards. However the
human voice frequency band ranges from approximately 300 Hz to 3400 Hz and hence, PVDF
could not serve as a very effective microphone as it wouldn’t respond to frequencies above 300
Hz as good as it would to below 300 Hz.
 44

4. APPLICATIONS

4.1. Pulse Sensor

Once while trying out the capabilities of PVDF, I placed a PVDF patch on my pulse and tried to
see if it detects anything in the oscilloscope. But since the sheet is very fragile on its own it
didn’t get placed very well and hence showed no change in the oscilloscope. So I covered the
PVDF patch with PDMS (Polydimethylsiloxane, a transparent rubber like substance) to protect it
and then again pressed the PDMS covered PVDF patch on my wrist. This time feeble changes
were noticed in the oscilloscope. But the main thing about those changes were that they were
periodic with the pulse rate. Hence PVDF patch was actually capturing the pulse.

(Fig 15)
 45

(Fig 16)

However the pulse detection in the oscilloscope was too less to be obvious. So I made an
amplifier circuit in order to amplify the signal that the pulse sent into oscilloscope and make the
detection more obvious.

(Fig 17)
 46

The above figure represents the amplifier circuit I made where the dark rectangle on the left
represents the PVDF patch. The amplifier circuit that I made consisted of a simple voltage
follower connected with an opamp whose negative end was connected to a potentiometer that
came from the output. Altering the potentiometer, altered the voltage gain. So one could keep
altering the potentiometer till he got the voltage gain of his choice. The two ground points in the
circuit diagram went to the oscilloscope, where the readings were recorded.

(Fig 18)

Then the PVDF patch covered in PDMS was again pressed against the wrist and the
potentiometer was altered to get a high voltage gain and to amplify the pulse signal in the
oscilloscope. After a good gain was observed, a sufficiently detectable pulse was recorded by
the oscilloscope.

Below is the screenshot from the Analog Devices Oscilloscope software, when it recorded the
ECG from PVDF patch:
 47

(Fig 19)

The graph above shows the pulse reading from the PVDF patch connected to the amplifier
circuit. The time period of pulse in the graph above is around 0.7 seconds, which gives a pulse
frequency of 1.42 Hz. So according to this data, the pulse rate (per minute) is 1.42*60 which
gives ~85 which is in correspondence to the actual pulse rate.

Hence using a simple PVDF patch and a simple amplifier circuit, one could record human
Electocardiograph.

Currently I am working to make this device a little more compact and turn it into a band, such
that the PVDF patch and the circuit can be encompassed in that band itself.

4.2 Breath Sensor

The same circuit that we discussed in the previous section can be used as breath sensor as
well. In order to record the breath pattern, I put the PVDF patch covered in PDMS with the
 48

amplifier circuit on my stomach and observed the breath pattern in the oscilloscope, which is
shown below:

(Fig 20)

Hence this way this sensor can prove quite beneficial in the field of medicine in various ways.

4.3. Concept of PVDF Weighing Scale

I didn’t not actually try it out experimentally, but I found the idea quite promising. The concept
was suggested to me by a friend of mine. The idea behind it is that when something tiny is
placed on stretched PVDF sheet, it would generate a small voltage because of piezoelectricity.
And depending on the weight placed on the PVDF sheet, the voltage generated would be
different. So by establishing a correspondence between the voltage generated and the weight
placed, one could find weights of objects to a very high precision. Currently, the apparatus used
for high precision measurements are quite expensive and difficult to operate, but using PVDF
for the task could make the whole process simpler and cheaper.
 49

5. SUMMARY

Research was conducted on piezoelectric effects of PVDF. A series of laboratory experiments

and surface characterization were carried out in order to obtain basic understanding of the
piezoelectricity in PVDF.

PVDF was prepared in lab by two different methods (basically different in their poling methods)
and also the concepts behind metal coating using Vacuum Coating Unit were discussed.

The PVDF sheets, both lab made and commercial ones, were characterized and their
piezoelectricity was compared using a sinusoidal valve also prepared in the laboratory.

The PVDF sheets were tested for their pyro electric properties by studying its response to
temperature. They were also exposed to different sound frequencies to see, how it responds to it
and the frequency spectrum of PVDF was made and studied.

Pulse sensor and Breath sensor were made in lab using PVDF and a simple amplifier circuit and
they were tested to give positive results.
 50

6. REFERENCES
Most of the background information used in this thesis was taken from www.wikipedia.org and a
few other articles on the internet.

Fig 1 and Fig 3