Chapter-9

Polymeric Materials

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 What is a polymer?
• The word is from Greek roots “poly” meaning many and
“meros” meaning parts .
• Many scientists prefer the word “macromolecule”.
• If one discounts the end uses, the differences between all
polymers, whether natural or synthetic, are determined by
the intermolecular and intramolecular forces that exist
between the molecules within the individual molecules and
by the functional groups they contain.

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 Polymers
• If we disregard metals and inorganic compounds, we observe
that practically everything else in the world is polymeric.
• This includes the protein, nucleic acid and sugars that make
up all cells and their extracellular matrix, the fibers in our
clothing, the food that we eat, the elastomers in our tires, the
paint, plastic wall and floor coverings, our foam insulation,
dishes, furniture of our homes, etc.

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 How are they used?

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 Polymeric Biomaterials are used in a
Broad Range of Products

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 MEDICAL PLASTIC MARKET FORECAST TO CROSS 2.6
BILLION POUNDS as Worldwide
• Plastic usage in the healthcare field encompasses several
distinct markets-including disposable or single use
biomaterials.
• Predominant are applications for medical devices and
related products and packaging.

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 Medical Plastics Market
• Non-disposables comprise slightly over 50% of total volume.
• Commodity thermoplastics currently dominate the market
with a little under 50% of total volume, having a consumption
level of 956 million pounds in 1999.
• Almost 80% of polymers used in the medical industry are
represented by PVC, polypropylene and polystyrene.

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 Medical Plastics Market
• Major nondisposable markets include testing/diagnostic
equipment, surgical instruments and related equipment,
prostheses/implants, dental/ophthalmic devices;
• Disposable products include syringes, kits, labware, tubing,
blood bags, utensils, gloves, trays, catheters, thermometers,
etc.

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 Polymer Science and Processing
Technology
Successful product design requires a knowledge of:
– the requirements of the final product;
– the behavior of polymeric materials;
– commercial polymer processing technology; and
– relevant cost and market factors.

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 Polymer Science and Processing
Technology
• At the heart of polymer
science and technology is
molecular structure.
• It dictates not only final
product properties, but the
type of polymer synthesis
and the potential
processing methods.

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 Molecular Arrangement of
Polymers
• Most polymers are large linear
macro-molecules.
• This chain is called the backbone.
• Normally, some of these atoms in
the chain will have small chains of
atoms attached to them. These
small chains are called pendant
groups.
• Pendant chains normally have
just a few atoms, but the
backbone chain usually has
hundreds of thousands of atoms.

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 The Structure of Polymers
• Below is a diagram of polyethylene, the simplest polymer
structure

• There are polymers that contain only carbon and hydrogen.

• These are referred to as hydrocarbons-exs. Polypropylene,
polybutylene, polystyrene, and polymethylpentene

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 Polymers have a Repeating
Structure
• We like to think that the atoms
that make up the backbone of
a polymer chain come in a
regular order, and this order
repeats itself all along the
length of the polymer chain.
• For example, in polypropylene,
the backbone chain is made up
of just two carbon atoms
repeated over and over again.

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 Material Science Logic

Performance/Application

Structure

Synthesis Properties
+processing •Physical
•Biological

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 Basics of Polymer Structure
• What distinguishes polymers from other organic compounds is molecular
weight and dimension?

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 Chemical Structure of Some
Common Polymers

Poly(methylmethacrylate) Poly(vinylacetate) “PAVc”

“PMMA”

Poly(acrylate) “PAA”
Poly(vinylchloride) “PVC”
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 Chemical Structure of Some
Common Polymers

Poly(vinylidene chloride)“PAVc” Poly(ethylene oxide)“PEO”

Poly(hexamethylene adipamide)
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Poly(caprolactam) “Nylon” 17
“Nylon 6,6”
 Chemical Structure of Some
Common Polymers

Poly(ethylene terephthalate)“PET” Poly(carbonate)

Poly(dimethyl siloxane) Poly(methyl styrene)

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 Classification- Chain Architecture:
Linear Structures
• Many thermoplastic
polymers are built so their
molecules consist of many
thousands of atoms
arranged into long linear
chains. But they don't have
to be long straight chains.

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 Polymer Structure
• Also we know that each such carbon to carbon
bond allows full rotation in both molecules, so
that in reality the chains are seldom extended
to their full contour length but are present in
many different shapes, or conformations.

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 HDPE vs LDPE

LDPE
HDPE

The branching increases the volume and thus reduces the density of the
polymer.

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 Star Polymers
• Sometimes the ends of
several polymer chains
are joined together at a
common center.
• Polymers like this are
called star polymers.
• They're often used as
additives or as coating
materials.

