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 mer
many repeat unit

Adapted from Fig. 14.2, Callister 7e.
C C C C C C
H H H H H H
H H H H H H
Polyethylene (PE)
Cl Cl Cl
C C C C C C
H H H
H H H H H H
Polyvinyl chloride (PVC)
H H
H H H H
Polypropylene (PP)
C C C C C C
CH
3

H H
CH
3
CH
3
H
repeat
unit
repeat
unit
repeat
unit
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







C C
H
H
H
H
H
H
C
n
H
2n+2

Unsaturated Hydrocarbons
Double & triple bonds relatively reactive can form new bonds
Double bond ethylene or ethene - C
n
H
2n









4-bonds, but only 3 atoms bound to Cs

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


C C
H
H
H
H
C C H H
Isomerism
Isomerism
two compounds with same chemical formula can have quite
different structures
Ex: C
8
H
18

n-octane




2-methyl-4-ethyl pentane (isooctane)
C C C C C C C C H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H H
3
C CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
=
H
3
C CH
CH
3
CH
2
CH
CH
2
CH
3
CH
3
H
3
C CH
2
CH
3
( )
6

Chemistry of Polymers
Free radical polymerization







Initiator: example - benzoyl peroxide


C
H
H
O O C
H
H
C
H
H
O
2
C C
H H
H H
monomer
(ethylene)
R +
free radical
R C C
H
H
H
H
initiation
R C C
H
H
H
H
C C
H H
H H
+
R C C
H
H
H
H
C C
H H
H H
propagation
dimer
R = 2
Chemistry of Polymers
Free radical polymerization (addition polymerization)







Initiator: example - benzoyl peroxide


C
H
H
O O C
H
H
C
H
H
O
2
C C
H H
H H
monomer
(ethylene)
R +
free radical
R C C
H
H
H
H
initiation
R C C
H
H
H
H
C C
H H
H H
+
R C C
H
H
H
H
C C
H H
H H
propagation
dimer
R = 2
Condensation Polymerization
Some of the original monomers materials are shed
(condensed out) during polymerization process
Process is conducted in the presence of a catalyst
Water, CO
2
are commonly condensed out but other
compounds can be emitted including HCN or other acids

Water is Condensed out
during polymerization of Nylon
Bulk or Commodity Polymers
NOTE: See Table 15.3 for commercially important
polymers including trade names
MOLECULAR WEIGHT
molecules of # total
polymer of wt total

n
M
i i
w
i i
n
M w M
M x M


M
w
is more sensitive to
higher molecular
weights
Molecular weight, M
i
: Mass of a mole of chains.
Lower M
higher M
Adapted from Fig. 14.4, Callister 7e.
Molecular Weight Calculation
Example: average mass of a class

N
i
M
i
x
i
w
i
# of students mass (lb)
1 100 0.1 0.054
1 120 0.1 0.065
2 140 0.2 0.151
3 180 0.3 0.290
2 220 0.2 0.237
1 380 0.1 0.204
M
n
M
w
186 lb 216 lb

i i
w
M w M

i i
n
M x M

i i
i
i i
all i
N M
w
N M

i
i
i
all i
N
x
N

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

i i
w
i i w
n
i i n
m f m
m
m
M
n w n
m
M
n x n

unit repeat of weight molecular average where

C C C C C C C C H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
C C C C
H
H
H
H
H
H
H
H
H
( ) n
i
= 6
mol. wt of repeat unit i Chain fraction
Covalent chain configurations and strength:
Direction of increasing strength
Adapted from Fig. 14.7, Callister 7e.
Molecular Structures
B ranched Cross-Linked Network Linear
secondary
bonding
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
E
B
A
D
C C
D
A
B
E
mirror
plane
C C
R
H H
H
C C
H
H
H
R
or C C
H
H
H
R
Tacticity
Tacticity stereoregularity of chain
C C
H
H
H
R R
H
H
H
C C
R
H
H
H
C C
R
H
H
H
C C
C C
H
H
H
R
C C
H
H
H
R
C C
H
H
H
R R
H
H
H
C C
C C
H
H
H
R R
H
H
H
C C
R
H
H
H
C C
R
H
H
H
C C
isotactic all R groups on
same side of chain


syndiotactic R groups
alternate sides


atactic R groups random
cis/trans Isomerism
C C
H CH
3
CH
2
CH
2
C C
CH
3
CH
2
CH
2
H
cis
cis-isoprene
(natural rubber)
bulky groups on same
side of chain
trans
trans-isoprene
(gutta percha)
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 B

random
block
graft

Adapted from Fig.
14.9, Callister 7e.
alternating
Polymer Crystallinity
Ex: polyethylene unit cell

