COURSE TITLE: Applied Chemistry for Emerging Electronics and Futuristic Devices (Electrical and Electronics Engineering Stream)

MODULE - 3

Functional Polymers in Flexible Electronics

Module–3 : Functional Polymers in Flexible Electronics (Syllabus) 08 hours

Polymer: Introduction, terminology, molecular weight of polymers - number and weight average
molecular weight of polymers, numerical problems. Conducting polymers: Introduction, synthesis,
conduction mechanism and applications of polyaniline in electronic devices. Synthesis, properties and
applications of polydimethylsiloxane (PDMS) in RFID (radio frequency identification). Synthesis,
properties and applications of polyvinylidene fluoride (PVDF) in E-nose devices.
Polymeric semiconductors: Introduction, n-type and p-type polymeric semiconductor materials, organic
photovoltaics - poly(3-hexylthiophene) (P3HT) as a donor and phenyl C61-butyric acid methyl ester
(PCBM) as an acceptor, construction, working and applications.
Polymer Composites: Introduction, synthesis and properties of epoxy resin- Fe₃O₄ composite for sensors
applications, synthesis of Kevlar Fiber Reinforced Polymer (KFRP)-properties and smart electronic
devices applications.
Self learning: Difference between organic and inorganic semiconductors.

INTRODUCTION

➢ Polymers are essential part of everyday household stuff and have profound applications in
industry as well.
➢ Paints (polyacrylate), adhesives (epoxy resin), fibres (nylon, polyester), elastomer (rubbers) are
used everywhere.
➢ Polyethylene and polypropylene are used in packing industry and electronic industry has also been
greatly benefitted from polymers. Thus it is of high importance and interest to understand the
chemistry behind such polymers so as to be better utilized by any community.
TERMINOLOGIES
Polymer: “A polymer is defined as a macromolecule of high molecular weight formed by the repeated
combination of several simple molecules called monomers of one or more type through covalent bonds”
Example- Polyethylene, nylon, PVC, Teflon, polyester, bakelite, etc.

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Monomer: Simple/small molecules which combine with each other to form polymer. Examples: Ethylene,
vinyl chloride, butylene, chloroprene etc.
Polymerization: It is defined as “the chemical reaction in which monomer is converted into polymer”
Degree of polymerization: The number of repeating units in a polymer.
Functionality: The number of bonding sites in a monomer molecule. For example, ethylene can add two
molecules of hydrogen or halogen. Hence, it is bifunctional (functionality two). Similarly, acetylene has a
functionality of four (tetrafunctional), as it can react with four atoms of hydrogen or halogen.

Molecular Mass of polymer

− During the formation of polymers, different polymers have different degrees of polymerization.
− Thus, molecular masses of individual macromolecules in a particular sample of polymer are
different. Hence, an average value of the molecular mass is taken.
− There are two ways through which average molecular masses can be calculated.
1. Number- average molecular mass (Mn)
2. Mass – average molecular mass (Mw)

1. Number Average Molecular weight (Mn):

− It is determined by measurement of colligative properties such as depression in freezing point,
elevation of boiling point, osmotic pressure and lowering of vapour pressure.
− It is defined as the total mass of all the molecules in a polymer sample divided by total number of
molecules present. Thus the number average molecular mass is given by:

∑𝑁 𝑀
𝑀 =

Where Mi is the molecular weight of a chain, Ni is the number of chains of that molecular weight,
and i is the number of polymer molecules.
2. Weight average molecular mass (Mw):
− It is obtained by light scattering and ultra centrifugation techniques, which measures/property
depends on the molecular size. It is given by

− The weight average molecular mass is always greater than number average molecular mass.

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Poly Dispersity Index (PDI): In order to obtain the idea of homogeneity of a polymer, the term poly
dispersity index is used. It is the ratio of mass average molecular mass to the number average molecular
mass.
PDI = Weight average molecular mass / Number Average molecular mass
Significance of PDI:
1. Polymers whose molecules have same or narrow range of molecular masses. Such polymers
are said to be monodisperse. For natural polymers, PDI is usually equal to one and they are
monodisperse.
2. Polymers which have wide range of molecular masses. Such polymers are called
polydisperse. Synthetic polymers generally have PDI > 1.