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 Cross-linked Polymers
• Sometimes, both ends of the
branch chains are attached to the
backbone chains of separate
polymer molecules.
• If enough branch chains are
attached to two polymer
molecules, it can happen that all
of the polymer backbone chains
in a sample will be attached to
each other in a giant 3-D
network.
• This is what happens in certain
hydrogels, polyelectrolytes,
rubber, silicone and certain
polyurethanes.

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 Types of Polymers
• Thermosets
• Thermoplastics Classification based on Processing
• Elastomers – Classification based on mechanical properties
• Hydrogels- Classification based on chemical properties
• Polyelectrolytes-Classification based on chemical
properties
• Natural-Classification based on origin
• Biodegradable-Classification based on bio stability

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 Thermosets

General properties: more durable, harder, tough, light.

Typical uses: automobile parts, construction materials.

Examples:

Unsaturated Polyesters: lacquers, varnishes, boat hulls, furniture

Epoxies and Resins: glues, coating of electrical circuits,

composites: fiberglass in helicopter blades, boats, …
 Plastic types: Elastomers

General properties: these are thermosets, and have rubber-like properties.

Typical uses: medical masks, gloves, rubber-substitutes

Examples:

Polyurethanes:mattress, cushion, insulation, toys

Silicones: surgical gloves, oxygen masks in medical applications

joint seals
Plastic types: Thermoplastics

General properties: low melting point, softer, flexible.

Typical uses: bottles, food wrappers, toys, …

Examples:

Polyethylene: packaging, electrical insulation, milk and water bottles, packaging

film
Polypropylene: carpet fibers, automotive bumpers, microwave containers,
prosthetics
Polyvinyl chloride (PVC): electrical cables cover, credit cards, car instrument
panels
Polystyrene: disposable spoons, forks, Styrofoam™
Acrylics (PMMA: polymethyl methacrylate): paints, fake fur, plexiglass
 Plastic Products

• Plastics can be shaped into a wide variety of products:

– Molded parts
– Extruded sections
– Films
– Sheets
– Insulation coatings on electrical wires
– Fibers for textiles

More Plastic Products

• In addition, plastics are often the principal ingredient in other

materials, such as
– Paints and varnishes
– Adhesives
– Various polymer matrix composites
• Many plastic shaping processes can be adapted to produce
items made of rubbers and polymer matrix composites
 Trends in Polymer Processing

• Applications of plastics have increased at a much faster rate than

either metals or ceramics during the last 50 years
– Many parts previously made of metals are now being made of
plastics
– Plastic containers have been largely substituted for glass bottles
and jars
• Total volume of polymers (plastics and rubbers) now exceeds that of
metals

• Almost unlimited variety of part geometries

• Plastic molding is a net shape process
– Further shaping is not needed
• Less energy is required than for metals due to much lower
processing temperatures
– Handling of product is simplified during production because
of lower temperatures
• Painting or plating is usually not required
Thermoplastics

These plastics are made up of lines of long chain molecules (below)

with very few cross linkages. This allows them to soften when
heated so that they can be bent into different shapes, and to
become stiff and solid again when cooled. This process can be
repeated many times.

Thermoplastics
Chemical structure remains
unchanged during heating and
shaping

More important commercially,

comprising more than 70% of total
plastics tonnage
 Plastic types: Thermoplastics

General properties: low melting point, softer, flexible.

Typical uses: bottles, food wrappers, toys, …

Examples:

Polyethylene: packaging, electrical insulation, milk and water bottles, packaging film
Polypropylene: carpet fibers, automotive bumpers, microwave containers, prosthetics
Polyvinyl chloride (PVC): electrical cables cover, credit cards, car instrument panels
Polystyrene: disposable spoons, forks, Styrofoam™
Acrylics (PMMA: polymethyl methacrylate): paints, fake fur, plexiglass
Polyamide (nylon): textiles and fabrics, gears, bushing and washers, bearings
PET (polyethylene terephthalate): bottles for acidic foods like juices, food trays
PTFE (polytetrafluoroethylene): non-stick coating, Gore-Tex™ (raincoats), dental floss
Thermosetting Plastics

These plastics are made up of molecules that are heavily

cross-linked (below). This results in a rigid molecular structure.
Although they soften when heated the first time, and can
therefore be shaped, they then become permanently stiff and
solid, and cannot be reshaped.

Thermosets
Undergo a curing process during
heating and shaping, causing a
permanent change (cross‑linking)
in molecular structure

Once cured, they cannot be remelted

 Plastic types: Thermo sets

General properties: more durable, harder, tough, light.

Typical uses: automobile parts, construction materials.

