POLYMERS

A WORD POLYMER IS A COMBINATION OF TWO GREEK WORDS,

“POLY” MEANS “MANY” AND “MEROS” MEANING “PARTS OR UNITS”

A POLYMER IS A MACRO MOLECULE FORMED BY

REPEATED LINKING OF THE SMALL MOLECULES CALLED
“MONOMERS”
 Crystallinity
 Glass transition
 Melting Point
 Viscoelasticity
 Solubility
Highly crystalline polymers are rigid, high melting, and less affected
by solvent penetration.
Crystallinity makes a polymers strong, but also lowers their impact
resistance.
Samples of polyethylene prepared under high pressure (5000 atm)
have high crystallinities (95 - 99%) but are extremely brittle.
 Polymer molecules are very large so it might seem that they could not
pack together regularly and form a crystal.

 Regular polymers may form lamellar (plate-like) crystals with a

thickness of 10 to 20 nm.

Degree of Crystallinity of Polymers

 Factors Affecting the Crystallinity of Polymers

1. The size of the side group.

2. The extent of branching.
3. Tacticity
4. The complexity of repeating unit.
5. Degree of secondary bonding.
 Experimental measurement of the
Degree of Crystallinity of Polymers

1. Density measurements
2. Differential scanning calorimetry
3. X-ray diffraction
4. Infrared spectroscopy (IR)
5. Nuclear magnetic resonance (NMR)
Polymers have both amorphous and crystalline regions.

 The amorphous regions can be either in the glassy or rubbery state

 The temperature at which the transition in the amorphous regions

between the glassy and rubbery state occurs is called the glass
transition temperature (Tg).
Glassy State Rubbery State
Brittle Viscous, Elastic
 Property of the Amorphous region

 Below Tg: Glassy solid

 Above Tg: Rubbery solid

The glass transition is not the same thing as melting. Melting is a transition which occurs in Crystalline polymers.
Melting happens when the polymer chains fall out of their crystal structures, and become a disordered liquid. The
glass transition is a transition which happens to amorphous polymers; that is, polymers whose chains are not
arranged in ordered crystals,

But even crystalline polymers will have a some amorphous portion.

This portion usually makes up 40-70% of the polymer sample. This is why the same sample of a polymer can have
both a glass transition temperature and a melting temperature. But you should know that the amorphous portion
undergoes the glass transition only, and the crystalline portion undergoes melting only.

some polymers have high Tg's, and some have low Tg's. The question we haven't bothered to ask yet is
this: why? What makes one polymer glass transition at 100 oC and another at 500 oC?

The very simple answer is this: How easily the chains move. A polymer chain that can move around fairly easily will
have a very low Tg, while one that doesn't move so well will have a high one. This makes sense. The more easily a
polymer can move, the less heat it takes for the chains to commence wiggling and break out of the rigid glassy
state and into the soft rubbery state.
What makes one polymer move more easily than another?
Backbone Flexibility
This is the biggest and most important one to remember.

The more flexible the backbone chain is, the better the polymer will move, and the lower
its Tg will be.

polydimethylsiloxane. This backbone is so flexible that polydimethylsiloxane has a Tg way

down at -127 oC! This chain is so flexible that it's a liquid at room temperature, and it's even
used to thicken shampoos and conditioners.
another extreme, poly(phenylene sulfone).

This polymer's backbone is just plain stiff. It's so rigid that it doesn't have a Tg! You can heat
this thing to over 500 oC and it will still stay in the glassy state. It will decompose from all the
heat before it lets itself undergo a glass transition! In order to make a polymer that's at all
processable we have to put some flexible groups in the backbone chain.
 Polymer Tg (oC)

Polyethylene (LDPE) -125

Polypropylene (atactic) -20

Poly(vinyl acetate) (PVAc) 28

Poly(ethyleneterephthalate) (PET) 69

Poly(vinyl alcohol) (PVA) 85

Poly(vinyl chloride) (PVC) 81

Polypropylene (isotactic) 100

Polystyrene 100

Latex -65
 The glass transition is a property of only the amorphous portion of a
semi-crystalline solid (Polymer)
 The crystalline portion remains crystalline during the glass transition.

 At a low temperature the amorphous regions of a polymer are in the

glassy state.

