Chapter 15:

Characteristics, Applications &

Processing of Polymers
ISSUES TO ADDRESS...
• What are the tensile properties of polymers and how
are they affected by basic microstructural features?
• 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 15 - 1
Mechanical Properties of Polymers –
Stress-Strain Behavior
brittle polymer

plastic
elastomer
elastic moduli
– less than for metals Adapted from Fig. 15.1,
Callister & Rethwisch 9e.

• _____________ of polymers ~ 10% of those for metals

• _____________ strains for polymers > 1000%
– for most metals, deformation strains < 10%
Chapter 15 - 2
 Mechanisms of Deformation—Brittle
Crosslinked and Network Polymers
Near σ(MPa) ____
Initial _____
______ Failure x brittle failure

x ___________

aligned, crosslinked e ________________

polymer Stress-strain curves adapted from Fig. 15.1,
Callister & Rethwisch 9e.

Chapter 15 - 3
 Mechanisms of Deformation —
Semicrystalline (Plastic) Polymers
σ(MPa) ________

Stress-strain curves adapted

x brittle failure ________
from Fig. 15.1, Callister & near
Rethwisch 9e. Inset figures onset of
failure
along plastic response curve necking ____________
adapted from Figs. 15.12 &
15.13, Callister & Rethwisch
9e. (From SCHULTZ, POLYMER x
MATERIALS SCIENCE, 1st Edition,
© 1974. Reprinted by permission of
Pearson Education, Inc., Upper
Saddle River, NJ.)1974, pp 500-501.)
unload/reload

e
crystalline
block segments
separate
__________
structure amorphous
________
regions
regions align
elongate
Chapter 15 - 4
 Predeformation by Drawing
• _________…(ex: monofilament fishline)
-- stretches the polymer prior to use
-- aligns chains in the ____________________
• Results of drawing:
-- increases the elastic modulus (E) in the
_________________
-- increases ____________________ (TS) in the
stretching direction Adapted from Fig. 15.13, Callister &
-- decreases ductility (%EL) Rethwisch 9e.
(From Schultz, Polymer Materials Science,
• _________ after drawing... 1st Edition, © 1974. Reprinted by permission
of Pearson Education, Inc., Upper Saddle

-- ___________ chain alignment River, NJ.)1974, pp 500-501.)

-- reverses effects of drawing (reduces E and

TS, enhances %EL)
• Contrast to effects of cold working in metals!

Chapter 15 - 5
 Mechanisms of Deformation—
Elastomers
σ(MPa)
x brittle failure Stress-strain curves
adapted from Fig. 15.1,
Callister & Rethwisch 9e.
Inset figures along
elastomer curve (green)
adapted from Fig. 15.15,
plastic failure
x Callister & Rethwisch 9e.
(Fig. 15.15 adapted from Z. D.
Jastrzebski, The Nature and
x Properties of Engineering
Materials, 3rd edition.
elastomer Copyright © 1987 by John
Wiley & Sons, New York.
final: chains Reprinted by permission of
John Wiley & Sons, Inc.)
are straighter,
e still
cross-linked
initial: amorphous chains are deformation
kinked, cross-linked. is reversible (elastic)!

• Compare __________________ of elastomers with the:

-- ____ behavior (of aligned, crosslinked & network polymers), and
-- plastic behavior (of __________ polymers)
(as shown on previous slides)
Chapter 15 - 6
 Thermoplastics vs. Thermosets
T
• Thermoplastics: Callister,
-- little __________ viscous rubber
Fig. 16.9
mobile liquid Tm
-- ductile tough
liquid
-- soften w/heating plastic
-- polyethylene Tg
polypropylene
partially
polycarbonate crystalline
polystyrene crystalline
solid
solid

• ______________: Molecular weight

Adapted from Fig. 15.19, Callister & Rethwisch 9e.
-- significant _____________ (From F. W. Billmeyer, Jr., Textbook of Polymer Science, 3rd edition.
Copyright © 1984 by John Wiley & Sons, New York. Reprinted by
(10 to 50% of repeat units) permission of John Wiley & Sons, Inc.)
-- hard and brittle
-- do NOT soften w/heating
-- __________ rubber, epoxies,
polyester resin, phenolic resin
7
Chapter 15 - 7
Influence of T and Strain Rate on Thermoplastics

