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Polymer Materials Background Info
Polymer Synthesis
Chain-Reaction / Growth or Addition Polymerization
• Two reactants, monomers and an initiator
– Monomer is typically an alkene or functionally substituted alkene
 Typically has a C=C
– Initiator can be a
 Radical (e.g., peroxide or azo compound, light) ÷Radical Polymerization
 Cation (e.g., Lewis acids) ÷Cationic Polymerization
 Anion (e.g., alkali metals, Lewis bases) ÷Anionic Polymerization
• Three step process
– Initiation
 Free-radical catalyst reacts with a double bonded carbon monomer, beginning the polymer chain
– Propagation
 Double bond of successive monomers is opened up when the monomer is reacted to the
reactive polymer chain
 Growth by C-C bond formation
– Termination
 Another free radical meets the end of the growing chain
• Single bonds of polymer chain more stable than monomer double bonds
– Pi-bond converts to sigma-bond, so chemical energy of system is lowered as chain grows
 Must be activated
– Fast, exothermic reactions that result in high molecular weight polymers
Polymer Synthesis
Step-Reaction / Growth or Condensation Polymerization
• Two different types of monomers with reactive end groups
– Polymer can grow in either direction via carbon-heteroatom (e.g., C-O, C-N) bond
formation
 Typically much slower process
 Often require heat (endothermic)
 Often produces a small molecular by-product (e.g., water)
 Any two species in reaction mixture can react with each other
 Late-stage polymerization often entails groups of shorter chains combining to form longer chains
 Produces lower molecular weight polymers
 Need > 99% conversion for higher molecular weights
– Functionality of monomer can dictate chemical structure
 Di-functional monomers (single reaction site on each side) result in linear chains
 Monomers with higher functionality can result in highly branched structures or cross-linked
networks
• Successful polymerization requires
– Very high purity monomers
– Proper stoichiometry
– No side reactions
– Accessability of mutually reacting groups
Polymerization and
Molecular Weight
• Molecular weight as a function of monomer conversion
Step-Growth Polymerization Chain-Reaction Polymerization
• Molecular weight is a measure of size in a polymer
system
– M
n
is the number average MW
– M
w
is the weight average MW
– Polydispersity = M
w
/ M
n
Chemical Structure (1)
• Linear chains – long continuous chains without
branches
– Result from cationic polymerization
• Branching – large main chains with smaller
molecular chains attached
– Result from chain transfer reactions in radical
polymerization
• Crosslinked networks – primary covalent bonds
formed between separate polymer chain
molecules
• Dendrimers and hyperbranched polymers
– Highly branched structures that have a lot of functional
groups at molecular exterior
Chemical Structure (2)
• Homopolymers – chains with single repeat unit
• Copolymers – chains with two or more types of
monomers
– Statistical or random
Different monomers arranged randomly
– Alternating
Different monomers arranged with alternating order
– Block
Different monomers arranged in groups
– Segmented
Different monomers arranged in repeating blocks
– Graft or comb
Appendages of one type of monomer are bonded to long
chain of the other monomer
• Polymer blends
– Physical mixture of two or more polymers
Physical Structure
• Configuration – the way bonds are
put together in a permanent
arrangement
– Can control through synthesis
– Tetrahedral arrangement of carbon
bonding gives rise to “planar zig-zag”
polymer backbone structure
– Tacticity
Isotactic – all X groups on one side
Syndiotactic – alternating X groups
Atactic – random arrangement of X groups
 Free radical polymerizations normally yield
atactic polymers
• Conformation – the shape the
polymer chain wants to adopt
– Random coil (atactic amorphous)
– Crystal (isotactic or syndiotactic)
Vinyl Family ( CH
2
CH )
X = H PE
X = CH
3
PP
X = Cl PVC
X = PS
x
Microstructure
• Amorphous polymers
– Exhibit no order
Chains are randomly arranged and entangled
 Random coil structures
Crosslinked structure
• Semi-crystalline polymers
– Have amorphous and crystalline domains
Crystallinity never 100%
– Requires regular chemical structure (e.g.,
homopolymers or alternating copolymers)
Branching disrupts ability to crystallize
– Polymer chains pack into crystals in rigid rod
conformation and form lamellae
Lamellae often grow radially from a nucleation site to
form spherulites
If polymer is stretched during crystallization, get fibrillar
microstructure
Thermoplastic Polymers
• Carbon containing polymers synthesized by addition or
condensation polymerization
– Strong covalent bonds along chains
– Weak van der Waals interactions between chains
Secondary bonds overcome by thermal energy such that thermoplastics
can be shaped or pressed into molds at elevated temperatures
 Retain shape upon cooling
• Linear or branched structures
• Amorphous or semi-crystalline
• Examples
– PMMA, PC, PS, polyamides (Nylons)
Thermosetting Polymers
• Cross-linked network structures