 In this state the molecules are frozen on place. They may be able to
vibrate slightly, but do not have any segmental motion in which
portions of the molecule wiggle around.
Factors Affecting the glass transition temperature (Tg)
of Polymers
1. Chain-flexibility.
Polypropylene Polyethylene
Tg = -20 oC Tg = -125 oC

Substitution
Polypropylene (atactic) Polypropylene (Isotactic)
Tg = -20 oC Tg = 100 oC

Configuration
Polypropylene Polyvinyl alcohol
Tg = -20 oC Tg = 85 oC

Secondary bonding (H-bonding)

Factors Affecting the glass transition temperature (Tg)
of Polymers

1. Chain-flexibility.
2. Molecular Weight.
3. Cross-links.
4. Plasticizers.
5. Coplymerisaion.
  Property of the crystalline region if polymer

 Below Tm: Ordered crystalline solid

 Above Tm: Disordered melt

 The temperature at which the Ordered crystalline solid converted into

disordered melt is called the Melting temperature (Tm).

 VISCOELASTICITY
 Viscoelastic materials are those which exhibit both viscous and elastic characteristics

 It occurs due to the diffusion of atoms or molecules inside an amorphous material.

 When a stress is applied to a viscoelastic material such as a polymer, parts of the long polymer chain change
positions. This movement or rearrangement is called creep.

 Polymers remain a solid material even when these parts of their chains are rearranging in order to
accompany the stress, and as this occurs, it creates a back stress in the material. When the back stress is the
same magnitude as the applied stress, the material no longer creeps.

 When the original stress is taken away, the accumulated back stresses will cause the polymer to return to its
original form. The material creeps, which gives the prefix visco-, and the material fully recovers, which
gives the suffix -elasticity.
• polymer is elastic because after a strain due to the application of a
stress, it is capable to recovers. On the other hand, polymers are
viscous because their capability to creep after the strain.
 Applications of Viscoelastic Materials

Creep and Recovery

 The disks in the human spine are viscoelastic.

 Most people are taller in the morning than in the

evening.

 Astronauts have gained up to 5cm in height under

near-zero gravity conditions.
Failure in the electric light bulb
Heartbeat
 Stress Relaxation
 The strings of a Classical Guitar are made of Nylon, a synthetic polymer.

 The great classical guitarists of the 19th Century did not have Nylon,
invented in 1938, but used Catgut strings, usually made from the
intestines of sheep; Catgut is a natural polymer.
 Energy Absorption

 Tall buildings vibrate when dynamically loaded by wind or earthquakes.

 Viscoelastic materials have the property of absorbing such vibrational energy.

https://www.youtube.com/watch?v=q9emsMcG8cc
https://www.youtube.com/watch?v=q9emsMcG8cc
• Solubility of polymers depend not only on physicsl properties but also
on their chemical structure
• Factors affecting solubility
• Polarity
• Mol,wt
• Branching
• Cross linking
• crystallinity
• Polar molecules like poly acryl amide are soluble in water
• Non polar molecule like polystyrene are soluble in nonpolar solvents
like benzene
• Increase of Mol wt of polymers decreases solubility of polymers
• Cross linking cross linkages inhibit the interactions between polymer
chains and solvent molecule preventing solubility of polymers in
solvents
• Branching : increases solubility by extruding into the solvents.
• Crystallinity decreases the rate of solubility
Microchips
MICROLITHOGRAPHY
 Factors Affecting the Solubility of Polymers

1. Molecular weight of the polymer

2. Nature of polymer and solvent
3. Free energy of mixing
4. Intermolecular forces
5. Hydrogen bonding
Polymer solubility in solvents is an important area of interest in polymer
science and engineering because of its many applications in industry such
as

1. Microlithography
2. Membrane science
3. Plastics recycling

4. Drug delivery
CASTING
General Characteristics of Compression Molding

• Thermoset performs or granules are used.