CONDUCTING POLYMERS

“An organic polymer with highly delocalized pi-electron system, having electrical conductance of the order
of a conductor is called a conducting polymer”. The electrical conductivity of polyacetylene can be
increased to 13 folds by doping with electron acceptors and donors. Tremendous applications would exist
as they are flexible, ease of fabrication, stability, ease of processability, etc.
Key structural feature of conducting polymer - linear structure with alternate single and double
bonds, i.e., extensive pi conjugation in the backbone.
The conducting polymers are synthesized by doping, in which charged species are introduced in organic
polymers having pi-backbone. The important doping reactions are (a) oxidative doping (p-doping) (b)
reductive doping (n-doping) & (c) protonic acid doping. The electrical conductivity of doped polyacetylene
(105 sm-1) is remarkable to Teflon (10-8 sm-1) but is marginally lower than copper (108 sm-1).
Examples are below are some of the conducting polymers

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POLYANILINE:
Synthesis: It is obtained by polymerization of aniline dissolved in 1M HCl at 3-40C in presence of
ammonium persulphate as an initiator.

Properties and Applications of conducting polyaniline:

1. It is used as an electrode in rechargeable solid state batteries (Li-PAn batteries). (This is due to its
reversible electrochemical response during anodic oxidation and cathodic reduction).
2. It is used in anodic passivation of metals as a means ns of corrosion control.
3. Polyaniline exhibits different colour in oxidized and reduced forms and hence it is used in humidity
sensors, gas sensors, radiation sensors.
4. Due to same property it is also used in electrochromic display windows.
5. It is used as conductive track on PCBs.

MECHANISM OF CONDUCTION IN POLYANILNE:

Conducting form of polyaniline is obtained from emaraldine base consisting of equal proportions of amines
(-NH-) and imine (=N-) sites. Protonation of each imine group introduces one +ve charge into polymeric
back bone. Positive charges once introduced into polymer chain can easily move along the chain and are
responsible for electrical conductivity.
Emaraldine base is protonated by treating with aqueous HCI (1M). Usually, two nearby imine sites are
protonated to form a bipolaron (dication salt). The bipolaron then undergoes a further rearrangement to
form two polarons in which positive charges are delocalized as shown in the reaction scheme. The resulting
emeraldine salt has delocalized +ve charges in the polymeric back bone which are responsible for electrical
conductivity. Positive charges are compensated by anions (chloride ions) of the acid. Thus polymer as a
whole is electrically neutral but contains delocalised positive charges on the polymer structure which
conducts an electric current. This type of protonic acid doping increases the conductivity of polyaniline by
9 to 10 times.
Only 1% of the charge carriers which are available in the Emeraldine salt actually contribute to its observed
conductivity. If all the available charge carriers were to contribute, the resulting conductivity at room
temperature would be - 10 S/ cm, which is comparable to that of copper.

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Mechanism of conduction in polyaniline (Emaraldine base)

POLY DIMETHYL SILOXANE (PDMS)

Synthesis, properties and applications of PDMS (Poly dimethyl siloxane) in (Radio Frequency
Identification) applications.
PDMS (Polydimethylsiloxane) is a very high-performance, transparent, and flexible silicone polymer. It is
a long chain made of repeating smaller units, called monomers. Chemical repeat unit of PDMS is -[Si(CH3)2-
O]-n. The backbone is made of silicon (Si) and oxygen (O) atoms, with two methyl groups (-CH3) attached

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to each silicon. Thus, PDMS is a flexible chain of silicon and oxygen, with soft "side arms" of methyl groups.

Synthesis of PDMS
PDMS is usually synthesized in two main steps:
Step 1: Hydrolysis of the Monomer
Monomer, Dichlorodimethylsilane ((CH3) SiCl2) is hydrolysed with water (H2O). The two chlorine (Cl)
atoms are replaced by hydroxyl (-OH) groups forming a very reactive intermediate called a silanol

Step 2: Condensation Polymerization

The silanol molecules don't stay separate for long. The hydroxyl (-OH) group of one silanol molecule reacts
with the -OH group of another. They link up by forming a strong siloxane (Si-O-Si) bond and release a
molecule of water. This is called a condensation reaction.

