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Mechanical Properties
Outline:
Mechanical properties
Stress-Strain Behavior
Deformation of Semicrystalline Polymers Deformation of Semicrystalline Polymers
Crystallization, Melting, Glass Transition
Thermoplastic and Thermosetting Polymers
Viscoelasticity
D f ti d El t
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Deformation and Elastomers
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Polymer Crystallinity
Ex: polyethylene unit cell
Crystals must contain the
Adapted from Fig.
14.10, Callister 7e.
y
polymer chains in some way
Chain folded structure
Adapted from Fig.
14.12, Callister 7e.
Polymer Crystallinity
crystalline
Polymers rarely exhibit 100% crystalline
Too difficult to get all those chains aligned
%Crystallinity: how much
is crystalline.
-- TS and E often increase
with % crystallinity.
-- Annealing causes
crystalline regions
crystalline
region
amorphous
region
y g
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, J ohn Wiley
and Sons, Inc., 1965.)
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Stress Strain Behavior (I)
A: Brittle Polymer
B: Plastic Polymer
C: Elastomer C: Elastomer
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Stress-strain behavior can be
brittle (A), plastic (B), and highly elastic (C)
Curve C is totally elastic (rubber-like elasticity). This class of
polymers - elastomers
Mechanical Properties
1 MPa =145 psi
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Mechanical Properties
Mechanical Properties
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Mechanical Properties
Mechanical Properties
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.
A polyethylene sample necking under
tension.
Mechanical Properties
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Mechanical Properties
Toughness
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Mechanical Properties
Stress Strain Behavior (III)
Moduli of elasticity
Polymers: ~ 10 MPa - 4 GPa
Metals: ~ 50 - 400 GPa
Tensile strengths
Polymers: ~ 10 - 100 MPa
Metals: 100s - 1000s MPa
El ti
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Elongation
Polymers: up to 1000 % in some cases
Metals: < 100%
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Stress Strain Behavior (II)
Elastic Modulus defined as for metals
Ductility (%EL) defined as for metals
Yield strength For plastic polymers (B)
maximum on curve just after the elastic region (different from metals) j g ( )
Tensile strength is defined at the fracture point and can be lower than the yield
strength (different from metals)
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Mechanical Properties
i.e. stress-strain behavior of polymers
brittle polymer
plastic
elastomer

FS
of polymer ca. 10% that of metals
elastic modulus
less than metal
Strains deformations >1000% possible
(for metals, maximum strainca. 100% or less)
Adapted from Fig. 15.1,
Callister 7e.
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Tensile Response: Brittle & Plastic
brittle failure
plastic failure
(MPa)
x
fibrillar
structure
near
failure
onset of
necking
Near Failure
plastic failure

x
crystalline
Initial
aligned,
cross
networked
case
unload/reload
crystalline
regions
slide
crystalline
regions align
semi-
crystalline
case
cross-
linked
case
case
amorphous
regions
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.)
Stress-strain curves
adapted from Fig. 15.1,
Callister 7e. Inset
figures along elastomer
Tensile Response: Elastomer Case
(MPa)
brittle failure
x
curve (green) adapted
from Fig. 15.15, Callister
7e. (Fig. 15.15 is from
Z.D. J astrzebski, The
Nature and Properties of
Engineering Materials,
3rd ed., J ohn Wiley and
Sons, 1987.)