• Materials are usually pre-heated
• Amount of material must be accurately measured to avoid excess
flash or insufficient material
• Metallic inserts may be molded in the product
• Shape must be free of undercuts
Used for manufacture of:
• Electrical parts
• Dinnerware
• Gears
• Buttons
• Buckles
• Knobs
• Handles and
• Large containers
 Blow Molding
• It is a process in which a heated hollow thermoplastic tube called
parison is inserted within a mold cavity and inflated the tube with
compressed air, to take the shape of the cavity and cooled it before
removing from the mold.
• Any hollow thermoplastic part can be blow molded
• Thin walled hollow products are formed
• Wall thickness can be increased by increasing the parison tube wall
thickness
• Extrusion Blow Molding
• Extrusion Blow Molding is commonly used for mass production of plastic bottles.
• The parison is extruded vertically in downward direction between two mold halves.
• When the parison reaches the required length the two mold halves close resulting in pinching the top
of parison end and sealing the blow pin in the bottom of the parison end.
• Parison is inflated by air blown through the blow pin, taking a shape conforming that of the mold cavity.
The parison is then cut on the top.
• The mold cools down, its halves open, and the final part is removed.
• Injection Blow Molding
• In Injection Blow Molding method a parison is produced by injecting a polymer into a hot injection
mold around a blow tube or core rod.
• Then the blow tube together with the parison is removed from the injection mold and transferred to a
blow mold.
• Following operations are similar to those in the extrusion blowing molding.
• Injection Blow Molding is more accurate and controllable process as compared to the Extrusion Blow
Molding.
• It allows producing more complicated products from a wider range of polymer materials.
 • ADVANTAGES
• This process lends itself to any designs involving hollow shapes.
• Equipment availability is good
• DISADVANTAGES
• Cycle times are slower than injection molding.
• prices are higher than injection molding.
Applications
• Disposable containers of various sizes and shapes,
• drums,
• recyclable bottles,
• automotive fuel tanks,
• storage tanks
• toys, tubs, small boats
 THERMOFORMING

57
• Thermoforming is a plastic manufacturing process in which the
thermoplastic sheets are formed with the application of heat and
pressure in a mold.
• The thermoplastic sheet is held horizontally over a mold surface and
clamped with a holding device. The sheet is heated up to predetermined
temperature using a heating element called heater.
• The thermoplastic sheet softens with the application of heat and is
pressed into or stretched over the mold surface by application of air
pressure or by any other means.
• The softened sheet conforms to the mold shape and it is held in place
until it cools. The mold cavity is opened and the thermoformed part is
released.
• The excess material is then trimmed out from the formed part. Excess
material can be reground, mixed with unused plastic, and again
reformed into thermoplastic sheets.
• High molecular weight thermoplastics mostly preferred for
thermoforming.

• There are mainly three different types of thermoforming process depending

upon the pressure required i.e., vacuum forming, pressure forming and
matched die forming.
CORPORATE TRAINING AND PLANNING 60
CORPORATE TRAINING AND PLANNING 61
 ADVANTAGES

• Tooling cost is inexpensive.

• Suitable for large parts
• Thin walled components can be made by this method only.
• Suitable for small number of parts, samples, prototypes etc.
• Low capital cost.
• Moulds can readily modified and quickly changed.

62
 Disadvantages

• Poor surface finish

• Parts may have non-uniform wall thickness.
• All parts need to be trimmed
•Limited number of materials can be used
•Very thick plastic sheets can’t be formed

63
 APPLICATION
• Refrigerator door liners
• Cheese containers
• Soft drink cups
• Packaging of Tablets and capsules
• Ice cream cups
• Plastic tray
• Helmets
• Telecommunication Joints
• Luggage
• Light and instrument panels.

64
 Synthesis of PET
• Trade name for Polyethylene Terephthalate, DECRON , PET

• Polyethylene Terephthalate is a resin of the polyester family that is used

to make beverage, food and other liquid containers, synthetic fibers etc .
 Chemically Speaking
Condensation Polymer

Polyethylene terephthalate is synthesized

by transesterification of two monomers:

Ethylene glycol and Dimethyl terephthalate

+
Transesterification
Transesterification is used in the synthesis of polyester, in which
diesters undergo transesterification with diols to form
macromolecules.
dimethyl terephthalate and ethylene glycol react to form polyethylene
terephthalate and methanol, which is evaporated to drive the
reaction forward.
Where can we find it?
Properties
• Clear, tough plastic with good gas and moisture barrier properties
• Crystalline with Tg 800C and melting point 295oC
• High tensile strength, high resistance to stretching
• High crease resistance ,does not form wrinkles on folding
• Used in blending with cotton, wool due to high wrinkle resistance
• Insoluble in water
Applications /uses
• Used in making soft drink bottles and other food storage bottles
• Used in making Magnetic recording tape and photographic film s
• Used in making artificial silk
• In making seat belts in car, conveyor belts
• Disposable medical garments
 Dacron in Medicine
• Cardiothoracic and Vascular grafts and implants
• Aneurysm repair
(Thoracic and Abdominal Aorta)
• Patch Angioplasty
• Vascular grafts
• Strong, flexible and treated
with collagen to keep blood
from soaking through
• Chemically inert and thus well
tolerated inside the body
• As the molecular mass increases, the polymer becomes more rigid.
• The properties of polycarbonates, their strength and remarkable transparency and their
biocompatibility make them ideal materials for medical appliances. They are used in dialysis
machines for kidney problems and, as shown here, for oxygenators which take over the work of the
heart and lungs during serious operations on them, for example in by-pass surgery.
Poly Methyl Methacrylate
What is PMMA?

