MM 152: Polymeric Materials

Poly (many)-mer (unit) Large molecules (macromolecules) made of several repeat units

Ethylene
molecule
(monomer)

Addition of two
ethylene monomers

Polymerization of ethylene
monomers gives polyethylene (PE)

Representation of a PE molecule
Perspective view of a PE molecule

Polytetrafluoroethylene (PTFE
also known as Teflon)

Poly(vinylchloride) (PVC)

Poly(propylene) (PP)

Common polymers

Some examples of bio-polymers

http://www2.estrellamountain.edu/faculty/farabee/biobk/
biobookglossg.html

http://www.ucmp.berkeley.edu/glossary/gloss3/dna.html

http://www.goldiesroom.org/Note%20Packets/04%20Biochemistry/02
%20Biochemistry--Lesson%202.htm

J van Mameren et al, Proc. Natl. Acad. Sci.,2009

Some examples of synthetic polymers

Six major commodity polymers: PE, PP, PVC, PET, PS, PC (98% of the plastics in use)
Long molecules in a polymer product make it stable against degradation
PE degradation by chain scission (random breaking of bonds) at 450C
Molecular weight upto 5 million
C-C bond energy 340 KJ/mol (3.5 eV/atom)
Large amounts of plastics
suspended beneath ocean
surface
700,000 15,000,000 sq km
80% from land based sources
3.34 pieces/ 5.1 mg per sq m

Biodegradable polymers
Poly(lactic) acid: derived from renewable sources such as corn
starch and sugarcane
Companies that make PLA: Natureworks (USA), Toyota (Japan),
PURAC (Netherlands)

Natureworks Ingeo biopolymer can be made

into both woven and non-woven products

PLA does not perform well at high temperatures

Polymer molecular weight

What is the weight of a polymer molecule? Monomer weight Number of monomers
How many monomers are present in a polymer molecule?

Mn

xi M i

Weight fraction

Number-average
molecular weight

Number fraction

Most of the synthetic polymerization processes do not yield polymer molecules of the
same length
The molecular weight of different polymer molecules in the same sample may be different
Define molecular weight averages for polymers instead of absolute molecular weights

Molecular weight (103 g/mol)

Degree of polymerization

DP

Mn
m

Weight-average
molecular weight

Mw

wi M i

Molecular structure

Linear

Branched

Single polymer
molecule in solution

Cross-linked

Network

Polymer crystallinity
Life inside a spherulite

Chain-folded structure for a plateshaped polymer crystallite

Polyethylene unit cell

Polyethylene single crystal

TEM showing the spherulitic

structure of polyethylene

Mechanical properties

Plastic polymer

Highly elastic
polymer

Strain
Stress (MPa)

Stress (MPa)

Brittle polymer

Influence of temperature on
mechanical behaviour of PMMA
ductile-to-brittle transition

Strain

Mechanical properties

Mechanical Deformation of semi-crystalline polymers

Stages in elastic deformation

Increase in lamellar
thickness (reversible)
Stage 1

Before
deformation

Stage 2

Elongation of
amorphous tie chains

Mechanical Deformation of semi-crystalline polymers

Stages in plastic deformation

Stage 5

Stage 4

Stage 3

State at the end of

elastic deformation

Tilting of lamellar
chain folds

Separation of
crystalline block
segments

Orientation of block
segments and tie
chains with the tensile
axis

Percent of crystallinity

Effect of degree of crystallinity

Brittle
waxes

Hard plastics
Tough
waxes

Soft
waxes

Soft plastics

Grease,
liquids

Molecular weight
Increase in crsytallinity leads to increase in tensile modulus, e.g., for PE modulus
increases almost 10 times as percentage crystallinity increases from 0.3 to 0.6.
Increase in molecular weight generally leads to an increase in tensile strength

Rubber Elasticity

Gutta percha (trans1, 4-polyisoprene)

tree

Gutta percha points

for root canal
treatment

Natural rubber (cis-1,

4-polyisoprene) latex
being collected from
rubber tree

Rubber Elasticity

Gutta percha points for root

canal treatment

Rubber Elasticity

Stress-strain curves for an alloy steel (crystalline material) and natural rubber
(elastomer/ rubbery material)

Molecular Structure of a Rubber

Ordered lattice
arrangement in crystalline
materials

Disordered network of
polymer chains in a
rubber

Stretching Polymer Chains

Stretching a single polymer chain

from its initial dis-ordered
arrangement. Stretching reduces
the entropy of the polymer

Similarly, polymer segments

between network points in a
rubber exist in a disordered,
coiled state prior to extension.
The degree of disorder
decreases when a tensile stress
is applied.

Affine Deformation

Stretching of a rubber
network
i

li
l0

Extension ratio in the i-direction

Affine Deformation

NkT
V
E

1
1

2
1

1
1

2
1