Examples:

Unsaturated Polyesters: lacquers, varnishes, boat hulls, furniture

Epoxies and Resins: glues, coating of electrical circuits,

composites: fiberglass in helicopter blades, boats, …
 SHAPING PROCESSES FOR PLASTICS

1. Compression Moulding
2. Transfer Moulding
3. Extrusion Moulding
4. Injection Moulding
5. Blow Moulding
6. Thermoforming
7. Calendering
8. lenPolymer Foam Processing and Forming
9. Product Design Considerations
Plastics Processing: Compression Molding compression molding
Plastic Processing : Compression Molding

Figure : Compression molding for thermosetting plastics:

(1) charge is loaded,
(2) and (3) charge is compressed and cured, and
(4) part is ejected and removed.
 Plastic Processing : Compression Molding

• Molding materials:
– Phenolics, melamine,
urea‑formaldehyde, epoxies,
urethanes, and elastomers
• Typical compression-molded products:
– Electric plugs, sockets, and housings;
pot handles, and dinnerware plates

• Simpler than injection molds

• No sprue and runner system in a compression mold
• Process itself generally limited to simpler part geometries due to lower
flow capabilities of TS materials
• Mold must be heated, usually by electric resistance, steam, or hot oil
circulation
 Plastics Processing: Compression Molding
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Plastics Processing: Compression Molding
 Transfer Molding
TS charge is loaded into a chamber immediately ahead of mold cavity,
where it is heated; pressure is then applied to force soft polymer to flow
into heated mold where it cures

• Two variants:
– Pot transfer molding - charge is injected from a "pot" through a
vertical sprue channel into cavity

– Plunger transfer molding – plunger injects charge from a heated

well through channels into cavity.
Transfer Molding

Pot Transfer Moulding

 Pot Transfer Molding

Figure : (a) Pot transfer molding: (1) charge is loaded into

pot, (2) softened polymer is pressed into mold cavity and
cured, and (3) part is ejected.
 Plunger Transfer Molding

Figure : (b) plunger transfer molding: (1) charge is

loaded into pot, (2) softened polymer is pressed into
mold cavity and cured, and (3) part is ejected.
Screw conveyor
Thermoplastic granules (right) are fed from a hopper
by a rotating screw through a heated cylinder.

The tapered shape of the screw (right) compacts the

plastic as it becomes plasticized. This part of the
process is similar to the heating and compacting
stages in the injection moulding process. The
difference being that the softened material is allowed
to flow out through a die in a continuous stream
( Extrusion moulding ) rather than be pumped
intermittently in measured amounts into a mould.
( Injection moulding )

The die (right) which is fitted to the end of the

extruder barrel determines the cross-section of the
 Extruder

Figure : Components and features of a (single‑screw) extruder for plastics

Compression process in which material is forced to flow through a die

orifice to provide long continuous product whose cross‑sectional shape
is determined by the shape of the orifice of a die

• Widely used for thermoplastics and elastomers to mass produce items

such as tubing, pipes, hose, structural shapes, sheet and film,
continuous filaments, and coated electrical wire

• Carried out as a continuous process; extrudate is then cut into desired

lengths
 Extruder Screw

• Divided into sections to serve several functions:

– Feed section - feedstock is moved from hopper and

preheated
– Compression section - polymer is transformed into fluid, air
mixed with pellets is extracted from melt, and material is
compressed
– Metering section - melt is homogenized and sufficient
pressure developed to pump it through die opening
 Die End of Extruder : Extrusion Die for Solid Cross Section

Figure : (a) Side view cross‑section of an extrusion die for solid regular shapes, such as
round stock; (b) front view of die, with profile of extrudate .
• Progress of polymer melt through barrel leads ultimately to the die zone
• Before reaching die, the melt passes through a screen pack - series of wire
meshes supported by a stiff plate containing small axial holes
• Functions of screen pack:
– Filter out contaminants and hard lumps
– Build pressure in metering section
– Straighten flow of polymer melt and remove its "memory" of circular
motion from screw
 Extrusion Die for Coating Wire

Figure : Side view cross‑section of die for coating of electrical wire by extrusion.

• Polymer melt is applied to bare wire as it is pulled at high speed through a die
– A slight vacuum is drawn between wire and polymer to promote adhesion
of coating
• Wire provides rigidity during cooling - usually aided by passing coated wire
through a water trough
• Product is wound onto large spools at speeds up to 50 m/s (10,000 ft/min)
Plastics Processing: Extrusion

open cross-sections (channels) closed cross-sections (tubes, pipes) pellets

Plastics Processing: Extrusion
Plastics Processing: Extrusion
Extrusion
This process can be compared to squeezing toothpaste from a tube. It is a continuous
process used to produce both solid and hollow products that have a constant
cross-section. E.g. window frames, hose pipe, curtain track, garden trellis.