– Covalent bonding holding chains together
– Always amorphous
• Even above T
g
, thermosets resist deformation
– Must prepare in molds and/or machine
• Advantages over thermoplastics
– High thermal stability and insulating properties
– High rigidity and dimensional stability
– Resistance to creep and deformation under load
• Examples
– Epoxies, vinyl esters, polyureas, polyurethanes, many
elastomers
Interactions in Polymers
• Intramolecular interactions
– Is chain unit flexible or stiff
-(-CH2-)- units are flexible lower thermal properties
Phenyl ( ) groups are stiff higher thermal properties
– Side groups
Side groups that hinder motion along backbone (steric effects)
Longer side chains and branching typically reduce thermal properties
• Interchain interactions
– Presence of polar groups on chains (e.g., hydrogen bonding)
increases chain-chain attractions, resulting in higher degrees of
crystallinity
Polyamides (Nylons) and polyureas have a
lot of interchain hydrogen bonding
• Polymer-solvent and polymer-polymer interactions
– Flory-Huggins _ parameter used to describe miscibility
Thermo-Mechanical Properties of Polymers
Thermal Properties
• Glass transition temperature, T
g
– Applies to amorphous polymers / domains
– Related to cooperative motion of chains
Below T
g
, chains are immobile
Near T
g
, chains begin to move
Above T
g
, chains are fully mobile
 Amorphous thermoplastics flow as a highly viscous liquid
 Amorphous thermosets soften to elastomeric materials
Can also have sub- T
g
transitions related to short range motions
• Melting temperature, T
M
(semi-crystalline polymers)
– Between T
g
and T
M
, amorphous chains are mobile, but molecular
flow prevented by crystalline regions
Solid polymer with high toughness
– Above T
M
, semi-crystalline polymer also flows
• Typical characterization techniques
– Differential Scanning Calorimetry (DSC)
– Dynamic Mechanical Analysis (DMA)
The Glass Transition
• The glass transition has aspects of a second-order
thermodynamic transition, but is only observed kinetically
in the laboratory
– Typically indicated by a break in a thermodynamic property
vs. T curve or jump in a thermo property derivative with T
 Phenomena depends on thermal history (e.g., cooling rate)
– Is it a real 2
nd
order transition or a kinetic transition?
• Upon cooling from a liquid state above T
g
, molecular
mobility slows down, with a dramatic reduction occuring
far below T
g
in the glassy state
– Dramatic increases in viscosity and relaxation times
• Two main theories
– Free volume (kinetic)
– Configurational entropy (thermodynamic)
• Polymer properties are very sensitive to T
g
and the fact
that the glass is a non-equilibrium material
– Importantly, polymers are used at a very high proportion of
the T
g
 E.g., T
g
of PC = 140ºC = 413 K
 T
ambient
/T
g
~ 0.7
Specific volume (left axis) and thermal
expansion coefficient (right axis) vs.
temperature for poly(vinyl acetate)
Mechanical Properties
• Mechanical Properties
– Polymers are viscoelastic
Temperature and strain rate / frequency
dependent
Can behave anywhere from an elastic solid
to a viscous fluid
– Yield stress often pressure dependent
– Behavior and properties in tension and
compression often different
• Typical characterization techniques
– Dynamic Mechanical Analysis (DMA)
Temperature and frequency dependence
– Traditional quasi-static testing
Tension, compression, shear (as a function
of rate)
Stress relaxation, creep-recovery
Typical engineering stress – strain curves for an amorphous polymer
as a function of temperature (or strain rate)
T <T
g
T<<T
g
T <<<T
g
T >T
g
Mechanical Response Relative to T
g
Rubber Elasticity
Elastomers
• Elastomers are cross-linked networks with T
g
well below the service temperature
– Often are lightly cross-linked polymers
 Low crosslink density, large molecular weight
between crosslinks
 T
g
is well below room temperature
• At very low temperatures, elastomers will
become glassy
– Relatively high modulus and brittle behavior
• Elastomers demonstrate reversible
deformations of as much as 1000 percent
Elastomers
• Elastic deformation can be directly related to
thermodynamics
– Initially, elastomer molecules have high entropy (disordered state)
– With a uniaxial stress applied, molecules align (more ordered
state), reducing entropy
This is in contrast to the enthalpic (energy) change related to changing
distances between atoms in metallic and ceramic materials
– Initially, elastic modulus is low, but as chains start to align, modulus
increases
Non-linear elastic behavior
Define extension ratios
3 3 2 2 1 1
1 1 1 c ì c ì c ì + = + = + =
TdS dU dA ÷ =
Entropy of Deformation
• Elastomers are nearly incompressible v ≈ 0.5
– Therefore, deformation is a constant volume process
– If we define
Then by symmetry 
• Helmholtz free energy:
– Elastic stored energy is small
– Entropy is decreasing with chain alignment
– By considering deformation of a single chain and then summing
over all chains
0 i
i
i
l
l
= ì
TdS dU dA ÷ =
z
x
y
l
z
l
x
l
y
z
x
y
l
z0
l
x0
l
y0
o
1
1 =
z y x
ì ì ì
ì ì = =
0 x x x
l l
2
1
1
|
.
|

