ME 382 Lecture 33

POLYMERS
• Polymers consist of long-chain C-C molecules (up to 105 atoms / chain)

• Atoms within a long-chain molecule are covalently bonded

• Chains consist of a repeated representative unit (“mer”)

• Degree of polymerization = number of repeated units (⇒ molecular weight)

• Properties of polymers depend on molecular weight & bonding between chains

• Commercial polymers have a range of molecular weights

∴ No unique set of properties

• Accurate design data for design must be measured or obtained from supplier
Unlike metals, no standards or well-defined properties that can be looked up
Databook values are approximate (even for modulus)

• General properties:
(i) ρ ≈ 1000 kg/m3; E ≈ 1-8 GPa (down to 1 MPa for an elastomer)
(ii) Design often stiffness limited (because of low modulus)
(iii) Properties sensitive to temperature (around room temperature) and time
(iv) Polymers are very sensitive to u/v radiation and O3 (become stiff & brittle)

• Three types of polymers determined by nature of bonding between chains

(i) Covalent cross links
(ii) Secondary bonding (Hydrogen or van der Waals)
(iii) Chain entanglements

Thermoplastics
• No covalent cross-links between chains

• Below glass transition temperature, Tg, there is secondary bonding between chains
Hydrogen or van der Waals

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• Above Tg secondary bonds melt leaving molecules free to slide over each other
Chain entanglements responsible for activation energy
Viscosity drops with increased temperature

• Thermoplastics can be melted and reformed

∴ Possible to recycle thermoplastics (if separated and not contaminated)

• Thermoplastics are often made by an addition reaction

• Molecules add to existing chains (at ends or branches) ⇒ no joining of chains

• Thermoplastics can be linear (such as High-Density Polyethylene (H.D.P.E.) “2”)

• Or they can be branched (such as Low-Density Polyethylene (L.D.P.E.) “4”)

Three types of packing

(i) Aligned fibers - draw fibers from the melt
Very stiff because of covalent bonding

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(ii) Crystalline - Chains fold

Can also form plates radiating

out of a sphere “spherulite”

(iii) Amorphous - random tangle of chains

Amorphous polymers are less dense than crystalline polymers
Have a lower modulus, because lower density of bonds between chains
More likely if branching, large side groups, or irregular side groups
(atactic polymers) - because ordered packing is more difficult
H.D.P.E. (milk bottles) is denser and stiffer than L.D.P.E. (plastic bags)

• Common thermoplastics (with recycling codes):

Polyethylene terephthalate (PET “1”) (CO-C6H4-CO-CH2-CH2-O)n
Polyethylene (HDPE-“2”, LDPE-“4”) (CH2)n
Polyvinylchloride (PVC - “3”) (CH2-CHCl)n
Polypropylene (“5”) (CH2-CHCH3)n
Polystyrene (“6”) (CH2-CHC6H5)n
Polytetrafluoroethylene (PTFE “Teflon”) (CF2)n
Plexiglass (PMMA) (CH2-C(CH3)(COOCH3))n

Thermosets
• Contain covalent cross-links to form a network of covalent bonds

• Thermosets cannot be melted

Covalent bonds in cross-links and chains melt at the same temperature
∴ Decomposition occurs rather than melting

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∴ Thermosets must be cast into final shape (with some machining possible)
Thermosets cannot be recycled

• Modulus of thermosets somewhat higher than modulus of thermoplastics

Below Tg: Secondary bonding & covalent cross-links between chains
Above Tg: Modulus drops as secondary bonding melts, but covalent
cross-links remain between chains

• Thermosets are formed by a condensation reaction

Two liquid components “resin” and “hardener” react ⇒ cross-linked solid

Cross linking if reagent has more than one (-OH) functional units

• Thermosets are generally amorphous with a random network structure

• Common thermosets:
Epoxy: (O-C6H4-C(CH3)2- C6H4-O-CH2-CH(OH)-CH2)n
Polyester: (CO-(CH2)m-CO-O-C(CH2OH)2)n

Elastomers
• Almost-linear polymers with occasional cross-links

• At room temperature, secondary bonding has melted

• Covalent cross-links are too few to affect the modulus

Applied stress ⇒ straightening out of molecular chains ⇒ large deformations
Light covalent cross-linking provide “memory” of original configuration
∴ Elastomer returns to original shape upon unloading

• Common elastomers:
Polybutadiene (synthetic rubber) (CH2-CH-CH-CH2)n
Polychloroprene (“neoprene”) (CH2-CH-CCl-CH2)n

Natural polymers: Proteins, cellulose, natural rubber, wool, silk, ....

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Modulus of lightly-cross-linked polymers

• Chains are stiff along their length, but carbon atoms can rotate relatively freely

• Thermal energy results in random rotations of each carbon atom along polymer chain

3-D random walk r = ! 2n/3

• Two effects:
(i) Chains get tangled
∴ Some structural integrity even if no bonding between chains
(ii) In absence of stress - chains relax to maximum entropy configuration

1 #% d 2G &
• Remember: G = H- TS & E=
! $ d" 2 '
1 #% d 2 H & T #% d 2S &
∴ E= (
! $ d" 2 ' ! $ d" 2 '
For crystalline materials, entropy can be ignored
For polymers, both energy effects and entropic effects can be important

• Application of stress causes chain to straighten out (reduces entropy)

dQ = TdS
Note that {
heat in

∴ If entropy decreases (dS < 0)

⇒ dQ < 0 (heat out)
∴ Stretch a rubber band and it gets hot
Relax it, and it gets cold
• After stress is removed, chains return to maximum entropy position

• Covalent bonds in the polymer chain are not stretched, and play no role in modulus

• Any bonding between chains also provides an energetic contribution to modulus

Below Tg secondary bonding & any covalent cross-linking contributes to modulus
Above Tg covalent cross-linking contributes to modulus
Chain motion is also impeded by tangles and side groups

• Extensive bonding between chains restricts motion and reduces entropic effects

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