CHAPTER 14/15: POLYMER STUDIES

Issues:
What are the basic microstructural features of a polymer?
How are polymer properties affected by molecular weight?
How do polymeric materials accommodate the polymer chain?
What are the tensile properties of polymers and how are they affected by
basic microstructural features?
Changing Polymer Properties: Hardening, anisotropy,
and annealing in polymers.
How does the elevated temperature mechanical response of
polymers compare to ceramics and metals?
What are the primary polymer processing methods?

Chapter 14 Polymers
What is a polymer?
Poly
many

mer
repeat unit

repeat
unit

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Polyvinyl chloride (PVC)

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

Polypropylene (PP)

Adapted from Fig. 14.2, Callister 7e.

H
C
CH3

Ancient Polymer History

Originally many natural polymers were used
Wood Rubber
Cotton Wool
Leather
Silk
Oldest known uses of Modern Polymers
Rubber balls used by Incas
Noah used pitch (a natural polymer)
for the ark as had all ancient mariners!

Polymer Composition
Most polymers are hydrocarbons
i.e. made up of H and C
(we also recognize Si-H silicones)
Saturated hydrocarbons
Each carbon bonded to four other atoms

H
C

H
C
H

CnH2n+2
H

Unsaturated Hydrocarbons
Double & triple bonds relatively reactive can form new bonds
Double bond ethylene or ethene - CnH2n

H
C C

4-bonds, but only 3 atoms bound to Cs

Triple bond acetylene or ethyne - CnH2n-2
H C C H

Isomerism

Isomerism
two compounds with same chemical formula can have quite
different structures
Ex: C8H18
n-octane
H H H H H H H H
H C C C C C C C C H

= H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3

H H H H H H H H

H3C ( CH2 ) CH3

6

2-methyl-4-ethyl pentane (isooctane)

CH3
H3C CH CH2 CH CH3
CH2
CH3

Chemistry of Polymers
Free radical polymerization
R

H H
H H

H H

C C

R C C

H H
monomer
(ethylene)

free radical

R C C

H H

initiation

H H

H H

H H H H

C C

R C C C C

H H

H H H H

propagation

dimer

Initiator: example - benzoyl peroxide

H

C O O C
H

H
H

C O
H

=2R

Chemistry of Polymers
Free radical polymerization (addition polymerization)
R

H H
H H

H H

C C

R C C

H H
monomer
(ethylene)

free radical

R C C

H H

initiation

H H

H H

H H H H

C C

R C C C C

H H

H H H H

propagation

dimer

Initiator: example - benzoyl peroxide

H

C O O C
H

H
H

C O
H

=2R

Condensation Polymerization
Water is Condensed out
during polymerization of Nylon

Some of the original monomers materials are shed

(condensed out) during polymerization process
Process is conducted in the presence of a catalyst
Water, CO2 are commonly condensed out but other
compounds can be emitted including HCN or other acids

Bulk or Commodity Polymers

NOTE: See Table 15.3 for commercially important

polymers including trade names

MOLECULAR WEIGHT
Molecular weight, Mi: Mass of a mole of chains.
Lower M

higher M

total wt of polymer
Mn
total # of molecules

M n x i M i
M w w i M i
Mw is more sensitive to
higher molecular
weights

Adapted from Fig. 14.4, Callister 7e.

Molecular Weight Calculation

Example: average mass of a class

M n xi M i
M w wi M i
xi

Ni

all i

wi

Ni M i

N M
i

all i

Degree of Polymerization, n
n = number of repeat units per chain
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 H

ni = 6

H H H H H H H H H H H H

Mn
nn x i ni
m

Mw
nw w i ni
m

where m average molecular weight of repeat unit

m fi mi
Chain fraction

mol. wt of repeat unit i

Molecular Structures
Covalent chain configurations and strength:

secondary

bonding

Linear

Branched

Cross-Linked

Network

Direction of increasing strength

Adapted from Fig. 14.7, Callister 7e.