PMMA - Poly Methyl Methacrylate (C₅O₂H₈)n

It is a thermoplastic and transparent plastic.

Chemically, it is a synthetic polymer of Methyl

Methacrylate

https://www.youtube.com/watch?v=Wl87nbp PMMA Pellets

BGgA
Preparation:
Transparent Property:

Density of PMMA: 1150 - 1190 kg/m³

Density of Glass: 2400 - 2800 kg/m³

It can transmit 97% of visible light ( 3-mm thickness)

Strength properties:
Tensile Strength of PMMA: 70 MPa

Tensile Strength of glass: 27 MPa to 62 MPa

PMMA breaks into large dull - edged pieces

Property:
Daylight Redirection:

PMMA can be used in laser - cut panels to redirect sunlight into a light pipe and
then spread it into a room.
 Applications: SCENARIO
• PMMA is a clear plastic acrylic material that can be used as a replacement
for glass.
• PMMA is commonly used in places where shatter-proof glass or windows
are required,
• CAR ROOF TOP MADE OF PMMA PMMA made LAMP GUARD
In Aquariums
Applications:
At residents:
Applications:
Viewing dome in airbus helicopters Exterior lights of automobiles:
Applications:
Helmet visor: Aircraft Windows Panes
Few more applications:
Acrylic paint:

Acrylic paint is nothing but

PMMA suspended in water.
Few more applications:
Acrylic glass:

Acrylic glasses are used to make

opaque objects translucent.
Recycling methods:

Pyrolysis:

Molecular breakdown of larger

molecules to smaller molecules

At extremely high temperature

In the absence of Oxygen Pyrolysis

machine
Recycling problems:

Requires a lot of energy

Contains toxic contents and potential environmental hazard

Not biodegradable
Recycling methods
Thermal depolymerization:

Heating PMMA until the monomers (C₅O₂H₈) are separate.

Polytetrafluorethylene (PTFE)
Discovery
• Accidentally discovered on April 6, 1938 by Roy Plunkett.
Teflon® Monomer

F F

C C

F F

tetrafluoroethylene
Teflon® Polymer
Toxicity
• The monomer TFE is a confirmed animal carcinogen with unknown
relevance to humans.
• The finished polymer in solid form is inert under ordinary conditions.
There is some indication that the powdered forms of PTFE may be
carcinogenic if inhaled.
BALENO with TEFLON coating : SCENARIO application
Uses
• By 1941, PTFE had been patented and had its first brand name
Teflon®.
• By 1946, the resin product was being used to produce machine parts
for military and industrial applications.
• In the 1960s it began its life in the arena of nonstick cookware.
• Today it has expanded into a whole family of polymers (resins, films,
coatings, moldable forms, powders) and sold under various brand
names, including Gore-Tex® and Zylon®.
• It is used in a wide range of industries from aerospace to
pharmaceuticals and is sold in over 40 countries worldwide.
Recycling of PTFE
• It is easy to recycle since no chemical reaction is necessary.
• Only the extruded forms are recycled (not the resin or powerdered
forms).
• The uses of recycled PTFE are restricted.
• It is typically ground up into fine powders and used as additives in
such products as inks, paints, and cosmetics.
POLYCARBONATE
• Polycarbonates (PC) are a group
of thermoplastic polymers containing carbonate groups in their chemical
structures.

• Polycarbonate, an amorphous thermoplastic,

• PC used in engineering are strong, tough material, and some grades are
optically transparent.(Lexan* 9030)

• Alternative titles :Lexan, Merlon,

 History
In 1953, polycarbonate was discovered independently by Dr. H.
Schnell of Bayer AG, Germany and by D. W. Fox of General Electric
Company, USA. It has been used in commercial applications since
the late 50's.

Polycarbonate was initially used for electrical and

electronic applications.
Structure

A polycarbonate molecule is composed by a Bisphenol A

part and a carbonate group.
Synthesis
Polycarbonate is synthesis by two ways :

1- Transesterification (or ester exchange)

2- Phosgene method
 Transesterification
Transesterification is the process of exchanging the organic group R″
of an ester with the organic group
R′ of an alcohol. often These reactions are
catalyzed by the addition of
an acid or base catalyst .

Alcohol + ester diff. alcohol + diff. ester

 +

Bisphenol-A diphenylcarbonate

NaOH

Bisphenol-A carbonate

POLYCARBONATE
Phosgene method
The main polycarbonate material is produced by the reaction
of bisphenol A (BPA) and phosgene COCl2

The overall reaction can be written as follows:

Due to their high impact resistance, PC panels are some of
the most shatter-proof glazing materials.

