Polymer Notes

Consisting of: A. Polymers notes and B. Polymer Processing notes

First read A (slides bearing numbers 6 to 38) then B (rest of the slides).
Slide numbering is non-standard, so use numbers marked on slides.
Both A and B are included for exams.

Polymers notes are selectively extracted from:

http://www-old.me.gatech.edu/jonathan.colton/me4210/polyrev.pdf
Prof. J.S. Colton copyright GIT 2011

Polymer Processing notes are selectively extracted from:

http://pioneer.netserv.chula.ac.th/~sanongn1/processing.pdf

Compilation for CL409 by jb@iitb.ac.in

 Polymers

poly = many
meros = units

long-chain hydrocarbons
1,000 - 10,000 units long
104 - 106 gm/gm-mole

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 Why are polymers good?
Light
Corrosion resistant
Strong
Easily formed into complex, 3D shapes
no further machining necessary
Good filters
water / gas - permeable / impermeable
reverse osmosis
oxygenators
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 Types of polymers

Thermoplastics
can be melted and solidified repeatedly
Thermosets
react to polymerize during forming
cross-linked networks

decompose with too much heat

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 Types of polymers

Elastomers
large, recoverable, elastic deformations
soft
low glass transition temperatures
partially cross-linked networks
can be thermoset or thermoplastic

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 Bakelite
Leo Baekeland
1863 1944
first synthetic polymer
(1907)
made from phenol and
formaldehyde

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 Polyethylene (PE)

trash bags, electrical

insulation
thermoplastic

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 Polypropylene (PP)

margarine tubs, food

containers
thermoplastic

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 Polystyrene (PS)

coffee cups
(styrofoam)
clear plastic boxes
thermoplastic

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 Polyvinylchloride (PVC)

credit cards
pipes
thermoplastic

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 PVC: low-cost, widely used
PVC: has C-Cl bonds having dipole. Makes the
base polymer brittle. So it usually needs and has
a plasticizer: an oily, soft viscous liquid, usually
safe in many applications.
 PVC: widely used for pipes
1. PVC: ordinary PVC has a plasticizer.
Variations:
1. UPVC: Un-Plasticized Polyvinyl Chloride
2. CPVC: Chlorinated Polyvinyl Chloride
 PET: Polyethylene terephthalate
cPET (crystalline) aPET (amorphous)

Biaxial orientation: stretching in two directions, gives molecular orientation and strength

Plastic bottles made from PET are widely used for soft drinks.
Certain specialty bottles, such as those designated for beer containment, PET
with a polyvinyl alcohol (PVOH) layer further reduces its oxygen permeability.

Biaxially oriented PET film (often known by one of its trade names, "Mylar") can
be aluminized by evaporating a thin film of metal onto it to reduce its permeability,
and to make it reflective and opaque (MPET). These properties are useful in
many applications, including flexible food packaging and thermal insulation (such
as space blankets). Because of its high mechanical strength, PET film is often
used in tape applications, such as the carrier for magnetic tape or backing for
pressure-sensitive adhesive tapes.
 Biaxial Orientation
1. Orient molecules
in one or two
directions by
stretching
2. Gives strength
3. Even bottles may
have this with
certain
manufacturing
processes
 Polycarbonate (PC)

Lexan
thermoplastic

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Polymethylmethacrylate (PMMA)

Lucite, plexiglas
thermoplastic

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 Polytetrafluroethylene (PTFE)

Teflon
bearings
coatings
thermoplastic

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 Polyester (PET)

bottles
carpets
thermoplastic

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 Epoxy
adhesive
composite matrix
thermoset

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 Rubber vulcanization (1844)

elastomer
thermoset

Charles Goodyear
1800-1860

Vulcan
Roman god of fire
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 Bonding
Leads to all mechanical properties
Primary
covalent (C-C, C-O, C-H, C-N)
along chain, interchain
Secondary
van der Waals
hydrogen
ionic
interchain
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 Bonding
Thermoplastics
covalent along chain
secondary between chains
2D structure
Thermosets
covalent along and between
(cross link) chains
3D network

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 Bonding

Elastomers
partially cross-linked
2.5 D network

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 Crystallinity
Short range order (1,000s of Å)
Amorphous
PS, PC
bulky side groups prevent packing

Semi-crystalline
PE, PP
small or no side groups allow packing

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 Crystallinity
Tightly packed
Rigid
Large secondary bonds

amorphous
region

crystal region

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 Crystallinity
Spherulites (PP)

Platelets (PE)

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 Effects of crystallinity

Increased stiffness
matrix reinforcement
Increased solvent resistance
large secondary bonds prevent solvent
molecules from entering
Crystallinity can go from 0 to 90+%

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 Melting properties
glassy
rubbery

amorphous
mechanical
property
semi-crystalline

Tg Tm

temperature
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 Transitions
o o
Material Tg ( C) Tm ( C)

PE -120 137

PVC 87 212

PP -18, -10 176

PS 100 none
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 Behavior

Polymers do not follow a linear stress-

strain rate curve

non-Newtonian behavior

At high stress, appears to drop

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 Power-law behavior -
shear thinning

1000000

100000
n

log 10000

1000

100
0.001 0.01 0.1 1 10 100

log( )

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 Elastic die swell

Extrudate can swell 2-3 times tube

diameter at high strain rate (~1/sec)

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 Release of elastic energy

In tube, molecules are stretched out

On release, molecules re-coil to

minimum energy state

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 Polymer Processing
There are many processes for plastics. Selection of
a process depends on many factors including:
- Quantity and production rate
- Dimensional accuracy and surface finish
- Form and detail of the product
- Nature of material
- Size of final product

In general, plastics processes have three phases:

1. Heating - To soften or melt the plastic
2. Shaping / Forming - Under constraint of some kind
3. Cooling - So that it retains its shape
Thermoplastics start as regular pellets or
granules and can be remelted.

