POLYMER STRUCTURES,

APPLICATIONS, & PROCESSING

• Naturally occurring polymers:

– Wood, rubber (Hevea brasiliensis, or Ficus
elastica), cotton, wool, leather, silk, starches, etc
etc
– Biopolymers RNA, DNA etc etc
• All livings things are made out of biopolymers
• Our brains are essentially bio-polymer processing units,
instead of the silicon ones in our computers…
• After WWII, synthetic polymers started taking
a hold of our daily lives…
– Hydrocarbons, Carbon and Hydrogen backbones

Chapter 14/15- 1
 Hydrocarbons (I)
• Saturated hydrocarbons molecules
– All single bonds
– All are gases at RT

Chapter 14/15-
 Hydrocarbons (II)

• Unsaturated hydrocarbons molecules

– Double or triple bonds between C atoms
– More active

Chapter 14/15-
 Hydrocarbons (III)
• RADICALS:
– Other organic groups can be involved in polymer molecules. In table
adjacent R represents radicals: Organic groups of atoms that remain as a
unit and maintain their identity during chemical reactions (e.g. CH3, C2H5,
C6H5)

Chapter 14/15-
 Polymers

• Polymer molecules are very large, gigantic in size:

called sometimes macromolecules
• Within these atoms are covalently bonded to each
other
• Most polymers consist of long and flexible chains with
a string of C atoms as a backbone.
– Side-bonding of C atoms to H atoms or radicals
• Double bonds possible in both chain and side bonds
• Repeat unit in a polymer chain (“unit cell”) is a mer
• A single mer is called a monomer
• Many mers is a polymer

Chapter 14/15-
 Chemistry of Polymerization
• Ethylene (C2H4) is a gas at STP (RT and pressure)
• Ethylene transform to poly-ethylene (solid) by forming active mer through reaction with
initiator or catalytic radical (R.)
• (.) denotes unpaired electron (active site)
• C-C bond length 0.154 nm

At certain T and P with polymerize

with the help of the Radicals

Chapter 14/15-
 Polymer Microstructure

• C-C bond is not 180º, but 109º

• Furthermore, chain rotations act as kinks
– Double or triple bonds are rigid
Chapter 14/15-
 POLMER MICROSTRUCTURE
• Polymer = many mers
mer mer mer
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH 3 H CH 3 H CH 3
Polyethylene (PE) Polyvinyl chloride (PVC) Polypropylene (PP)
Adapted from Fig. 14.2, Callister 6e.

• Covalent chain configurations and strength:

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.

Chapter 14/15- 2
More on Polymer Microstructure

Chapter 14/15-
 Molecular Weight (I)
• Very large molecules can be found in
polymers
• Final molecular weight (chain length) is
controlled by relative rates of initiation,
propagation, termination steps of
polymerization
• Not all chains will grow to the same size
hence, formation of macromolecules
during polymerization results in
distribution of chain lengths and molecular
weights
• The average molecular weight can be
obtained by averaging the masses with
the fraction of times they appear
(number-average molecular weight) or
with the mass fraction of the molecules
(weight-average molecular weight).

Chapter 14/15-
 Molecular Weight (II)
• Melting / softening
temperatures increase with
molecular weight (up to ~
100,000 g/mol)
• At room temperature, short
chain polymers (molar
weight ~ 100 g/mol) are
liquids or gases, intermediate
length polymers (~ 1000
g/mol) are waxy solids, solid
polymers have molecular
weights of 104 - 107 g/mol

Chapter 14/15-
 Molecular Shape
• Molecular chains can bend, coil and
kink due to single C-C bonds
rotating on each other
• Neighboring chains may intertwine
and entangle
• Large elastic extensions of rubbers
correspond to unraveling of these
coiled chains and getting straighter
• Mechanical / thermal characteristics
depend on the ability of chain
segments to rotate, remember double
C=C bonds are stiffer.

Chapter 14/15-
 Molecular Structure
1. Linear polymers: Weak or Van der Waals
bonding between chains. Examples are
polyethylene, nylon, and PVC.

2. Branched polymers: Chain packing

efficiency is reduced compared to linear
polymers - lower density

3. Cross-linked polymers: Chains are

connected by covalent bonds. Often achieved
by adding atoms or molecules that form
covalent links between chains. Many rubbers
have this structure.