Uncrystallized polycarbonate has excellent transparency and

have high refractive index of about 1.584.

The relative rigidity of the chain causes high viscosity in the

liquid state.

Non- toxic in nature and easily coloured.

Highly recyclable and cost effective.

Benzene rings restrict the flexibility of the molecule.

Due to bisphenol-A it Is amorphous in nature.

Due to rigid backbone Tg =145 °C and 225-250 °C Tm =

Excellent resistance to shock even when cold.

Chemical Properties
Resistance to dilute mineral acid but poor resistance to
aromatic, alkali, chlorinated hydrocarbons.
Thermal properties
PC has good heat and cold stability.

Above the glass transition point of +140ºC however, PC

starts to soften rapidly.

PC is practically self-extinguishable i.e., resistant to fire.

Dimensional properties
Polycarbonate, as other amorphous polymer , offer limited
retraction when molded(>0.6%)
Its low absorption of humidity gives it good dimensional
stability in a humid atmosphere.
PC has good creep resistance, especially when reinforced
with fiber glass.
Electrical properties:
Polycarbonate has good insulating properties little affected
by variations in temperature
or humidity.
 Application
Electrical and Electronics components:- due to good
insulating and high dielectric strength pc is used for
making of-

Protective case for mobile phones

 LED
Switch board

Film capacitors
Electric charger
TRANSPARENT
ENCLOSURES
Construction materials
PC’s outstanding strength makes it suitable for bullet-
resistant or shatter-resistant glass application.

PC wall for sound

insulation
STRUCTURAL GLAZING
Data storage

Compact disk Digital versatile disc

Medical application
Filters housing, tube connectors, surgical staples
(due to strength, purity, transparency, ability to stand all
sterilization(steam,
gamma-rays etc..) ) which shows its bio- inertness
General application.
Due to its low weight and high impact
resistance, polycarbonate is the dominant
material for making automotive headlamp
lenses.

The cockpit canopy of jet fighter is made

from a piece of high optical quality
polycarbonate.
Passenger cars fleet of train is made of
polycarbonate.

PC’s relatively low weight in comparison

to other high strength materials and its
high ductility make it attractive to be
used in lenses and windows
What is made with PC/PBT
Automotive bumpers

Automotive side moldings

Lawn and garden tractor hoods

Hand tool housings

Irrigation components

Wire connectors
Phenolic and amino resins

1
 HISTORY
•The First phenolic resins were produced by poly condensation
of phenol with aldehyde in 1860.

•In 1860 ‘VON BAYER’ First reported the reaction between

phenol and aldehyde.

•The phenol resin condensation was used industrially in 1902 by

‘BLUMMER’ for production of novalacs.
Phenol-formaldehyde (PF) resins are formed by the
polycondensation between phenol and formaldehyde,
The polycondensation reaction can be catalyzed either by acids or bases.
The acid-catalysed reaction proceeds as follows:

127
128
In both the cases further condensation between methylol phenols and phenols occurs to
give the methylene compounds:

129
the reaction allowed to continue to
almost all the available ortho- and para-
positions of phenol molecules, a cross-
linked three-dimensional polymer will
ultimately result:

130
Low stage of polymerization, leading only to linear molecules is done in two ways:

• 1) phenol is reacted with 75% of the stoichiometric quantity of

formaldehyde using an acid catalyst .In this case, owing to an
insufficient quantity of the formaldehyde , only linear molecules are
formed :

The resin formed can be stored for any length of time without hardening , and further
cross-linking, whenever necessary, can be effected by: adding excess of formaldehyde
and then heating. These types of PF resins are called 'novlak' resins or 'BakeIite'
resins.

131
132
The resols are used for making laminates.

Paper, fabric or asbestos cloth are impregnated with the resols, and many layers
of the impregnated material are pressed together in a hydraulic press and heated
to around 150oC.

The resin cures under pressure and bonds the various layers
firmly ,to form a single sheet of a. greater thickness.

Phenolic laminates are used in electrical circuits, Resols as well as- novolak resins
are used as coating compositions also. Mixed with sand, they fined use as core
binders in foundries.

133
Urea-formaldehyde RESINS

Urea can condense with formaldehyde to form Urea- formaldehyde (UF)

resins.

The reaction proceeds in a manner similar to the formation of the phenol-

formaldehyde (PF) resin. Here also, mono- and dimethylol derivatives are
formed, which further condense with urea to give the final resin
structure.