x
final: chains
are straight,
still
cross-linked
elastomer
plastic failure
x
Compare to responses of other polymers:
-- brittle response (aligned, crosslinked & networked polymer)
-- plastic response (semi-crystalline polymers)
initial: amorphous chains are
kinked, cross-linked.
Deformation
is reversible!
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Mechanical properties of polymers
change dramatically with temperature,
going from glass-like brittle behavior at
low temperatures to a rubber-like
behavior at high temperatures.
Polymers are also very sensitive to the
t f d f ti ( t i t )
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rate of deformation (strain rate).
Decreasing rate of deformation has the
same effect as increasing T.
Stress Strain Behavior (IV)
Temperature increase leads to:
Decrease in elastic modulus
Reduction in tensile strength g
Increase in ductility
polymethyl methacrylate (PMMA)
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Stress-Strain Test
specimen specimen
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machine
Tensile Test
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Important Mechanical Properties
from a Tensile Test
Young's Modulus: This is the slope of the linear
portion of the stress-strain curve, it is usually
ifi t h t i l t t k l specific to each material; a constant, known value.
Yield Strength: This is the value of stress at the
yield point, calculated by plotting young's modulus
at a specified percent of offset (usually offset =
0.2%).
Ultimate Tensile Strength: This is the highest
25
g g
value of stress on the stress-strain curve.
Percent Elongation: This is the change in gauge
length divided by the original gauge length.
Melting vs. Glass Transition Temp.
What factors affect T
m
and T
g
?
Both T
m
and T
g
increase with ot
m
a d
g
c ease t
increasing chain stiffness
Chain stiffness increased by
1. Bulky sidegroups
2. Polar groups or
sidegroups
3. Double bonds or aromatic
h i chain groups
Regularity (tacticity) affects
T
m
only
Adapted from Fig. 15.18,
Callister 7e.
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The Glass Transition
The Glass Transition
The glass transition is a property of only the amorphous portion of a
semi-crystalline solid
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. The crystalline portion remains crystalline during
the glass transition.
At a lowtemperature the amorphous regions of a polymer are in the glassy At a low temperature the amorphous regions of a polymer are in the glassy
state. In this state the molecules are frozen on place. They may be able to
vibrate slightly, but do not have any segmental motion in which portions of
the molecule wiggle around. In the glassy state, the motion of the red
molecule in the schematic diagram at the right would NOT occur. When the
amorphous regions of a polymer are in the glassy state, it generally will be
hard, rigid, and brittle.
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The Glass Transition
If the polymer is heated it eventually will reach its glass transition
temperature. At this temperature portions of the molecules can start to
wiggle around as is illustrated by the red molecule in the diagram above.
The polymer nowis in its rubbery state The rubberystate lends softness The polymer now is in its rubbery state. The rubbery state lends softness
and flexibility to a polymer.
You may have experienced the glass transition of chewing gum. At body
temperature the gum is soft and pliable, which is characteristic of an
amorphous solid in the rubbery state. If you put a cold drink in your mouth
or hold an ice cube on the gum, it becomes hard and rigid. The glass
transition temperature of the gum is somewhere between 0
o
C and 37
o
C.
The Glass Transition
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The Glass Transition
The Glass Transition
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Factors Influencing T
g
Factors Influencing T
g
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Factors Influencing T
g
Stronger intermolecular forces lead to a higher T
g
. PVC has
stronger intermolecular forces than polypropylene because
Intermolecular Forces
stronger intermolecular forces than polypropylene because
of the dipole-dipole forces from the C-Cl bond.
Factors Influencing T
g
Pendant Groups
1. Bulky pendant groups, such as a benzene ring, can
catch on neighboring chains like a "fish hook" and restrict
rotational freedom
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This increases T rotational freedom
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. This increases T
g
.
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Factors Influencing T
g
2. Flexible pendant groups, such as aliphatic
chains, tend to limit how close chains can pack.
This increases rotational motion and lowers T
g
.
g
Factors Influencing T
g
The presence of cross-links between chains restricts rotational motion and
raises Tg.
Cross-Linking
Plasticizers
Plasticizers are low molecular weight compounds added to plastics to increase
their flexibility and workability. They weaken the intermolecular forces between
the polymer chains and decrease T
g
. Plasticizers often are added to semi-
crystalline polymers to lower the value of T
g
below room temperature. In this
case the amorphous phase of the polymer will be rubbery at normal
temperatures, reducing the brittleness of the material.
Plasticizers are added to the plastic used for automobile upholstery. In older Plasticizers are added to the plastic used for automobile upholstery. In older
automobiles, the plasticizer may be distilled from the upholstery during hot
weather so that it becomes brittle over time.
Some plasticizers have been identified as major health and environmental
problems. Before 1977, Polychlorinated biphenyls (PCBs) were used as
plasticizers in paints and plastics. Because they are toxic and possible
endocrine disruptors, PCBs no longer are used.
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Crystallization, Melting, Glass Transition
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Dependence of melting and glass transition
temperatures and polymer properties on molecular
weight
Thermoplastics:
-- little crosslinking
-- ductile
Thermoplastics vs. Thermosets
Callister,
Fig. 16.9
T
T
m
mobile
li id
viscous
liquid
rubber
t h
-- soften w/heating
-- polyethylene
polypropylene
polycarbonate
polystyrene
Thermosets:
AdaptedfromFig 15 19 Callister 7e (Fig 15 19is fromF W Billmeyer
Molecular weight
T
g
liquid tough
plastic
partially
crystalline
solid
crystalline
solid
-- 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,
J r., Textbook of Polymer Science, 3rd ed., J ohn Wiley and Sons, Inc.,
1984.)
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Polymer Additives
Improve mechanical properties, processability,
durability, etc.
Fillers 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
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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
ld th l th ll f th ti 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, J r., Textbook of
Polymer Science, 3rd ed.,
J ohn Wiley & Sons, 1984. )
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Processing Plastics - Molding
Injection molding
thermoplastic &some thermosets thermoplastic & some thermosets
Adapted from Fig. 15.24,
Callister 7e. (Fig. 15.24 is from
F.W. Billmeyer, J r., Textbook of
Polymer Science, 2nd edition,
J ohn Wiley & Sons, 1971. )
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Processing Plastics Extrusion
Adapted from Fig. 15.25,
Callister 7e. (Fig. 15.25 is from
Encyclopdia Britannica, 1997.)
Blown-Film Extrusion
Adapted from Fig. 15.26, Callister 7e.
(Fig. 15.26 is from Encyclopdia
Britannica, 1997.)