Chapter 15:

Characteristics, Applications &

Processing of Polymers
Study: 15.1-15.14
Read: 15.15-15.24
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?

Chapter 15 - 1
 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, bakelyte

Chapter 15 - 2
 Thermoplastics vs. Thermosets
T
Thermoplastics: Callister,
viscous rubber
-- little crosslinking Fig. 16.9
mobile liquid Tm
-- ductile tough
liquid
-- soften w/heating plastic
-- polyethylene Tg
polypropylene
partially
polycarbonate crystalline
polystyrene crystalline
solid
solid

Thermosets: Molecular weight

Adapted from Fig. 15.19, Callister 7e. (Fig. 15.19 is from F.W. Billmeyer,
-- large crosslinking Jr., Textbook of Polymer Science, 3rd ed., John Wiley and Sons, Inc.,
1984.)
(10 to 50% of mers)
-- hard and brittle
-- do NOT soften w/heating
-- vulcanized rubber, epoxies,
polyester resin, phenolic resin
Chapter 15 - 3
 Polymer Types: Elastomers
Elastomers rubber
Crosslinked materials
Natural rubber
Synthetic rubber and thermoplastic elastomers
SBR- styrene-butadiene rubber
styrene

butadiene

Silicone rubber

Chapter 15 - 4
 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

Chapter 15 - 5
 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

Chapter 15 - 6
 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. 10% or less)
Chapter 15 - 7
t15_01_pg526 Chapter 15 -
 Youngs Moduli: Comparison
Graphite
Metals Composites
Ceramics Polymers
Alloys /fibers
Semicond

1200
10 00
8 00
Diamond

6 00
Si carbide

4 00
Tungsten Al oxide
Carbon fibers only
Molybdenum Si nitride
E(GPa) 2 00
Steel, Ni
C
FRE(|| fibers)*
Si crystal
Tantalum <111>
Platinum
<100>
Aramid fibers only
10 0
Cu alloys
8 0

Zinc, Ti
A
FRE(|| fibers)*
Glass - soda
Silver, Gold
6 0 Aluminum Based on data in Table B2,

Glass fibers only
G FRE(|| fibers)*
4 0
Magnesium,
Tin Callister 7e.
Concrete Composite data based on
GFRE*
109 Pa 2 0 CFRE *
reinforced epoxy with 60 vol%
G FRE( fibers)*
of aligned
10

G raphite
8
carbon (CFRE),
C
FRE( fibers) *
6 AFRE( fibers) *
aramid (AFRE), or
4
Polyester
PET
glass (GFRE)
fibers.
2 PC
PS
Epoxy only
PP
1 HDP E
0.8
0.6
Wood( grain)
0.4
PTF E

0.2 LDPE Chapter 15 - 9

 Tensile Response: Brittle & Plastic
(MPa) fibrillar
Near Failure structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload

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 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.) Chapter 15 - 10
 Polymer Crystal Forms
Spherulites fast
growth forms lamellar
(layered) structures

Spherulite
surface

Nucleation site Adapted from Fig. 14.13, Callister 7e.

Chapter 15 - 11
 Polymer Fracture
Crazing Griffith cracks in metals
spherulites plastically deform to fibrillar structure
microvoids and fibrillar bridges form

alligned chains

microvoids Adapted from Fig. 15.9,

fibrillar bridges crack Callister 7e.

Chapter 15 - 12
 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 Adapted from Fig. 15.13, Callister
-- decreases ductility (%EL) 7e. (Fig. 15.13 is from J.M.
Schultz, Polymer Materials
Annealing after drawing... Science, Prentice-Hall, Inc.,
1974, pp. 500-501.)
-- decreases alignment
-- reverses effects of drawing.
Compare to cold working in metals!

Chapter 15 - 13
 Tensile Response: Elastomer Case
(MPa)
x brittle failure Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset
figures along elastomer
curve (green) adapted
from Fig. 15.15, Callister
plastic failure
x 7e. (Fig. 15.15 is from
Z.D. Jastrzebski, The
Nature and Properties of
x Engineering Materials,
elastomer 3rd ed., John Wiley and
Sons, 1987.)
final: chains
are straight,
still
cross-linked
initial: amorphous chains are Deformation
kinked, cross-linked. is reversible!

Compare to responses of other polymers:

-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
Chapter 15 - 14
 T and Strain Rate: Thermoplastics

Decreasing T...
(MPa)
-- increases E 80 4C Data for the
-- increases TS semicrystalline
-- decreases %EL 60 polymer: PMMA
20C (Plexiglas)
Increasing 40 40C
strain rate...
-- same effects 20
as decreasing T. to 1.3
60C
0
0 0.1 0.2 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.)

Chapter 15 - 15
 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 effects Tm only

Adapted from Fig. 15.18,

Callister 7e.
Chapter 15 - 16
t15_02_pg547

Chapter 15 -
 Time Dependent Deformation
Stress relaxation test: Data: Large drop in Er
-- strain to and hold. for T > Tg. (amorphous
5 polystyrene)
-- observe decrease in 10 rigid solid
Er (10s) 3 (small relax) Adapted from Fig.
stress with time. in MPa 10
15.7, Callister 7e.
transition (Fig. 15.7 is from A.V.
tensile test 10 1 region Tobolsky, Properties
and Structures of
Polymers, John
o strain 10-1 Wiley and Sons, Inc.,
viscous liquid 1960.)
(t) 10-3 (large relax)
60 100 140 180 T(C)
time Tg
Relaxation modulus: Sample Tg(C) values:
PE (low density) - 110
PE (high density) - 90
Selected values from
PVC + 87 Table 15.2, Callister
PS +100 7e.

PC +150
Chapter 15 - 18
 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 7e:
-- Easier to form and recycle
Elastomers (rubber): Good overview
-- Large reversible strains! of applications
and trade names
Thermosets (epoxies, polyesters):
of polymers.
-- Larger E, y, Tapplication
-- Smaller Kc

Chapter 15 - 19
 Chapter 15 -
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 Chapter 15 -
t15_03_pg551
 Chapter 15 -
t15_04_pg553