134
135
 The hydrogen atoms of the Imide group in the linear polymer can be further replaced
with methylol groups if excess of formaldehyde is used:

 As in the case of PF resins, the final composition of the polymer depends on

the ratio of the urea to formaldehyde.

 If the linear polymers heated subsequently with more

formaldehyde a three dimensional network of the polymer will be produced
with the following structure :

136
 DENDRIMERS
1
 INTRODUCTION

 Dendrimers are repetitively branched molecules

 The name comes from Greek word “dendron”which
means “tree”.
 Also called as ‘’arborols/ cascade molecules’’.

 They are family of nanosized, highly branched three

dimensional molecules.
 Dendrimers are highly defined nanoparticles.

2
 STRUCTURE OF DENDRIMER
 Basic dendrimer components are
1) An interior core
2) Interior layers composed of repeating units radically attached to cores.
3) Exterior layer (terminal functionality) attached to interior generations.

139
3D STRUCTURE OF DENDRIMER

140
 IDEAL PROPERTIES OF
DENDRIMERS
1) Inert and non-toxic.
2) Biodegradable.
3) Non-immunogenic.
4) Able to cross barriers such as intestine, blood-tissue
barriers, cell membranes etc/
5) Able to stay in circulation for the time needed to have a clinical effect.
6) Able to target to specific structures
7) Compatible with guest molecules.
8) Must protect the drug until it reaches to the desired site of action and release
the drug.

141
 PHYSICOCHEMICAL PROPERTIES OF DENDRIMERS
 Nanoscale size.
 high solubility, miscibility and reactivity due to the presence of many
chain ends.
 These carriers have significantly lower viscosity than linear
polymers.
 Size and molecular weight can be controlled during synthesis.

142
 CHARACTRIZATION OF
DENDRITIC POLYMERS
 Spectroscopy -UV-Visible, IR, NMR.
 Microscopy - TEM , SEM.

 physical properties – DSC,DMA,TGA

 Scattering techniques.

 Electrical techniques.

 Solubility .

 Determination of Melting Point .

 Elemental Analysis (Nitrogen).

143
SYNTHESIS OF DENDRIMERS

DENDRIMER
SYNTHESIS

Convergent method
Divergent method

144
DIVERGENT METHOD
 Divergent method was introduced by Tomali.
 dendrimer grows outwards from a multifunctional core molecule.

 The core molecule reacts with monomer molecules containing one

reactive and two dormant groups giving the first generation
dendrimer.
 Then the new periphery of the molecule is activated for reactions
with more monomers.
 The process is repeated for several generations
and a dendrimer is built layer after layer.

145
DIVERGENT METHOD

146
DIVERGENT METHOD

 DISADVANTAGE
1. Can cause trailing generations.
2. Difficult to purify the product.
3. relative size differences between perfect and
imperfect dendrimers is very small.

147
 CONVERGENT METHOD
 Dendrimer grows starting from end groups and progresses
inward.
 Method makes impurity removal easier monodisperse
dendrimers are obtained.
 But stearic effects along the core limits the size.

148
TYPES OF DENDRIMERS

149
 PAMAM DENDRIMER
 PAMAM or Poly (Amido Amine) dendrimers are spheroidal or
ellipsoidal in shape.
 These are synthesized by the divergent method using ammonia or
ethylenediamine as a starting material.
 The high solubility and reactivity of these are due to presence of a
number of functional end groups and empty internal cavities.
 Commercially available as methanol solutions.

150
 PAMAM DENDRIMER
 Starburst is a trademark name for a sub-class of PAMAM
dendrimers based on a trisaminoethylene- imine core.

151
 TECTO DENDRIMER
 These are composed of a core dendrimer, which surrounded by
other dendrimers,
 each dendrimer perform a specific function.

 It used in smart therapeutic system.

 which can simultaneously diagnose the diseased state and deliver

API to the recognized diseased cell

152
 TECTO DENDRIMER
 Different compounds perform varied functions, such as diseased cell
recognition, diagnosis of disease state, drug delivery, reporting
outcomes of therapy, etc..,

153
 LIQUID CRYSTALLINE
DENDRIMERS
 These are highly-branched oligomer or polymer of dendritic
structure.

154
 CHIRAL DENDRIMERS
 Chiral dendrimers produced using different but chemically similar
branches.

155
 HYBRID DENDRIMERS
 These are hybrids (block or graft polymers) of dendritic and linear
polymers having characters of both.

156
 AMPHIPHILIC DENDRIMERS
 These are composed of two segregated sites of chain end.
 In these dendrimers one half is electron donating and the other
half is electron withdrawing.