4. Network polymers: 3D networks made from

trifunctional mers, covalent bonds. Have
distinct mechanical and thermal properties
Examples: epoxies, phenolformaldehyde.
Chapter 14/15-
 Isomerism
• Hydrocarbon compounds with same composition can assume different atomic
arrangements.
– Physical properties may also depend on isomeric state (e.g. boiling
temperature of normal butane is -0.5 °C, of isobutane -12.3 °C)

• There are two main types of isomerism and each have

sub groups underneath:
– Stereoisomerism: spatial pattern of atoms or
functional groups attaching themselves to the chain
link
• Isotatic=> all at the same side
• Syndiotactic=> alternating sides
• Atactic=> random positions

Chapter 14/15-
Summary

Natural rubber

Inelastic natural latex

-used in early golf ball cores

Chapter 14/15-
 Copolymers
• Copolymers, are
polymers which has
at least two different
types of mers.
• They can differ in
the way the mers
are arranged:

Chapter 14/15-
 Polymer Crystallinity (I)

polyethylene
Atomic arrangement in polymer crystals is more complex than in
metals or ceramics.
The unit cells are typically very large and complex as molecules or
chains replace ions and or atoms in these structures.
Think of it as packing of molecular chains in a geometrical array
Chapter 14/15-
 Polymer Crystallinity (II)
• Molecular substance such as water, methane etc solidify as
crystals and are totally amorphous in liquid phase
• Polymer molecules are often partially crystalline (semicrystalline),
with crystalline regions dispersed within amorphous material.
Because, any disorder, kink in the long chains induce an
amorphous region.
– Degree of crystallinity:

Factors effecting crystallinity:

• Rate of cooling during solidification: time is necessary for chains to move and align into a crystal
structure
• Mer complexity: crystallization less likely in complex structures, simple polymers, such as polyethylene,
crystallize relatively easily
• Chain configuration: linear polymers crystallize relatively easily, branches inhibit crystallization, network
polymers almost completely amorphous, crosslinked polymers can be both crystalline and amorphous
• Isomerism: isotactic, syndiotactic polymers crystallize relatively easily - geometrical regularity allows
chains to fit together, atactic difficult to crystallize
• Copolymerism: easier to crystallize if mer arrangements are more regular - alternating, block can
crystallize more easily as compared to random and graft

• Chapter 14/15-
More crystallinity: higher density, more strength, higher resistance to dissolution and softening by heating
Polymer Crystallinity (III)

Chapter 14/15-
Examples

Chapter 14/15-
MOLECULAR WEIGHT & CRYSTALLINITY
• Molecular weight, Mw: Mass of a mole of chains.

smaller M w larger M w

• Tensile strength (TS):

--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.
• % Crystallinity: % of material that is crystalline.
--TS and E often increase
with % crystallinity. crystalline
--Annealing causes region
crystalline regions
to grow. % crystallinity amorphous
region
increases.

Adapted from Fig. 14.11, Callister 6e.

(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,Chapter 14/15- 3
and J. Wulff, The Structure and Properties of Materials, Vol. III, Mechanical Behavior,
John Wiley and Sons, Inc., 1965.)
 TENSILE RESPONSE: BRITTLE & PLASTIC
Near Failure (MPa)
brittle failure
60 x
near
onset of
failure
necking p lastic failure
40 x
Initial
20 unload/reload

0 
0 2 4 6 8
aligned, networked
cross- case crystalline
linked regions
case slide
semi-
crystalline amorphous
crystalline
case regions
regions align
elongate
Stress-strain curves adapted from Fig. 15.1, Callister 6e. Inset figures along plastic response curve (purple) adapted from Fig.
15.12, Callister 6e. (Fig. 15.12 is from J.M. Schultz, Polymer Materials Science, Prentice-Hall, Inc., 1974, pp. 500-501.)
Chapter 14/15- 4
 Stress-Strain Behavior of Polymers (I)
• Overall similar to metals, but…
• The stress-strain behavior can be brittle (A),plastic (B), and highly elastic
(C)
• Deformation shown by curve C is totally elastic (rubberlike elasticity). This
class of polymers - elastomers

Elastic Modulus: same as metals

Ductility (%EL): same as metals
Yield strength: type B curves, maximum on the
curve right after elastic region
Tensile Strength: defined as the fracture strength,
can be lower than YS; different than14/15-
Chapter metals
 TENSILE RESPONSE: ELASTOMER CASE
(MPa)
60 x brittle failure
Stress-strain curves
adapted from Fig. 15.1,
Callister 6e. Inset figures
along elastomer curve
plastic failure (green) adapted from Fig.
40 x 15.14, Callister 6e. (Fig.
15.14 is from Z.D.
Jastrzebski, The Nature
and Properties of
20 x Engineering Materials, 3rd
elastomer ed., John Wiley and Sons,
1987.)
final : chains
0  are straight,
0 2 4 6 8 still
cross-linked
initial: amorphous chains are Deformation
kinked, heavily cross-linked. is reversible!