• ___________ T... σ(MPa)

-- increases E 80 4ºC Plots for
-- __________ TS semicrystalline
-- decreases %EL 60 PMMA (Plexiglas)
20ºC
• _____________ 40 40ºC
strain rate...
-- same effects 20
as decreasing T. to 1.3
60ºC
0
0 0.1 0.2 e 0.3
Adapted from Fig. 15.3, Callister & Rethwisch 9e. (Reprinted with permission
from T. S. Carswell and H. K. Nason, “Effect of Environmental Conditions on the
Mechanical Properties of Organic Plastics,” in Symposium on Plastics. Copyright ASTM
International, 100 Barr Harbor Drive, West Conshohocken, PA 19428.)

8
Chapter 15 - 8
 Melting & Glass Transition Temps.
What ______________________?
• Both Tm and Tg __________ with
increasing chain stiffness
• Chain stiffness ___________ by
presence of
1. Bulky sidegroups
2. Polar groups or sidegroups
3. Chain double bonds and
aromatic chain groups

• _____________ of repeat unit

arrangements – affects Tm only

Adapted from Fig. 15.18,

Callister & Rethwisch 9e.

Chapter 15 - 9
 Time-Dependent Deformation
• Stress ___________ test: • There is a large ________ in Er
-- strain in tension to eo for T > Tg. (amorphous
5
and hold. 10 rigid solid polystyrene)
Er (10 s) 3 (small relax) Fig. 15.7, Callister &
-- observe ________ in in MPa 10
Rethwisch 9e.
transition (From A. V. Tobolsky,
stress with time. 1 region
Properties and Structures
10 of Polymers. Copyright ©
1960 by John Wiley &
tensile test 10-1
Sons, New York.
Reprinted by permission
viscous liquid of John Wiley & Sons,
eo strain 10-3 (large relax)
Inc.)

60 100 140 180 T(ºC)

σ(t) Tg
time • Representative Tg values (C):
• ____________ modulus: PE (low density) - 110
PE (high density) - 90
Selected values from
________ + 87 Table 15.2, Callister
PS +100 & Rethwisch 9e.

________ +150
Chapter 15 - 10
 Crazing During Fracture of
Thermoplastic Polymers
_______ formation prior to cracking
– during crazing, ________________ of spherulites
– and formation of __________________________
aligned chains

fibrillar bridges microvoids crack

Fig. 15.9, Callister & Rethwisch 9e.
(From J. W. S. Hearle, Polymers and Their Properties, Vol. 1,
Fundamentals of Structure and Mechanics, Ellis Horwood, Ltd.,
Chichester, West Sussex, England, 1982.)
Chapter 15 - 11
 Polymer Formation
• There are two types of ____________
– ___________________ polymerization
– ___________________ polymerization

Chapter 15 - 12
 Addition (Chain) Polymerization

– Initiation

– ____________

– ____________

Chapter 15 - 13
Condensation (Step)
Polymerization

Chapter 15 - 14
 Polymer Additives
Improve mechanical properties, processability,
durability, etc.
• Fillers
– Added to improve _____________________
resistance, toughness & decrease cost
– ex: carbon black, silica gel, wood flour, glass,
limestone, talc, etc.
• _______________
– Added to ________ the glass transition
temperature Tg below room temperature
– Presence of _______ transforms brittle polymer to a
_______ one
– Commonly added to PVC - otherwise it is brittle

Chapter 15 - 15
 Polymer Additives (cont.)
• Stabilizers
– ________________
– UV protectants
• ________________
– Added to allow __________________
– polymer “slides” through _____ easier
– ex: sodium stearate
• Colorants
– ______________________
• _____________________
– Substances containing chlorine, fluorine, and boron

Chapter 15 - 16
 Processing of Plastics
• ____________________
– can be reversibly _______________, i.e. recycled
– heat until soft, ____________________, then cool
– ex: polyethylene, polypropylene, polystyrene.
• Thermoset
– when heated _______________________________
(chemical reaction)
– _________ (doesn’t melt) when heated
– a prepolymer molded into desired shape, then
chemical reaction occurs
– ex: urethane, epoxy

Chapter 15 - 17
 Processing Plastics – Compression Molding
Thermoplastics and thermosets
• _________________________ placed in mold cavity
• mold ___________________________________
• _________________ assumes shape of mold

Fig. 15.23, Callister & Rethwisch 9e.

