Lecture 1.1

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THERMOPLASTIC
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Synthetic Polymers
(Based on First Order Structures)
Homopolymers
Copolymers Polymer Blends and IPNs

polyA + polyB
-A-A-A-A-A-A-A-A-
Statistical
Copolymers
Alternating
Copolymers
Block
Copolymers
Graft
Copolymers
-B-B-A-B-A-A-B- -A-B-A-B-A-B-A-B- -A-A-A-A-B-B-B-B- -A-A-A-A-A-A-A-A-A-A-A-B-B-B-A-A-AB

B
B
B
B
B
Homopolymer: Formal definition: a polymer derived from one species of monomer.

Structure-based definition: a polymer whose structure can be represented by
multiple repetition of single type of repeat unit which may contain one or more
species of monomer units (structural units).
Copolymer: Formal definition: a polymer derived from more than one species of
monomer. Structure-based definition: a polymer whose molecule contains two or
more different types of repeat unit (polymers such as PET, Nylon are usually
considered as homopolymers.)
Polymer Blends and IPNs: Linked together through secondary (physical) forces.
IPNs: interpenetration polymer networks.
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Thermoplastic ( Monomer Composition)

Homopolymers
Copolymers
Block
Graft
Alternating
Statistical
Homopolymers
Consist of only one type of constitutional repeating unit (A)
AAAAAAAAAAAAAAA
Homopolymer
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Copolymers
Consist of two or more constitutional repeating units (A-B )
Several classes of copolymer are possible
Statistical copolymer (Random)
ABAABABBBAABAABB
two or more different repeating unit
are distributed randomly
Alternating copolymer
ABABABABABABABAB
are made of alternating sequences
of the different monomers
Block copolymer
AAAAAAAAABBBBBBBBB
long sequences of a monomer are
followed
by long sequences of another monomer
Graft copolymer
AAAAAAAAAAAAAAAAAA
B
B
B
B
B
B
Consist of a chain made from one type of
monomers with branches of another type
Statistical
Alternating
Block
Graft
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EXAMPLE : POLYPROPYLENE (PP)

H
Homopolymer of PP
H H
-c-c-c-c-c-c-c-c-c-c-c-c-c-c-cH
Copolymer of PP
cH3 H
cH3
cH3
cH3
cH3
cH3
cH3
H H
-c-c-c-c-c-c-c-c-c-c-c-c-c-c-cH
cH3 H
cH3
cH3
Block Copolymer of PP
PP-PP-PP-PP-PP-PE-PE-PE-PE-PE
Random Copolymer of PP
PP-PE-PP-PP-PP-PE-PE-PP-PE-PE
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Commodity and
Engineering Thermoplastics
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Commodity Thermoplastics
Commodity: Polyethylene (PE), Polystyrene
(PS), Polypropylene (PP), Polyvinyl Chloride
(PVC or vinyl) 80% of all thermoplastics!!
Also, Styrene Acrylonitrile (SAN)
Flows at elevated temperatures.
Long polymer chains
Can be remelted and recycled.
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Engineering Thermoplastics
Engineering Plastics: Polycarbonate
(PC), Acrylonitrile-butadiene-styrene
(ABS), Polyamide (Nylons, PA)
Engineered plastics account for
about 10% of all plastic usage.
Generally have higher tensile
strength and elongation than
commodity plastics
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Thermoplastis
- Can be heat-softened in order to process into a desired form.
- Can be melt-processed by a variety of methods including extrusion
and molding.
- Waste thermoplastics can be recovered and refabricated by heat
and pressure.
SOLID
heat
LIQUID/SOFT/RUBERRY cool
SOLID
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Thermoplastics never achieve 100% crystallinity

(when solidify), but instead are semi-crystalline
(partially crystalline) with both crystalline and
amorphous domains.
The crystalline phases of such polymers are
characterized by their melting temperature (Tm).
Many thermoplastics are completely amorphous
and incapable of crystallization, these amorphous
polymers (and amorphous phases of
semicrystalline polymers) are characterized by
their glass transition temperature (Tg).
Tg is the temperature at which they transform
abruptly from the glassy state (hard) to the
rubbery state (soft).
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Tg
Amorphous
Tm
Tg
Semi-Crystalline
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POLYMERS IN THE SOLID STATE
Amorphous
Semi-crystalline
Glassy
Rubbery
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Glass Transition Temperature (Tg)

The glass transition, Tg, is temp. below which a
polymer OR glass is brittle or glass-like; above that

temperature the material is more plastic.
The Tg to a first approximation is a measure of the
strength of the secondary bonds between chains in a
polymer; the stronger the secondary bonds; the
higher the glass transition temperature.
Polyethylene Tg = 0C;
Polystyrene = 97 C
PMMA (plexiglass) = 105 C.
Since room temp. is < Tg for PMMA, it is brittle at
room temp.
For rubber bands: Tg = - 73C.
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Crystallinity
Crystallization in linear polymers: achieving a very regular arrangement
of the mers
Induction of crystallinity
cooling of molten polymer
evaporation of polymer solution
annealing heating of polymer at a specific temperature
drawing stretching at a temperature above Tg
Effects:
Increased Density
Increases Stiffness (modulus)
Reduces permeability
Increases chemical resistance
Reduces toughness
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Crystalline polymers (vs amorphous polymers)

tougher, stiffer (due to stronger interactions)
higher density, higher solvent resistance (due to closely
packing morphology)
more opaque (due to light scattering by crystallites)
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Elastomers
Butyl, natural rubber (polyisoprene),
EPDM, neoprene, nitrile, etc..
Characterized by high deformation
(extremely flexible) generally
greater than 100%.
Almost all are thermosetting with
exception of TPEs
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Vulcanization
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Thermoset
Materials
Cross-linked
Natural rubber
Synthetic rubbers
Thermoplastic elastomers
Phenol-formaldehyde
Urea-formaldehydes
Amino-formaldehydes
Unsaturated polyesters
Epoxide resins
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Thermoset
Materials
Thermosets (PF, UF, MF)
Bakelite radio 1930
Picnic set (UF) 1940s
Adhesives and impregnating resins

Electrical fittings
Kettle/iron/soucepan handles
Tableware/picnicware
Parts for domestic appliences
Decorative laminates for work surfaces
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Thermoset
Materials
Thermosets (GRP, Epoxy resin)
Blondecell
Marine mouldings
Aircraft components
Racing car components
Sports equipment
Risho
Electrical insulators
Adhesives

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Copolymers Polymer Blends and IPNs

-B-B-A-B-A-A-B- -A-B-A-B-A-B-A-B- -A-A-A-A-B-B-B-B- -A-A-A-A-A-A-A-A-A-A-A-B-B-B-A-A-AB

Homopolymer: Formal definition: a polymer derived from one species of monomer.

Thermoplastic ( Monomer Composition)

EXAMPLE : POLYPROPYLENE (PP)

Thermoplastics never achieve 100% crystallinity

POLYMERS IN THE SOLID STATE

Glass Transition Temperature (Tg)

polymer OR glass is brittle or glass-like; above that

Crystalline polymers (vs amorphous polymers)

Bakelite radio 1930

Picnic set (UF) 1940s

Adhesives and impregnating resins

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