This process repeats over and over, with more and more molecules linking together to form long, liquid
chains of the polymer.

Step 3: Curing (Turning the Liquid into a Solid Rubber)

The condensation produces linear chains of PDMS which is a thick honey like liquid. To get the useful, solid,
rubbery material, it is further treated with cross-linking agents like tetraethyl orthosilicate, TEOS and Pt-
based catalysts. These introduces chemical bridges between the long polymer chains. This turns the liquid
into a solid, 3D network, giving PDMS its characteristic strength and elasticity.

Properties of PDMS

PDMS has a unique combination of properties:

1. It is flexible and elastic because of its Si-O bonds which are stronger and more flexible than C-C
bonds in polymers. It can be stretched 100-300%, twisted, and bent without breaking, just like skin.
2. It is biocompatible. It is non-toxic and FDA-approved for medical use. It doesn't cause reactions with
human skin or tissue. This is a must-have for any wearable or implantable device.
3. It has high optical transparency. It is crystal clear. This is useful for LEDs or optical sensors

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applications.
4. It is hydrophobic due to methyl side groups. It naturally repels water, which helps protect
electronics from sweat and moisture.
5. It is permeable to gases. It allows gases like oxygen and carbon dioxide to pass through. Thus it can
breathe in e-skin applications.
6. It is a very good electrical insulator. It does not conduct electricity, making it a perfect base
(substrate) on which to build electronic circuits.
7. It is stable up to 200°C and decomposes above 300°C stable due to Si-O bond energy

Applications in RFID (Radio Frequency Identification):

RFID is a technology used for wireless identification using electromagnetic waves. RFID tag is a wireless
barcode tag with antennas that send info when scanned by radio waves. These are used for tracking
everything from products in a store to people like in metro cards, toll tags, inventory tracking and patient
monitoring.

PDMS is used as a base substrate for RFID tags due to following reasons:

1. By building the RFID antenna on a PDMS substrate, we can create tags that are not flat and rigid but
flexible and wearable. These can be bent or even embedded into clothing. It acts as a protective
encapsulation layer for fragile RFID circuits.
2. PDMS layer can hold a stretchable conductive antenna. It can integrate stretchable conductive
patterns like Cu, Ag nanowires, graphene, CNTs for RFID antennas.
3. Because PDMS is biocompatible, an RFID chip can be encapsulated within it and safely implanted
under the skin as implantable tag. It is not rejected by body and can be used for medical
identification or secure access.
4. The washable and waterproof nature of PDMS protects the fragile RFID antenna and chip from
physical damage and moisture. This makes the tags much more durable for use in harsh
environments.

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POLYVINYLIDENE FLUORIDE (PVDF)

Synthesis:
PolyVinylidene Fluoride (PVDF) is a semi-crystalline polymer of Vinylidene Fluoride (VDF) monomer with

repeat unit: . PVDF is made by free radical polymerization of VDF using dibenzoyl peroxide
or ammonium persulfate as initiator.

The "Smart" Properties of PVDF

PVDF can exist in several crystalline phases:
a) -phase which is a most common phase. It is non-polar and has twisted chain structure. The dipoles
of C-F bonds are arranged in alternating directions and they cancel out. Hence, no net polarization.
b) -phase is highly polar where the dipoles (C-F bonds) are aligned in one direction. Hence, it has
strong net polarization. It has dipole moment 2.1 D per unit. It has straight chain structure. This is
responsible for unique piezoelectric and pyroelectric properties. a-phase can be converted into B-
phase by stretch the film 3-5 times at 80-100°C. Also by applying strong electric field while heating
to 70- 100°C. This aligns the dipoles (positive-negative ends). This is called as poling.
c) - and -phases are less common.