Polymers Molecular Shape

Conformation Molecular orientation can be
changed by rotation around the bonds
note: no bond breaking needed
Adapted from Fig.
14.5, Callister 7e.

Polymers Molecular Shape

Configurations to change must break bonds
Stereoisomerism
H

H
C C

H H

H R
or

C C
R

C C

H R

H H

C
B

D
mirror
plane

Tacticity
Tacticity stereoregularity of chain

isotactic all R groups on

same side of chain

syndiotactic R groups
alternate sides

H H H H H H H H
C C C C C C C C
H R H R H R H R
H H H R H H H R
C C C C C C C C
H R H H H R H H
H H H H H R H H

atactic R groups random

C C C C C C C C
H R H R H H H R

cis/trans Isomerism
CH3

H
C C

CH2

CH2

CH3

C C

CH2

CH2
H

cis

trans

cis-isoprene
(natural rubber)

trans-isoprene
(gutta percha)

bulky groups on same

side of chain

bulky groups on opposite

sides of chain

Copolymers
two or more monomers
polymerized together
random A and B randomly vary
in chain
alternating A and B alternate in
polymer chain
block large blocks of A alternate
with large blocks of B
graft chains of B grafted on to A
backbone
A

Adapted from Fig.

14.9, Callister 7e.

random

alternating
block

graft

Polymer Crystallinity
Adapted from Fig.
14.10, Callister 7e.

Ex: polyethylene unit cell

Crystals must contain the

polymer chains in some way
Chain folded structure

Adapted from Fig.

14.12, Callister 7e.

Polymer Crystallinity
Polymers rarely exhibit 100% crystalline
Too difficult to get all those chains aligned
crystalline
region

Crystallinity: how much

is crystalline.

-- TS and E often increase

with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases.
amorphous
region
Adapted from Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.)

Mechanical Properties
i.e. stress-strain behavior of polymers
brittle polymer

FS of polymer ca. 10% that of metals

plastic
elastomer
elastic modulus
less than metal

Adapted from Fig. 15.1,

Callister 7e.

Strains deformations > 1000% possible

(for metals, maximum strain ca. 100% or less)

Tensile Response: Brittle & Plastic

Near Failure

(MPa)

fibrillar
structure

x brittle failure
onset of
necking

near
failure

plastic failure

x
Initial
unload/reload

aligned, networked
crosscase
linked
case

crystalline
regions
slide
semicrystalline
case

amorphous
regions
elongate

crystalline
regions align

Stress-strain curves adapted from Fig. 15.1, Callister 7e. Inset figures along plastic response curve adapted from
Figs. 15.12 & 15.13, Callister 7e. (Figs. 15.12 & 15.13 are from J.M. Schultz, Polymer Materials Science, PrenticeHall, Inc., 1974, pp. 500-501.)

Predeformation by Drawing
Drawing(ex: monofilament fishline)
-- stretches the polymer prior to use
-- aligns chains in the stretching direction
Results of drawing:
-- increases the elastic modulus (E) in the
stretching direction
-- increases the tensile strength (TS) in the
stretching direction
-- decreases ductility (%EL)
Annealing after drawing...
-- decreases alignment
-- reverses effects of drawing.

Comparable to cold working in metals!

Adapted from Fig. 15.13, Callister

7e. (Fig. 15.13 is from J.M.
Schultz, Polymer Materials
Science, Prentice-Hall, Inc.,
1974, pp. 500-501.)

Tensile Response: Elastomer Case

(MPa)
x brittle failure

plastic failure

elastomer

initial: amorphous chains are

kinked, cross-linked.

final: chains
are straight,
still
cross-linked

Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset
figures along elastomer
curve (green) adapted
from Fig. 15.15, Callister
7e. (Fig. 15.15 is from
Z.D. Jastrzebski, The
Nature and Properties of
Engineering Materials,
3rd ed., John Wiley and
Sons, 1987.)

