Chapter 15:

Characteristics Applications &

Characteristics,
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
• i.e. stress-strain behavior of polymers
brittle polymer

TS of polymer ca. 10% that of metals

plastic
elastomer
elastic
l ti modulus
d l
– less than metal

Adapted from Fig. 15.1,

Strains – deformations > 1000% p possible Callister 7e.

(for metals, maximum strain ca. 10% or less)

Chapter 15 - 2
 Temperature
p influence

Chapter 15 -
Strain rate influence: slow => High T
Elastic behavior (σ = Eε )

Increaasing T
Viscoelastic behavior

Viscous behavior

Chapter 15 -
f15 05 pg528
Viscoelastic
relaxation modulus
σ ((tt )
Er (t ) =
ε0
constant strain ε 0

Creepp modulus

σ0
Ec (t ) =
ε (t )
constant stress σ 0

Chapter 15 -
f15_06_pg529
A: highly crystallized
B: Rubber or elastomeric
C: amorphous

Chapter 15 -
 Polymer Fracture
Crazing
– 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 - 7
 Tensile Response: Brittle & Plastic
Near Failure σ(MPa) fibrillar
structure
x brittle failure
near
onset of
failure
necking plastic failure
x
Initial
unload/reload
l d/ l d

ε
aligned, networked
cross- case crystalline
linked regions
case slide
semi- amorphous
crystalline regions crystalline
case elongate regions align

Chapter 15 - 8
 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 (~ 3 times)
-- increases the tensile strength (TS) in the
stretching direction (~2-5 times) Adapted from Fig
Fig. 15
15.13,
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
g
-- reverses effects of drawing.
• Compare to cold working in metals!

Chapter 15 - 9
 Other factors that influence the mechanical
properties
p p of semicrystalline
y polymers
p y
• Molecular Weight…
A
TS = TS ∞ −
Mn
TS ∞ tensile strength with infinite molecular weight
A a constant; M n number - average molecular weight

• Degree of Crystallinity
closely
l l packedk d in
i an ordered
d d andd parallelll l arrangement...
t
Increase tensile molulus, strength, brittleness

• Heat treating for undrawn polymers…

increase in the percent crystallinity, crystal size and
perfection
increase in tensile modulus, yield strength and breittleness
Chapter 15 - 10
 Tensile Response: Elastomer Case
σ(MPa)
x brittle failure •Amorphous,
not easily
crystallize
•Chain bonds
plastic failure
x easily rotate in
responding to
x applied force
elastomer
•Delayed plastic
final: chains
deformation
ε are straight,
t i ht
still
cross-linked
initial: amorphous
p 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 - 11
 Crystallization, melting and glass
transition in polymers
• Crystallization:
-- Nucleation and ggrowth
-- follow Avrami Equation
y=1-exp(-ktn)
-- polyethylene
polypropylene
polycarbonate
polystyrene

• Melting:
-- melting over a range of T
-- Tm depends
p on history
y of the p
polymer,
y , crystallization
y P/T
-- Tm depends on heating rate, higher rate => higher Tm
• Glass transition:
-- transition from rubbery to rigid state
-- reversible at Tg
Chapter 15 - 12
 Thermoplastics vs. Thermosets
T
• Thermoplastics:
viscous rubber
little crosslinking
g
mobile liq id
liquid Tm
-- ductile liquid tough
-- soften w/heating plastic T
g
-- polyethylene
polypropylene
partially
polycarbonate highly
crystalline
polystyrene crystalline
solid
solid
Molecular weight
• Thermosets: 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
-- rubber,
bb epoxies,i
polyester resin, phenolic resin
Chapter 15 - 13
 Melting vs. Glass Transition Temp.
What other factors affect Tm
and Tg?
• Both Tm and Tg increase with
increasing chain stiffness
• Ch i stiffness
Chain tiff iincreaseddbby
1. Bulky sidegroups
2. Polar groups (e.g.Cl)
3. Double bonds chain groups

• Normally 0.5T
0 5Tm <T
Tg <0
0.8T
8Tm

Adapted from Fig. 15.18,

Callister 7e.
Chapter 15 - 14
t15_02_pg547

Chapter 15 -
 Polymer types
Plastics Elastomers Fibers

Relative Rubbery
Rigid High TS

Any degree of amorphous Highly

crystallinity crystallinity
Highly twisted
and high
All molecular ki k d andd
kinked
molecular
structures and coiled
weight
configurations crosslinked
molecular
Work below h i
chains
Tm or Tg , e.g.
crosslinked e.g. polyamide
e.g. Natural (nylon),
polyamide ppolyisoprene
y p polyester
(nylon), (rubber),
polystyren chloroprene
Chapter 15 - 16
 Addition (Chain) Polymerization

– Initiation

– Propagation
P ti

– Termination

Chapter 15 - 17
Condensation (Step)
Polymerization

Chapter 15 - 18
 Polymer Additives
Improve mechanical properties, processability,
durability, etc.
• Fillers
– Added to improve tensile strength & abrasion
resistance, toughness & decrease cost
– ex: carbon
b bl black,
k silica
ili gel,
l woodd flflour, glass,
l
limestone, talc, etc.
• Plasticizers
– Added to reduce the glass transition
temperature Tg
– commonly l added
dd d tto PVC - otherwise
th i it iis b brittle
ittl
• Stabilizers • Colorants
– Antioxidants – Dyes
y or p pigments
g
• Flame Retardants
– UV protectants
– Cl/F & B Chapter 15 - 19
 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
d d ((nott melts)
lt ) when
h h heated
t d
– mold the prepolymer (linear polymer) then allow
further reaction (curing with heating or catalysts) to
form crosslinked or network structures.
– ex: urethane, epoxy

Chapter 15 - 20
 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,
F.W. Billmeyer Jr.,
Jr Textbook of
Polymer Science, 3rd ed.,
John Wiley & Sons, 1984. )
Chapter 15 - 21
 Processing Plastics - Molding
• Injection molding
– thermoplastic & some thermosets
Adapted from Fig. 15.24,
Callister 7e. (Fig. 15.24 is from
F W Billmeyer,
F.W. Billmeyer Jr.,
Jr Textbook of
Polymer Science, 2nd edition,
John Wiley & Sons, 1971. )

Chapter 15 - 22
Processing Plastics – Extrusion

Adapted from Fig. 15.25,

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

Chapter 15 - 23
Fabrication of fibers (spinning)

Melt spinning: molten

Dry spinning:
dissolved in volatile
solvent which will be
evaporated

Wett spinning:
W i i
precipitate solvent
with second solvent

www.madehow.com/Volume-1/Rayon.html

Chapter 15 - 24
Blown-Film Extrusion

Adapted from Fig. 15.26, Callister 7e.

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

Chapter 15 - 25
 Summary
• General drawbacks to polymers:
-- E, σy, Tapplication are generally small.
-- Deformation
D f ti iis often
ft T and d titime d
dependent.
d t
• Thermoplastics (PE, PS, PP, PC):
-- Smaller E, σy, Tapplication
-- Larger Kc (fracture strength)
-- Easier to form and recycle Table 15.3 Callister 7e:
• Elastomers ((rubber): )
-- Large reversible strains! Good overview
of applications
• Thermosets (epoxies, polyesters): and trade names
E σy, Tapplication
-- Larger E, off polymers.
l
-- Smaller Kc

Chapter 15 - 26
 Homework
Reading:

Core Problems: 15.15

15.28

Self help Problems:

Self-help

Chapter 15 - 27