PVDF with -phase has unique properties. Few of them are given below:

1. It shows Piezoelectric property. It Generates electric charge when mechanically deformed. If you
press, bend, or stretch it, it generates a small voltage. Conversely, if you apply a voltage to it, it will
slightly change its shape (expand or contract). This happens because in the beta phase, the dipoles
(C-F bonds) are aligned in one direction.
2. It also shows Pyroelectric property. It generates a voltage when temperature changes. This makes
it useful for thermal sensors.
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3. It is ferroelectric and can hold charge. It has dielectric constant of 8-12 which is good for capacitors.
4. PVDF exhibits high chemical resistance. It is hydrophobic (repels water), resistant to acids, solvents,
and other harsh chemicals. It is thermally stable up to ~170 °C. It is UV stable and lasts 20+ years
outdoors without yellowing.
5. PVDF is a strong and tough polymer with high flexibility compared to other fluoropolymers.

Applications in E-nose
E-nose is an artificial nose that mimics the human sense of smell by using an array of sensors to
detect and identify different gases or odors. PVDF films are used as the sensing layer because they are
piezoelectric. When gas molecules adsorb on PVDF film, they change mass or strain on the surface. This
causes a measurable change in electrical signal. They can be coated with nanoparticles, enzymes, or
polymers to selectively detect different gases/odors.

In an electronic nose, a thin PVDF is coated on an electrode which can adsorb certain gas molecules
(the "smell"). The PVDF sensor is made to vibrate at its natural high frequency using its piezoelectric
property. When the target gas molecules land on the coating, they add a tiny amount of mass to the sensor.
This extra mass changes the vibration frequency of the PVDF. Piezoelectric effect converts this change into
electrical signal. This signal is analysed to identify the odor (like detecting food spoilage, environmental
gases, explosives). By using an array of PVDF sensors with different coatings, the e-nose can identify the
unique "frequency fingerprint" of a complex smell.

POLYMERIC SEMICONDUCTORS:
Introduction
Semi-conducting polymers are having the energy gap between the valence band and conduction band
(band gap) are not so large and not so small. They have low conductivity.

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Due to the low conductivity, these are not used in practical field. The conductivity of these semiconductor
however enhances by many ways
1. Doping
2. Filled with conducting polymer
3. Blending with conducting polymer
Doping :
The conduction power of semiconductor can be enhanced by input some foreign material or
impurities. These impurities are called doping agent or dopant. Appropriate doping agent increase the
conductivity of semiconductors many folds. The increase in conduction is due to participation of impurity
elements in between the valence band and conduction band and thus making a bridge through which
electrons can jump easily from the valence band to the conduction band.
Doping are mainly two types,
i) p-type doping through oxidation of materials: In this type of doping some electrons from the
conjugated bonds are removes through oxidation, creating a positive hole called polaron inside the
polymer. The positive hole or polaron can move throughout the polymeric chain and make it
conducting polymer. Lewis acids(FeCl3,AlCl3) are generally use as doping agent.

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ii) n-type doping through reduction of materials: In this type of doping some electrons are
introduced to the conjugated bonds through reduction creating a negative hole or charge inside
the polymer. The negative hole or charge can move throughout the polymeric chain and make
it conducting polymer.
Lewis bases are generally use as doping agent.

POLYMER COMPOSITES
An ideal structural material (air craft industry) should have properties such as: (a) Low density (b)
High strength and stiffness (c) Corrosion resistance and (d) Abrasion and impact resistance. No single
metal, alloy, ceramic or polymeric materials are known that can offer combination of aforesaid properties.
This is because a strong material is relatively dense and an increase in stiffness generally results in a
decrease in impact strength. The search for materials possessing above properties led to the development
of composite materials. They are initially developed for military and aerospace applications in 1940’s and
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are currently used for house decoration, bridge repair, mooring cables, structural strengthening and other
applications.

“A combination of two or more distinct components to form a new class of material suitable for structural
applications is referred as composite materials”.

Polymer composites are generally made of two components, namely (i) matrix and (ii) fibre. The fibre is
generally embedded in the matrix in order to make the matrix stronger. The matrix is usually a thermoset
material such as epoxy resin and it holds the fibre together. Fibre is most often glass; other synthetic fibres
include carbon fibre, Kevlar etc. Naturally occurring fibres such as wood - lignin, cellulose can also be
employed.