Deformation
is reversible!

Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)

Thermoplastics vs. Thermosets

Thermoplastics:
-- little crosslinking
-- ductile
-- soften w/heating
-- polyethylene
polypropylene
polycarbonate
polystyrene

Thermosets:

T
viscous
liquid

mobile
liquid

crystalline
solid

Callister,
rubber
Fig. 16.9
tough
plastic

Tm
Tg

partially
crystalline
solid

Molecular weight
Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W.
Billmeyer, Jr., Textbook of Polymer Science, 3rd ed., John Wiley and
Sons, Inc., 1984.)

-- large crosslinking
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin

T and Strain Rate: Thermoplastics

Decreasing T...
-- increases E
-- increases TS
-- decreases %EL

Increasing
strain rate...
-- same effects
as decreasing T.

(MPa)
80 4C
60

20C

40

Data for the

semicrystalline
polymer: PMMA
(Plexiglas)

40C

20
0

60C
0

0.1

0.2

to 1.3
0.3

Adapted from Fig. 15.3, Callister 7e. (Fig. 15.3 is from T.S. Carswell and
J.K. Nason, 'Effect of Environmental Conditions on the Mechanical
Properties of Organic Plastics", Symposium on Plastics, American Society
for Testing and Materials, Philadelphia, PA, 1944.)

Melting vs. Glass Transition Temp.

What factors affect Tm
and Tg?

Both Tm and Tg increase with

increasing chain stiffness

Chain stiffness increased by

1. Bulky sidegroups
2. Polar groups or
sidegroups
3. Double bonds or
aromatic chain groups

Regularity (tacticity) affects

Tm only
Adapted from Fig. 15.18,
Callister 7e.

Time Dependent Deformation

Stress relaxation test:
-- strain to and hold.
-- observe decrease in
stress with time.
tensile test

for T5 > Tg.

10

rigid solid
(small relax)

Er (10s) 3
in MPa 10

transition
region

10

strain

10-1

(t)

10-3 (large relax)

time

Relaxation modulus:
(t )
E r (t )
o

Data: Large drop in Er

viscous liquid

(amorphous
polystyrene)
Adapted from Fig.
15.7, Callister 7e.
(Fig. 15.7 is from
A.V. Tobolsky,
Properties and
Structures of
Polymers, John
Wiley and Sons, Inc.,
1960.)

60 100 140 180 T(C)

Tg

Sample Tg(C) values:

PE (low density)
PE (high density)
PVC
PS
PC

- 110
- 90
+ 87
+100
+150

Selected values from

Table 15.2, Callister
7e.

Polymer Fracture
Crazing Griffith cracks in metals
spherulites plastically deform to fibrillar structure
microvoids and fibrillar bridges form
alligned chains

fibrillar bridges

microvoids

crack

Adapted from Fig. 15.9,

Callister 7e.

Polymer Additives
Improve mechanical properties, processability, durability,
etc.
Fillers
Added to improve tensile strength & abrasion resistance,
toughness & decrease cost
ex: carbon black, silica gel, wood flour, glass, limestone,
talc, etc.

Plasticizers
Added to reduce the glass transition
temperature Tg
commonly added to PVC - otherwise it is brittle

Polymer Additives
Stabilizers
Antioxidants
UV protectants

Lubricants
Added to allow easier processing
slides through dies easier ex: Na stearate
Colorants
Dyes or pigments
Flame Retardants
Cl/F & B

Processing of Plastics
Thermoplastic
can be reversibly cooled & reheated, i.e. recycled
heat till soft, shape as desired, then cool
ex: polyethylene, polypropylene, polystyrene, etc.