157
 MICELLAR DENDRIMERS
 These are unimolecular micelles of water soluble hyper branched
polyphenylenes micelles.

158
APPLICATION OF DENDRIMERS

159
APPLICATION OF DENTRIMERS

MEDICAL NON MEDICAL

160
 MEDICAL APPLICATIONS
 Dendrimers in biomedicafield
 Dendrimers are analogous to protein, enzymes and
viruses .
 PAMAM dendrimers can be used to target tumour cells.
 Targeting groups can be conjugated to the host
dendrimers surface.

161
MEDICAL APPLICATIONS
 Dendrimer as magnetic resonance imaging contrast
agents
Dendrimer based metal chelates act as a magnetic
resonance imaging contrast agent.
Larger hydrophilic agents were useful for blood and
lymphatic imaging.
Smaller sized used for kidney imging

162
 MEDICAL APPLICATIONS
 Dendrimers in gene transfection
o It is used for studying mutations and regulation
processes of genes or inducing over
expression of desired proteins.

163
MEDICAL APPLICATIONS
 Dendrimers in gene transfection

164
 NON MEDICAL APPLICATIONS
 Dendrimers as catalysts/enzymes
 The combination of high surface area and high solubility makes
dendrimers useful as nanoscale catalysts.
 Dendrimershave a multifunctional surface and all catalytic sites are
always exposed towards the reaction mixture.

165
 NON MEDICAL APPLICATIONS
Dendrimers for additives, printing inks and paints
Dendritic polymers used in polyurethane paints impart surface
hardness, scratch resistance, chemical resistance, light, fastness,
weathering resistance as well as high gloss.

166
NON MEDICAL APPLICATIONS
Dendrimers as a separating agent
Dendrimer is able to form micelle structure.

which can be easily separated and recovered by ultra filtration

membrane.

167
Conducting Polymers
 OUTLINE
• Introduction
• What is conductivity?
• What makes amaterial conductive?
• How can plastic become conductive?
• Doping process.
• Factors that affect the conductivity.
• Applications.
• Conclusion.
• Bibliography search.
 Introduction
Polymers (or plastics as they are also called) are known to have
good insulating properties.

• Polymers are one of the most used materials in the modern world. Their
uses and application range from containers to clothing.
• They are used to coat metal wires to prevent electric shocks.
 What is conductivity?
Conductivity can be defined simply by Ohms Law.
V= IR
Where R is the resistance, I the current and V the voltage present in the material. The conductivity
depends on the number of charge carriers (number of electrons) in the material and their mobility.In
a metal it is assumed that all the outer electrons are free to carry charge and the impedance to flow
of charge is mainly due to the electrons "bumping" in to each other.

Insulators however have tightly bound electrons so that nearly no electron flow occurs so
they offer high resistance to charge flow. So for conductance free electrons are needed.
 What makes the material conductive?
Three simple carbon compounds are diamond, graphite and polyacetylene. They may be regarded as
three- two- and one-dimensional forms of carbon materials .

Diamond, which contains only σ bonds, is an insulator and its high

symmetry gives it isotropic properties.
Graphite and acetylene both have mobile π electrons and are, when
doped, highly anisotropic metallic
conductors.
Yet Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa have changed this view with their discovery that a
polymer, polyacetylene, can be made conductive almost like a metal.
How can plastic become conductive?

Plastics are polymers, molecules that form long chains, repeating themselves. In becoming electrically
conductive, a polymer has to imitate a metal, that is, its electrons need to be free to move and not bound to
the atoms.
Polyacetylene is the simplest possible conjugated polymer. It is obtained by polymerisation of acetylene,
shown in the figure.
 Two conditions to become conductive:
1-The first condition for this is that the polymer consists of alternating single and double bonds, called
conjugated double bonds.

In conjugation, the bonds between the carbon atoms are alternately single and double. Every bond
contains a localised “sigma” (σ) bond which forms a strong chemical bond. In addition, every double
bond also contains a less strongly localised “pi” (π) bond which is weaker.
2-The second condition is that the plastic has to be disturbed - either by removing electrons
from (oxidation), or inserting them into (reduction), the material. The process is known as
Doping.
• There are two types of doping:
1-oxidation with halogen (or p-doping).

CH n   3x
I  CH n   I 3


2
2- Reduction with alkali metal (called n-doping).

CH n   xNa  CH n  x

 xNa 
• The game offers a simple model of a doped polymer. The pieces cannot move unless there is at least
one empty "hole". In the polymer each piece is an electron that jumps to a hole vacated by another
one. This creates a movement along the molecule - an electric current.
 Doping process
• The halogen doping transforms polyacetylene to a good conductor.