Importance as structure material

❖ Matrix binds the fibers together and can transmit and distribute any externally applied stress to the
fibers.
❖ Matrix protects individual fiber from surface damage due to mechanical abrasion or any chemical
reaction with the surroundings.
❖ The strength of the composite material is primarily due to the bonding forces between fibers and
matrix.

EPOXY RESIN-MAGNETITE (Fe3O4) COMPOSITE

Introduction

Epoxy resin-magnetite (Fe3O4) composites are hybrid materials that combine the mechanical strength and
chemical stability of epoxy resins with the magnetic. electrical, and sensing properties of magnetite
nanoparticles (Fe3O4).

Such composites have attracted significant interest for sensor applications, electromagnetic shielding, and
smart materials due to their tunable electrical conductivity, magnetic response, and dielectric properties.

Epoxy resin is a thermosetting polymer containing epoxide (-C-O-C-) groups that can crosslink with
hardeners (like amines). It has high mechanical strength, good adhesion and chemical resistance, and
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electrical insulation and thermal stability.

Magnetite (Fe3O4) is a ferrimagnetic iron oxide nanoparticle. It has strong magnetic moment, electrical
conductivity due to Fe2+/Fe3+ ions, high surface area and it is biocompatible.

Synthesis of Epoxy Resin- Fe3O4 Composite (Ultrasonication Method)

The ultrasonication method is a simple, efficient route to disperse nanoparticles uniformly within a
polymer matrix.

Materials required are epoxy resin (e.g., diglycidyl ether of bisphenol A, DGEBA), Hardener (e.g.,
triethylenetetramine, TETA), Fe3O4 nanoparticles (synthesized or commercially obtained) and Solvent
(optional): acetone or ethanol (to aid dispersion).

2.2 Synthesis Steps

Step 1: Preparation of Fe3O4 Nanoparticles (if synthesized in-lab)

Chemical co-precipitation method: Mix FeCl3.6H2O and FeCl2.4H2O in a 2:1 molar ratio. Add to NaOH or
NH4OH solution under stirring at 60-80 °C. Black precipitate of Fe3O4 forms. Wash and dry the
nanoparticles.
Fe2+ + 2Fe³+ + 8OH- ⇾ Fe3O4 + 4H2O
Step 2: Dispersion of Fe3O4 Nanoparticles (Ultrasonication)

Add a specific wt% of Fe3O4 nanoparticles (e.g., 1-10%) into epoxy resin. Use an ultrasonic probe or bath
(20-40 kHz) for 30-60 minutes to achieve uniform dispersion and prevent agglomeration. The high-
frequency ultrasound waves create cavitation, which breaks particle clusters and distributes them evenly
in the resin.

Step 3: Mixing with Hardener and Curing

Add the hardener to the Fe3O4-epoxy mixture in the proper ratio (usually 10:1 or as recommended). Stir
gently to avoid air bubbles. Pour into molds and cure at room temperature or elevated temperature (60-
80 °C) for several hours.

Step 4: Post-Curing and Finishing: After curing, remove the samples and post-cure (if required) to ensure
full crosslinking. The resulting composite is solid, smooth, and magnetically active.

Properties of Epoxy Resin- Fe3O4 Nanocomposite

The composite exhibits synergistic properties from both the polymer matrix and the magnetic
nanoparticles.

1. Structural and Morphological Properties: Interfacial bonding between Fe:O4 and epoxy enhances
mechanical strength. Nanoparticle size (typically 10-50 nm) influences electrical and magnetic
performance.

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2. Mechanical Properties: Increased hardness and tensile strength with optimal nanoparticle loading.
Improved toughness due to good stress transfer between FesO4 and epoxy.
3. Electrical and Dielectric Properties: Addition of FesO4 increases electrical conductivity and
dielectric constant. The composite transitions from insulating to semiconducting behavior.
Dielectric loss increases slightly due to interfacial polarization (Maxwell-Wagner effect)
4. [Link] Properties: The composite becomes magnetically responsive (superparamagnetic or
ferrimagnetic). Magnetic saturation decreases slightly compared to pure FesO4 due to the polymer
matrix. Useful for magnetic field sensing and electromagnetic shielding.
5. Thermal Properties: Enhanced thermal stability and glass transition temperature (Tg). FesO4
nanoparticles act as heat dissipation centers.

