Polymers

Rubber band experiment - feeling the

temperature change when stretching and
releasing a rubber band
warmer cooler

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A Typical Polymer - Polyethylene
• Typically used in household containers, electrical
insulation, chemical containers, tubings, packaging,
prosthetic implants etc.
• Chemical formula: – CH2 – CH2 – CH2 – CH2 –…,
or (–C2H4–)n
• Polymer = many units
• Properties controlled by average molecular weight
or average n
• n = degree of polymerization
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Paraffin Boili ng Point (C)

CH4  164

C2H6  89

C3H8  42

C4H10 1

C5H12 36

C6H14 69

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 Polymer Structures
• Stereoisomers
• Linear
• Branched
• Cross-linked
• Networked

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 Stereoisomers
• Start with polyethylene (–C2H4–)n
• Replace one of the H atoms with Cl - polyvinyl
chloride
• Replace one of the H atoms with benzene ring -
polystyrene
• Location of the replacement species?

C C
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Stereoisomers
isotactic

syndiotactic

atactic
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 Linear Polymers
• Linear chains
• When the backbone consists of single-
bonded carbon atoms, the chain is flexible,
e.g., polyethylene
• When the backbone consists of  bonded
carbon atoms, the chain is much more rigid,
e.g. Kevlar

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 109.5

carbon hydrogen

Average length L of polyethylene (–

C2H4–)n given by:

L  d 2n
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linear

branched

branches

Cross-linking
typically with S
cross-linked

network

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Can We Crosslink with Oxygen?

O O

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 glucose fructose

H CH2OH
H
C C O CH2OH
OH H
H H O C
OH C C C CH2OH
C H
H OH OH C OH
OH C
OH H

– H2O

sucrose

H CH2OH

C CH2OH H
C O
OH H
O C
H H C
OH C C H CH2OH
C O
H C OH
OH C
OH H 11
 sucralose

Cl CH2OH

C CH2Cl H
C O
H H O
H H C
OH C C C CH2Cl
C H
H O OH
C C
OH
OH H

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 Effects of Branching
• Interferes with sliding ---> stronger
• Difficult to pack molecules tight --> lower
density and lower degree of crystallinity

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 Effects of Cross-linking and
Networking
• More rigid
• Less ductile (more brittle)
• Network polymers are so rigid that they are
formed and set into a fixed shape defined by
the mold. They cannot be melted and
molded into a different shape (thermosets) -
--> cannot be recycled easily (cf.
polyethylene - thermoplastics)

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 Common Applications
• Polyvinyl chloride (PVC): electrical insulation
pipes, siding, upholstery, floor covering
• Polyacrylonitrile: fibers for clothing and blankets
• Teflon (polytetrafluoroethylene, PTFE): nonstick
coatings, seals, chemical containers and pipes,
cable insulation
• Polymethylmethacrylate (PMMA): plexiglass
windshields for aircraft, outside signs, safety
shields and goggles, dental materials

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 Common Applications
• Bakelite (phenol-formaldehyde): electrical
connectors and switches, motor and
telephone housing, billiard balls
• Polycarbonate: safety shields, helmets,
prescirption lenses, aircraft components,
boat propellers

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Common Polymers

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Common Polymers

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Common Polymers

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 Copolymers (Solid Solutions)
• Copolymer = solid solution of two mer units
• Properties do not always obey the rule of
mixtures
• Mer units can be arranged in 4 ways
– Random
– Alternating
– Block
– Graft
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alternating Copolymers

random

block

graft

A
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B
 Copolymers
• For example, modern automobile tires are made
of random copolymers of
butadiene –CH2–CH=CH–CH2– and
styrene –CH2–C(C6H5)H–
or butadiene and acrylonitrile –CH2–CHN–.
• Addition of styrene or acrylonitrile inhibits
sliding of chains relative to one another, thus
improving rigidity of the rubber.

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 Crystallinity
• Most polymers are amorphous or semi-crystalline
• Reasons
– Long and bulky (low mobility)
– Difficult to pack complex molecules into
regular shapes
• Generally, polymers with bulky side groups,
network polymers, atactic polymers or random
copolymers are difficult to crystallize

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 Mechanical Properties

Aramid (Kevlar-49): density = 1.3 gm/cm3; elastic

modulus = 130 GPa
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 Mechanical Properties:
temperature effects
4C (brittle)
PMMA
40C (plastic)
stress

60C (elastomeric)

strain

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Due to thermally activated motion of molecules
Semicrystalline Polymer Structure

Crystalline
phase

Amorphous
phase

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 Deformation of
Semicrystalline Polymers
Uncoiling of tie
chains in amorphous
phase

stress

Re-orientation of
the crystalline
phase

Break-up of the
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crystalline phase
 Strengthening Strategies
• Increasing crystallinity
• Attaching side groups to interfere with
sliding
• Attaching polar atoms
• Introducing electronegative atoms into the
main chain
• Cross-linking
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 Glass Transition Temperature
• Below a certain temperature Tg, there is
insufficient thermal energy to activate the
motion of large chain segments
• Polymers below the glass transition
temperature Tg are rigid and brittle
• Above Tg, they become rubbery, are easily
deformable, and have improved fracture
toughness

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 Glass Transition Temperature
• Typically, Tg is about 0.5 – 0.8 times the melting
point Tm
• Generally, any polymer modification or processing
that strengthens inter- or intra-molecular interaction
raises Tg and Tm
• Take a typical amorphous polymer
– Below Tg: glass (supercooled liquid)
– Above Tm: viscous liquid
– Between Tg and Tm: rubbery solid (viscoelasticity)

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 Selected Electro-Optical
Applications
• Lenses and windows
• Liquid crystal displays
• Nonlinear optical materials
• Polymer electrolytes

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 Lenses and Windows
• Polycarbonates
• Refractive index similar to glass
• Tougher and lighter
• Prescription lenses, aircraft windows,
laminates for car windshields

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 General Structure of Liquid
Crystals

Example: CH3 – CH2 – CH2 – CH2 – CH2 – – CN

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 Electro-Optical Properties
• Because of the large electronegativity of N,
the molecule is charged negatively on the N
end --> polar molecule
• Intermolecular attraction --> some long-
range order even when the temperature is a
few degrees above melting point --->
thermotropic liquid crystals
• Apply electric field --> align molecules -->
affect light scattering ---> basic LC display
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 Electro-Optical Properties
• Because the molecule is not symmetric, this
alignment also endows the molecule with
nonlinear optical properties, e.g., sum
frequency generation and frequency
doubling
• Applications in optical communications

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 Polymer Electrolytes
• In Li-ion batteries and solid-electrolyte fuel cells,
need lightweight and robust electrolytes for efficient
ion transport
• Polyethylene oxide and its variants work well as
solid electrolytes: : (–O– CH2–CH2–)n
• Reasons
– Because oxygen is more electronegative than carbon, it is
charged negatively and becomes the preferred adsorption
site for positive ions, e.g. Li+
– Distance between oxygen atoms short enough for
efficient ion transport
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 Polymers and Proteins
The main linkage between mer units in nylon
and Kevlar is
O

–C–N–

This is the same linkage (peptide bond) in a

protein molecule between units (amino acids)

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 Lessons learned from chapter 6
• Polymers are made of repeating units
• Properties depend not only on individual mers, but
also on the structure (stereoisomers, linear,
branched, network, and cross-linked)
• Copolymers - analogous to solid solutions in alloys
• Mechanical properties and strengthening strategies
• Concept of glass transition temperature
• Electro-optical applications
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