Thermoset
when heated forms a network
degrades (not melts) when heated
mold the prepolymer then allow further reaction
ex: urethane, epoxy

Processing Plastics - Molding

Compression and transfer molding
thermoplastic or thermoset

Adapted from Fig. 15.23,

Callister 7e. (Fig. 15.23 is from
F.W. Billmeyer, Jr., Textbook of
Polymer Science, 3rd ed.,
John Wiley & Sons, 1984. )

Processing Plastics - Molding

Injection molding
thermoplastic & some thermosets
Adapted from Fig. 15.24,
Callister 7e. (Fig. 15.24 is from
F.W. Billmeyer, Jr., Textbook of
Polymer Science, 2nd edition,
John Wiley & Sons, 1971. )

Processing Plastics Extrusion

Adapted from Fig. 15.25,

Callister 7e. (Fig. 15.25 is from
Encyclopdia Britannica, 1997.)

Polymer Types: Elastomers

Elastomers rubber
Crosslinked materials
Natural rubber
Synthetic rubber and thermoplastic elastomers
SBR- styrene-butadiene rubber

butadiene

Silicone rubber

styrene

Polymer Types: Fibers

Fibers - length/diameter >100
Textiles are main use
Must have high tensile strength
Usually highly crystalline & highly polar
Formed by spinning
ex: extrude polymer through a spinnerette
Pt plate with 1000s of holes for nylon
ex: rayon dissolved in solvent then pumped through
die head to make fibers

the fibers are drawn

leads to highly aligned chains- fibrillar structure

Polymer Types

Coatings thin film on surface i.e. paint, varnish

To protect item
Improve appearance
Electrical insulation

Adhesives produce bond between two adherands

Usually bonded by:
1. Secondary bonds
2. Mechanical bonding

Films blown film extrusion

Foams gas bubbles in plastic

Blown-Film Extrusion

Adapted from Fig. 15.26, Callister 7e.

(Fig. 15.26 is from Encyclopdia
Britannica, 1997.)

Advanced Polymers
Ultrahigh molecular weight
polyethylene (UHMWPE)
Molecular weight
ca. 4 x 106 g/mol
Excellent properties for
variety of applications

UHMWPE

bullet-proof vest, golf ball

covers, hip joints, etc.
Adapted from chapteropening photograph,
Chapter 22, Callister 7e.

The Stem, femoral head, and the AC socket are made from Cobalt-chrome metal alloy or ceramic, AC
cup made from polyethylene

ABS A Polymerized Alloy

ABS, Acrylonitrile-Butadiene-Styrene
Made up of the 3 materials: acrylonitrile, butadiene and styrene. The material is located under
the group styrene plastic. Styrene plastics are in volume one of the most used plastics.
Properties

The mechanical properties for ABS are good for impact resistance even in low temperatures.
The material is stiff, and the properties are kept over a wide temperature range. The
hardness and stiffness for ABS is lower than for PS and PVC.
Weather and chemical resistance

The weather resistance for ABS is restricted, but can be drastically improved by additives as
black pigments. The chemical resistance for ABS is relatively good and it is not affected by
water, non organic salts, acids and basic. The material will dissolve in aldehyde, ketone,
ester and some chlorinated hydrocarbons.
Processing

ABS can be processed by standard mechanical tools as used for machining of metals and wood.
The cutting speed need to be high and the cutting tools has to be sharp. Cooling is
recommended to avoid melting of the material. If the surface finish is of importance for the
product, the ABS can be treated with varnish, chromium plated or doubled by a layer of
acrylic or polyester. ABS can be glued to it self by use of a glue containing dissolvent.
Polyurethane based or epoxy based glue can be used for gluing to other materials.

A Processing Movie:

Calloway Golf:

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
-- Easier to form and recycle

Elastomers (rubber):
-- Large reversible strains!

Thermosets (epoxies, polyesters):

-- Larger E, y, Tapplication
-- Smaller Kc

And Remember:
Table 15.3 Callister 7e
Is a Good overview of
applications and trade
names of polymers.