Thermosetting materials start as liquids/syrups,

often called " resins" , as powders or partially
cured products (" preforms" ) which need heat for
the shaping phase. The shaping is accompanied
by a chemical reaction, which means that the
material does not soften on reheating. The
reaction may be exothermic (giving heat out), in
which case cooling is required.
 Processes
1. Thermoforming
2. Compression and transfer molding
3. Rotational molding and sintering
4. Extrusion
5. Extrusion-based processes
6. Injection molding
7. Blow molding
8. Plastic foam molding
1.Thermoforming
-air pressure and plug
assisted forming of the
softened sheet.
-invariably automated and
faster cycle times
-only thermoplastics sheet
can be processed by this
method.
-The largest application is
for Food Packaging.
-Other industries include
Toiletries, Pharmaceuticals
and Electronics
-Food related applications
such as Meat Trays,
Microwave & Deep Freeze
Containers, Ice Cream and
Margarine Tubs, Snack
Tubs, Bakery and
Patisserie packaging,
Sandwich Packs and
Vending Drink Cups
-Manufacturing Collation
trays, Blister packaging
and Point of Sale display
trays.
2. Compression and transfer molding
-place a pre-weighed amount of
material in a matched metal
mold and closing the mold.
-heat and pressure cause the
material to liquify and flow into
the voids in the tool where it
chemically reacts and hardens
into the final shape.
-very large shapes can be
molded in compression presses.
Advantages of compression molding (compared
with injection molding)
-Low scrap arisings
-Low orientation in the moldings
-well distributed fibrous fillers
-low residual stress product
-retained mechanical and electrical properties
-low mold maintenance
-low capital and tooling costs
 4.Extrusion

-the forcing of a plastic or molten material through a

shaped die by means of pressure.
Single screw extruder

Twin screw extruder

-screw has one or two ‘flights’ spiraling along its
length.
- to outside of the flight is constant along the
length to allow the close fit in the barrel.
-core is of varying and so the spiraling channel
varies in depth.
-in general, the channel depth from feed end to die
end pressure
The zones in an extruder
1. Feed zone
-preheat polymer and convey it to the subsequent
zones.
-screw depth is constant
2. Compression zone
-channel depth
-expel air trapped between original granules
-heat transfer from the heated barrel walls is
improved ‘coz material thickness
-density change during melting is accommodated
melt sharply very short compression zone
melt gradually very long compression zone
3.Metering zone
-constant screw depth
-homogenize the melt
-supply to the die region material which is of
homogeneous quality at constant T & P
4. Die zone
-breaker plate - screen pack (perforated steel
plate)
a) sieve out extraneous material, e.g. ungeled
polymer, dirt and foreign bodies
b) allow head P to develop by providing a
resistance for the pumping action of the
metering zone
c) remove ‘turning memory’ from the melt
Flow mechanisms: Conveying
-Drag flow
-dragging along by the screw of the melt as the
result of the frictional forces
-equivalent to viscous drag between stationary and
moving plates separated by a viscous medium.
-constitute output component for the extruder.
-Pressure flow
-P gradient along the extruder (high P at the output
end, low at the feed end
-Leak flow
-finite space between screw and barrel through
which material can leak backwards.
Total flow = drag flow – pressure flow – leak flow
 The extrusion die
1. Basic flow patterns
Maintain laminar flow
2. Die entry effects
Tensile stress exceed the tensile strength of the melt
å extrudate will be of irregular shape
å called melt fracture
Pipe extrusion
 Sheet extrusion

Film thickness: 0.5 – 20 mil (1 mil = 0.001 inch)

Tubular blown film extrusion
Netting
-Garden uses, fruit packaging
-Made with annular dies but with outer die and the
central mandrel counter-rotating and close fitting
-Both parts have slots so that concentric sets of
filaments extrude
-When counter-rotation starts the filaments cross
one another to form welded junctions and a net
pattern.
Co-extrusion
-Extrusion of more than one type of
polymer at once to give a laminate
product.
-Require a separate extruder for each
polymer
-Multilayer product forming at a die
-‘tie-layers’: bond the functional layers
together
 Multi-Layer … Mono Material
For non-demanding applications, a mono material
sheet is usually specified. This is a sheet in which
there is only one material. With a more demanding
application, a multi-layer sheet is used. Multi head
extruders feed into the extrusion die with the
differing materials.
Multi layer sheeting, with a heat compliant top layer,
can used to make heat-sealed applications. PVC / PE
for Meat Trays, and CPET / APET for Meat Trays and
Ready Meals.
 6. Injection molding
Injection molding is accomplished by forcing molten
plastic under pressure into a cavity formed between two
matched metal mold halves. Once the plastic cools, the
molds are opened and the part is removed.
-Part cost - low
-Tooling cost - high
-Production Rate - high
-Can produce intricate
parts
-Large variety of polymers
gives wide range of
properties.
-Can produce a wide
range of part sizes with
different press sizes.
mold
Functions:
1. Allow rapid freezing of
polymer: isolate the
cavity and permits
withdrawal of the screw
2. Narrow and thin solid
section: be sheared off
easily after demolding
3. Increase shear rates as
melt flows through:
lower viscosity to ease
rapid and complete filling
of complex shapes
Plastic mesh
Multi-
filament
extrusion
to mesh
Net extrusion with counter-rotating dies
Plastic mesh
Film blowing
Multi-extruder setup
EVOH is ethylene vinyl alcohol , a
copolymer of ethylene and vinyl alcohol
Extrusion head or die
Extrusion head or die
Extrusion for 3D
printing
Free-form extrusion: a pen extruder