Crystals must contain the
polymer chains in some way
Chain folded structure

Adapted from Fig.
14.10, Callister 7e.
Adapted from Fig.
14.12, Callister 7e.
amorphous
region
Polymer Crystallinity
% Crystallinity: how much
is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
to grow. % crystallinity
increases.
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.)
crystalline
region
Polymers rarely exhibit 100% crystalline
Too difficult to get all those chains aligned
Mechanical Properties
i.e. stress-strain behavior of polymers
brittle polymer
plastic
elastomer

FS
of polymer ca. 10% that of metals
Strains deformations > 1000% possible
(for metals, maximum strain ca. 100% or less)
elastic modulus
less than metal
Adapted from Fig. 15.1,
Callister 7e.
Tensile Response: Brittle & Plastic
brittle failure
plastic failure

(MPa)
e
x
x
crystalline
regions
slide
fibrillar
structure
near
failure
crystalline
regions align
onset of
necking
Initial
Near Failure
semi-
crystalline
case
aligned,
cross-
linked
case
networked
case
amorphous
regions
elongate
unload/reload
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, Prentice-
Hall, 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.)
Compare to responses of other polymers:
-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
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.)
Tensile Response: Elastomer Case

(MPa)
e
initial: amorphous chains are
kinked, cross-linked.
x
final: chains
are straight,
still
cross-linked
elastomer
Deformation
is reversible!
brittle failure
plastic failure
x
x
Thermoplastics:
-- little crosslinking
-- ductile
-- soften w/heating
-- polyethylene
polypropylene
polycarbonate
polystyrene
Thermosets:
-- large crosslinking
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin
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.)
Thermoplastics vs. Thermosets
Callister,
Fig. 16.9
T
Molecular weight
T
g

T
m

mobile
liquid
viscous
liquid
rubber
tough
plastic
partially
crystalline
solid
crystalline
solid
Decreasing T...
-- increases E
-- increases TS
-- decreases %EL

Increasing
strain rate...
-- same effects
as decreasing T.
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.)
T and Strain Rate: Thermoplastics
20
4 0
6 0
8 0
0
0 0.1 0.2 0.3
4C
20C
40C
60C
to 1.3

(MPa)
e
Data for the
semicrystalline
polymer: PMMA
(Plexiglas)
Melting vs. Glass Transition Temp.
What factors affect T
m

and T
g
?
Both T
m
and T
g
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
T
m
only

Adapted from Fig. 15.18,
Callister 7e.
Stress relaxation test:
-- strain to eo and hold.
-- observe decrease in
stress with time.
o
r
t
t E
e

) (
) (
Relaxation modulus: Sample T
g
(C) values:
PE (low density)
PE (high density)
PVC
PS
PC
- 110
- 90
+ 87
+100
+150
Selected values from
Table 15.2, Callister
7e.
Time Dependent Deformation
time
strain
tensile test
e
o

(t)
Data: Large drop in E
r
for T > T
g
.
(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.)
10
3
10
1
10
-1
10
-3
10
5
60 100 140 180
rigid solid
(small relax)
transition
region
T(C)
T
g

E
r
(10s)
in MPa
viscous liquid
(large relax)
Polymer Fracture
fibrillar bridges
microvoids
crack
alligned chains
Adapted from Fig. 15.9,
Callister 7e.
Crazing Griffith cracks in metals
spherulites plastically deform to fibrillar structure
microvoids and fibrillar bridges form
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 T
g

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
styrene
Silicone rubber
butadiene
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 10
6
g/mol
Excellent properties for
variety of applications
bullet-proof vest, golf ball
covers, hip joints, etc.
UHMWPE
Adapted from chapter-
opening 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, 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.
ABS A Polymerized Alloy
A Processing Movie:
Calloway Golf:
General drawbacks to polymers:
-- E,
y
, K
c
, T
application
are generally small.
-- Deformation is often T and time dependent.
-- Result: polymers benefit from composite reinforcement.

Thermoplastics (PE, PS, PP, PC):
-- Smaller E,
y
, T
application

-- Larger K
c
-- Easier to form and recycle

Elastomers (rubber):
-- Large reversible strains!

Thermosets (epoxies, polyesters):
-- Larger E,
y
, T
application

-- Smaller K
c

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