(From F. W. Billmeyer, Jr., Textbook of
Polymer Science, 3rd edition. Copyright ©
1984 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley &
Sons, Inc.)
Chapter 15 - 18
Processing Plastics – Injection Molding
__________________ and some thermosets
• when ram retracts, plastic pellets drop from _______ into barrel
• ram forces plastic into the heating chamber (around the
spreader) where the _________________________________
• molten plastic is forced under pressure (_______) into the mold
__________ where it assumes the shape of the mold

Fig. 15.24, Callister & Rethwisch 9e.

(From F. W. Billmeyer, Jr., Textbook of
Polymer Science, 3rd edition. Copyright ©
1984 by John Wiley & Sons, New York.
Reprinted by permission of John Wiley &
Sons, Inc.)

Barrel
Chapter 15 - 19
Processing Plastics – Extrusion
_____________________
• plastic pellets drop from hopper onto the ____________
• plastic pellets melt _____________ pushes them forward
by the heaters
• molten polymer is forced under pressure through the
shaping die to form the final product (___________)

Fig. 15.25, Callister & Rethwisch 9e.

(Reprinted with permission from Encyclopædia
Britannica, © 1997 by Encyclopædia Britannica, Inc.)

Chapter 15 - 20
Processing Plastics – Blown-Film
Extrusion

Fig. 15.26, Callister & Rethwisch 9e.

(Reprinted with permission from Encyclopædia
Britannica, © 1997 by Encyclopædia Britannica, Inc.)

Chapter 15 - 21
 Polymer Types – Fibers
Fibers - length/diameter >100
• Primary use is in _____________.
• Fiber characteristics:
– ___________________________
– high degrees of crystallinity
– structures containing ________ groups
• Formed by spinning
– extrude polymer through a ____________ (a die
containing many small orifices)
– the spun fibers are drawn under tension
– leads to highly aligned chains -
_________________

Chapter 15 - 22
 Polymer Types – Miscellaneous
• _______ – thin polymer films applied to surfaces – i.e.,
paints, varnishes
– _____________________________
– decorative – improves appearance
– _____________________________
• Adhesives – bonds two solid materials (____________)
– bonding types:
1. Secondary – van der Waals forces
2. ___________________________________________
• ______ – produced by blown film extrusion
• ______ – gas bubbles incorporated into plastic

Chapter 15 - 23
 Advanced Polymers
Ultrahigh Molecular Weight Polyethylene (UHMWPE)

• Molecular weight ca. ____________

• Outstanding properties
– ______________________
– resistance to wear/abrasion
– ______________________ UHMWPE
– self-lubricating surface
• Important applications
– _____________________ Adapted from chapter-
opening photograph,
– golf ball covers Chapter 22, Callister 7e.

– hip implants (acetabular cup)

Chapter 15 - 24
 Advanced Polymers
Thermoplastic Elastomers
Styrene-butadiene _______________
______
component
styrene
domain

________ soft
component
domain
Fig. 15.21(a), Callister & Rethwisch 9e. Fig. 15.22, Callister & Rethwisch 9e.

Chapter 15 - 25
 Summary
• Limitations of polymers:
-- E, σy, Kc, Tapplication are generally small.
-- Deformation is often time and temperature dependent.
• Thermoplastics (PE, PS, PP, PC):
-- Smaller E, σy, Tapplication
-- Larger Kc
-- Easier to form and recycle Table 15.3 Callister &
• Elastomers (rubber): Rethwisch 9e:
-- Large reversible strains!
Good overview
• Thermosets (epoxies, polyesters):
of applications
-- Larger E, σy, Tapplication and trade names
-- Smaller Kc of polymers.

Chapter 15 - 26
 Summary
• Polymer Processing
-- compression and injection molding, extrusion,
blown film extrusion
• Polymer melting and glass transition temperatures
• Polymer applications
-- elastomers -- fibers
-- coatings -- adhesives
-- films -- foams
-- advanced polymeric materials

Chapter 15 - 27