• Compare to responses of other polymers:

--brittle response (aligned, cross linked & networked case)
--plastic response (semi-crystalline case)
Chapter 14/15- 6
 Stress-Strain Behavior of Polymers (II)
Some points with polymers:

• Moduli of elasticity are ~ 10 MPa - 4 GPa (metals ~ 50 - 400 GPa)

• Tensile strengths are ~ 10 - 100 MPa (metals ~ 100 MPa to 10 GPa)
• Percent elongation can be up to 1000 % in some cases (< 100% for
metals)
• WHY ?

• Mechanical properties of polymers change dramatically with temperature,

going from glass-like brittle behavior at low temperatures to a rubber-like
behavior at high temperatures.
• Polymers are also very sensitive to the rate of deformation (strain rate).
Decreasing rate of deformation has the same effect as increasing…

Chapter 14/15-
 Stress-Strain Behavior of Polymers (III)
Impact of temperature:
– Decrease in elastic modulus
– Reduction in tensile strength
– Increase in ductility

polymethyl methacrylate
(PMMA)
plexiglass

Chapter 14/15-
 Deformation (I)
Elastic deformation:
• Basic mechanism of elastic deformation is
elongation (straightening) of chain molecules in the
direction of the applied stress. Elastic modulus is
defined by elastic properties of amorphous and
crystalline regions and by the microstructure.
Plastic deformation:
• Plastic deformation is defined by the interaction
between crystalline and amorphous regions, and is
partially reversible.
Stages of plastic deformation:
1. elongation of amorphous chains
2. tilting of lamellar crystallites towards the tensile axis
3. separation of crystalline block segments
4. stretching of crystallites and amorphous regions along
tensile axis

IMPORTANT: where are the dislocations ?

Chapter 14/15-
 Deformation (II)
• The macroscopic deformation involves necking. Neck region gets stronger since
the deformation aligns the chains and increases local strength in the neck region
(up to 2-5 times) Neck will expand along the specimen.

• What is different from metals is ? The neck region will expand ! Whereas in
metals deformation will be limited to the neck region !

Chapter 14/15-
 Factors that influence mechanical properties (I)
• Temperature and strain rate
• Chain entanglement, strong intermolecular bonding (van der
Waals, cross-links) increase strength

• Drawing, analog of work hardening in metals, corresponds to the neck

extension. Is used in production of fibers and films. Molecular chains
become highly oriented:
– properties of drawn material are anisotropic
• perpendicular to the chain alignment direction strength is reduced

• Heat treatment - changes in crystallite size and order

– undrawn material: Increasing annealing temperature leads to
• increase in elastic modulus
Note that these changes are
• increase in yield/tensile strength opposite from metals
• decrease in ductility
– drawn material: opposite changes (due to recrystallization and loss of chain
orientation)

Chapter 14/15-
 Factors that influence mechanical properties (II)
• Tensile strength increases with molecular weight – effect of
entanglement
• Higher degree of crystallinity – stronger secondary bonding -
stronger and more brittle material

Chapter 14/15-
 SUMMARY
• General drawbacks to polymers:
-- E, y, Kc, Tapplication are generally small.
-- Deformation is often T and time dependent.
-- Result: polymers benefit from composite reinforcement.
• Thermoplastics (PE, PS, PP, PC):
-- Smaller E, y, Tapplication
-- Larger Kc Table 15.3 Callister 6e:
-- Easier to form and recycle
Good overview
• Elastomers (rubber):
of applications
-- Large reversible strains! and trade names
• Thermosets (epoxies, polyesters): of polymers.
-- Larger E, y, Tapplication
-- Smaller Kc

Chapter 14/15- 10
 ANNOUNCEMENTS
Reading: Chapters 14 and 15

Core Problems:

Self-help Problems:

Chapter 14/15- 0