Sensor Applications of Epoxy-Fe:O Nanocomposite

1. Magnetic Field Sensors: Detects changes in magnetic field via variations in resistivity or inductance.
Useful for non-contact sensing and position detection.
2. Pressure and Strain Sensors: Electrical resistance of the composite changes under deformation.
Suitable for flexible or structural health monitoring sensors.
3. Temperature Sensors: Resistance varies with temperature due to magnetoresistive effects. Hence,
can be used in temperature sensor.
4. Gas and Chemical Sensors: Surface-modified Fe3O4-epoxy composites show selective gas adsorption
leading to resistance change. Hence, it can be used in Gas and Chemical Sensors

KEVLAR FIBER REINFORCED POLYMER (KFRP) COMPOSITES

Synthesis and Properties for Smart Electronic Devices Applications

Kevlar Fiber Reinforced Polymer (KFRP) composites are advanced materials where high-strength Kevlar
(aramid) fibers are embedded in a polymer matrix, like epoxy or polypropylene. They are lightweight,
durable structures with exceptional mechanical and thermal properties. Kevlar is renowned for its five
times the strength of steel at one-fifth the weight. It makes KFRP ideal for demanding applications. In smart
electronic devices such as wearables, flexible sensors, and structural supercapacitors, these composites
enable multifunctional designs that combine mechanical robustness with electrical functionality,
supporting trends toward flexible and sustainable electronics.

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Synthesis of KFRP Composites

Synthesis involves combining Kevlar fibers with a polymer matrix through processes that ensure strong
fiber-matrix bonding for load transfer. The goal is uniform dispersion and minimal voids, achieved via
chemical treatments or advanced fabrication. Key steps and methods:

b. Kevlar Fiber Preparation: Kevlar fibers (Kevlar 29 or 49, diameter 10-20 µm) are used fibers.
c. Matrix Selection and Mixing: Thermoset matrices (e.g., epoxy from bisphenol A + epichlorohydrin)
or thermoplastics (e.g., polypropylene) are used.
d. Fabrication Techniques: Additive Manufacturing: This technique is used for obtaining composites
suitable for electronics. It prints continuous Kevlar- reinforced filaments at 220-250°C nozzle
temperature. Achieves anisotropic strength up to 200 MPa along fibers.

Properties of KFRP Composites

1. Mechanical Properties: It exhibits exceptional tensile strength (200-500 MPa for composite) with
2. higher Young's modulus 70-130 GPa.
3. Thermal Properties: It is stable in the temperature range -196 to +204°C. Low thermal conductivity
for insulation.
4. Electrical Properties: It has low dielectric constant (3-4), making it suitable for insulating flexible
circuits. Kevlar's conductivity is near-zero, but doping with CNTs raises it to 10-3 S/cm for
antistatic uses.
5. It's density is 1.4-1.6 g/cm³. It is a lightweight polymer. It has high chemical resistance to oils and
acids).

Applications in Smart Electronic Devices

KFRP is used in the following smart electronics applications due to its flexibility, strength, and low weight:

1. Wearable Electronics: It is used in flexible sensors in smartwatches/fitness trackers. It provides

bendable, impact-resistant housing; elongation >3% prevents cracks during motion.
2. Structural Supercapacitors: It is used as energy-storing composites for EVs/drones. It acts as load-
bearing electrode due high 200 MPa strength.
3. Flexible PCBs/Antennas: It is used in bendable circuit boards for IoT devices. It is insulating
substrate with EMI shielding and thermal stability for high- speed signals.
4. Portable Chargers/Smart Textiles: It is used in solar-integrated fabrics or foldable batteries. It's
lightweight reinforcement and vibration damping extends device life in mobiles.

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