Process
The photo below shows a typical thermoplastic extruder.
Plastics Processing: Extrusion
 Injection Molding

Polymer is heated to a highly plastic state and forced to flow

under high pressure into a mold cavity where it solidifies and
the molding is then removed from cavity

• Produces discrete components almost always to net shape

• Typical cycle time 10 to 30 sec, but cycles of one minute
or more are not uncommon
• Mold may contain multiple cavities, so multiple moldings are
produced each cycle
Injection Molding Machine
Two principal components:

Injection unit
Melts and delivers polymer melt
Operates much like an extruder

Clamping unit
Opens and closes mold each injection cycle
Plastics Processing: Injection Molding
 Plastics Processing : Injection Molding Machine

Figure : Diagram of an injection molding machine, reciprocating screw

type (some mechanical details are simplified).
Plastics Processing: Injection Molding

(1) mold is closed (2) melt is injected into cavity.

(3) screw is retracted. (4) mold opens and part is ejected.

Cycle of operation for injection molding
 Process & machine schematics

Schematic of thermoplastic Injection molding machine

New developments- Gas assisted
injection molding
 Blow Molding
Molding process in which air pressure is used to inflate soft plastic
into a mold cavity
• Important for making one‑piece hollow plastic parts with thin
walls, such as bottles
• Because these items are used for consumer beverages in
mass markets, production is typically organized for very high
quantities

Blow Molding Process

• Accomplished in two steps:
1. Fabrication of a starting tube, called a parison
2. Inflation of the tube to desired final shape
• Forming the parison is accomplished by either

– Extrusion or
– Injection molding
 Extrusion Blow Molding

Figure : Extrusion blow molding: (1) extrusion of parison; (2) parison

is pinched at the top and sealed at the bottom around a metal blow
pin as the two halves of the mold come together; (3) the tube is
inflated so that it takes the shape of the mold cavity; and (4) mold is
opened to remove the solidified part.
 Extrusion Blow Molding

Extrusion Blow Molding involves manufacture of parison by conventional extrusion

method using a die similar to that used for extrusion pipes.
Extrusion Blow Molding is commonly used for mass production of plastic bottles.

The production cycle consists of the following steps:

1.The parison is extruded vertically in downward direction between two mold

halves.
2. 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.
3.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.
4.The mold cools down, its halves open, and the final part is removed.
1 3

2 4
5
 Injection Blow Molding

Figure : Injection blow molding: (1) parison is injected

molded around a blowing rod; (2) injection mold is opened
and parison is transferred to a blow mold; (3) soft polymer
is inflated to conform to the blow mold; and (4) blow mold is
opened and blown product is removed.
 Injection Blow Molding

1. 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.

2.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.

3. 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.

4. However production rate of Injection Blow Molding

method is lower than that of Extrusion Blow Molding.
The photo (below) shows fluid containers used in hospitals, ready to be
trimmed. A wide variety of colours can be achieved by adding a colouring
agent to the mix of thermoplastic granules (about 1% by volume).
 Calendering Feedstock is passed through a series of rolls to
reduce thickness to desired gage

• Expensive equipment, high production rates

• Process is noted for good surface finish and
high gage accuracy
• Typical materials: rubber or rubbery
thermoplastics such as plasticized PVC
• Products: PVC floor covering, shower
curtains, vinyl table cloths, pool liners, and
inflatable boats and toys

Calendering is a process where a large amount of molten plastic is placed between rollers and
rolled to turn it into sheets. The rollers are hot and keep the plastic in its semi - molten state
allowing it to be rolled thinner and thinner as it passes through rollers which are closer and
closer together. When it is at the required thickness it is rolled through cold rollers to enable it
to go hard and is then wound into rolls.

Figure : A typical roll configuration in calendering

Embossing
 Welding of Plastics

Plastics welding is the process of joining two pieces

of Thermoplastics at heated state and under a
pressure as a result of cross linking of their polymer
molecules. The work pieces are fused together with or
without filler material. The joint forms when the parts
are cooled below the Glass Transition Temperature
(for amorphous polymers) or below the melting
temperature (for crystalline polymers).

Thermo sets (thermosetting resins) in cured condition

cannot be welded, since cross-linking of their
molecules has completed.

Plastics welding processes:

Hot Gas Welding

Hot Plate Welding
Ultrasonic Welding
Spin Welding
Vibration Welding
Welding of Plastics : Hot gas Welding
Welding of Plastics : Hot Plate Welding
Welding of Plastics: Ultrasonic Welding
Welding of Plastics : Friction ( Spin ) Welding
Welding of Plastics : Vibration Welding