Oxidation with iodine causes the electrons to be jerked out of the polymer, leaving
"holes" in the form of positive charges that can move along the chain.
• The iodine molecule attracts an electron from the polyacetylene chain and becomes I3ֿ. The
polyacetylene molecule, now positively charged, is termed a radical cation, or polaron.

• The lonely electron of the double bond, from which an electron was removed,
can move easily. As a consequence, the double bond successively moves along
the molecule.
• The positive charge, on the other hand, is fixed by electrostatic attraction to the
iodide ion, which does not move so readily.
 DOPING - FOR BETTER
MOLECULE PERFORMANCE
• Doped polyacetylene is, e.g., comparable to good conductors such as copper and silver, whereas in
its original form it is a semiconductor.

Conductivity of conductive polymers compared to those of other materials, from quartz

(insulator) to copper (conductor). Polymers may also have conductivities corresponding
to those of
semiconductors.
The conductivity of conductive polymers decreases with falling temperature in contrast
to the conductivities
of typical metals, e.g. silver, which increase with falling temperature.
 Applications
Conducting polymers have many uses. The most documented are as follows:
• Light weight batteries than lead acid batteries
• Sensors to detect pH,CO2.SO2 etc
• Ion exchange membranes
• In drug delivery systems
• Telecommunication systems
• Photovoltaic cells
• Electromagnetic shielding for computers "Smart Windows"
A second generation of conducting polymers have been developed these have industrial
uses like:
• Transistors
• Light Emitting Diodes (LEDs)
• Lasers used in flat televisions
• Solar cells
• Displays in mobile telephones and mini-format television screens
Shield for computer screen
against electromagnetic
smart" windows
"smart" windows
radiation

Solar cell
Photographic Film Light-emitting diodes
 Conclusion
• For conductance free electrons are needed.
• Conjugated polymers are semiconductor materials while doped polymers
are conductors.
• The conductivity of conductive polymers decreases with falling temperature
in contrast to the conductivities of typical metals, e.g. silver, which increase
with falling temperature.
• Today conductive plastics are being developed for many uses.
Composite Survey: Fiber
Particle-reinforced Fiber-reinforced Structural

• Fibers themselves are very strong

– Provide significant strength improvement to material
– Ex: fiber-glass
• Continuous glass filaments in a polymer matrix
• Strength due to fibers
• Polymer simply holds them in place and environmentally protects them
• Fibers are available in 3 forms
• i) Long fiber continuous fibers- arranged parallel
• ii) short chopped fibers- distributed randomly
• iii) cloth woven fibers
• FRCs are light weight durable rigid composites
• :
• Materials in which Fiber reinforcing material is Filler that are strong with low densities and
filamental polymers with high aspect ratio ,stiffness and high tensile strength.
• Examples include glass, carbon and aramid fibres
• Glass fibers- thin glass filaments easy to couple with polymer
• Types of FRCs
• 1. Glass fiber composites
• Thin filaments of Glass is used
as fibers
• Low density
• High tensile strength
• High impact resistance
• Excellent resistance to corrosion and chemicals
• Cannot be used as structural composites
• Used in storage tanks, automobile parts
• Carbon fiber reinforced composites

• Carbon fibers are reinforced

• High performance composites are obtained
• High cost
• Excellent corrosion resistance
• Low density
• Retain properties even at high temperatures
• Can be used as structural composites like wings and body of aeroplane , sports goods
and defence materials
Carbon fiber reinforced
• Cellulose fibers or polyacrylo nitrile carbon fibers are Reinforced into polyester or
epoxy resins
 Aramid fiber composites
• They are heat resistant strong synthetic fibers
• It is prepared from a combination of amine group with carboxylic group and halide group
• They are further classified into two types
• Short fiber aramid composite and long fibre aramid composite
• Short fiber aramid composite
• Give more effective reinforcement due to their high aspect ratio
• High surface area, toughness, strength, heat stability high wear resistance
 Aramid fibres
• They are Spinning liquid crystal polymers commonly called as kevlars
• High performance reinforced into polyesters or epoxides
• Stable at high temperatures upto 2000 C
• Excellent toughness and impact strength.
• But weak in compression and less resistant to acids and bases
• Long fiber aramid reinforced composites
• They are ductile and respond to compressive strength ,absorbs energy,
• Used as structural material in aircrafts, helicopterparts,
• Boing -747 and airbus 320 uses 3-5% aramid fiber composites