\
|
= =
ì
ì ì
z y
f
dl
dS
T
dl
dU
dl
dA
= = ÷ = force
Constant T deformation
dl
dS
T f ÷ =
( )
|
.
|

\
|
÷ + ÷ = ÷ + + ÷ = A 3
2
2
1
3
2
1
2 2 2 2
ì
ì ì ì ì Nk Nk S
z y x
Entropy of Deformation (2)
• For small strains, ì = 1
ì ì d l dl
l
l
x
x
x
0
0
= =
dl
dS
T f ÷ =
( )
|
.
|

\
|
÷ + ÷ = ÷ + + ÷ = A 3
2
2
1
3
2
1
2 2 2 2
ì
ì ì ì ì Nk Nk S
z y x
|
.
|

\
|
÷ + ÷ = ÷ 3
2
2
1
2
ì
ì NkT TdS
|
.
|

\
|
÷ ÷ =
2
0
1
ì
ì
x
l
NkT
f

|
.
|

\
|
÷ =
|
.
|

\
|
÷ ÷ =
2 2
0 0 0
1
1 1
ì
ì
ì
ì o nkT
l l l
NkT
z y x
c
m V
N
n
µ
= =
|
.
|

\
|
÷ =
2
1
1
ì
ì
µ
o
c
M
RT

|
.
|

\
|
+ = =
3
1
1
2
1
ì
µ
c
o
c
M
RT
d
d
E
c
M
RT
E
µ 3
=
c
M
RT
G
µ
=
( ) c ì + =1
General Comments
|
.
|

\
|
+ =
3
2
1
ì
µ
c
M
RT
E
c
M
RT
E
µ 3
=
• These equations were developed just by considering
deformation of individual chains
• By analogy, treating chain linkages as molecular
entanglements rather than chemical crosslinks
e
M
RT
E
µ 3
=
e
M
RT
G
µ
=
o
c, ì
Chains uncoiling and aligning; E decreases
Chains aligning; finally
pulling on C-C bonds
Time for a Break!
Linear Viscoelasticity
Viscosity
• In fluid mechanics, viscosity of a liquid is defined as the ratio
of applied shear stress to shear strain rate
– Newton’s Law of viscosity
• Let’s define tensile viscosity as
– Viscosity is somewhat like a modulus, relating stress to strain rate
rather than stress to strain
For a Newtonian fluid, viscosity is the amount of resistance to shear flow
• Many amorphous solids can be thought of as liquids with
very high viscosities
– Applied stress causes molecules or groups of molecules to move
relative to one another in a time-dependent manner
This is a diffusion process and is enhanced with increasing temperature,
which increases oscillations of atoms about their equilibrium position
¸
t
q
t

=
c
o
q

=
Viscoelasticity
• Polymers, in general, are always viscoelastic at any
temperature due to the nature of the way long chain
molecules behave under stress
– Extremely temperature dependent
• For semicrystalline polymers, elastic behavior due to
– Crystalline regions bonds stretch and bend (enthalpic spring)
– Amorphous regions
Bonds stretch & bend (below T
g
)
Chains uncoil (above T
g
) entropic spring
• Viscous behavior due to diffusive type of motion of polymer
chains
• Polymers will not creep indefinitely and will recover upon
removal of load
– Contrast with metals, for which creep is a plastic deformation
process (no recovery) requiring temperature to activate
mechanisms
Relaxation Processes in Polymers
• Local processes
– Length scales ~ 1 nm
– Rapid rearrangement of a few adjacent monomers or side groups
– Activated at low temperatures
• Cooperative processes
– Length scales ~ 10 nm
– Conformation changes that occur over several monomer sequences
– Activated at higher temperatures
– Basis for rubber elasticity and viscoelastic behavior
• Processes that involve the whole chain
– Length scales ~100 nm
– Depends on molecular weight
– Activated at the highest temperatures
– Control the flow behavior
Linear Viscoelasticity – Creep
• Easiest to understand / define using
creep and stress relaxation as examples
• Creep:
• Define creep compliance:
o
o
1
t
o
o
2
t
¸
1
t t
1
t
2
¸
2
t t
1
t
2
¸
o
t
2
t
1
( ) ( )
2
1 2
1
1 1
o
¸
o
¸ t t
=
( )
( )
o
¸ t
t J =
Shear 
( )
( )
o
c t
t D = Tension 
t=0 t=0
• Just like for linear elasticity, linear viscoelasticity (in
general) is applicable at low strain levels only
• Consider creep-recovery response:
– ¸
1
= time-independent elastic response (glassy)
– ¸
2
= delayed recoverable deformation
– ¸
3
= Newtonian flow
– J
1
represents the “glassy” or unrelaxed response, J
U
Observed at shortest experimentally accessible times
– J
2
+ J
3
represents the “rubbery” or relaxed response, J
R
Observed at times sufficiently long for all relaxation mechanisms to have
occurred
J
3
can be neglected if
 T << T
g
 Polymer is crosslinked or highly crystalline
Linear Viscoelasticity – Creep
o
t
¸
t
¸
1
t=0
¸
2

3
( )
3 2 1
¸ ¸ ¸ ¸ + + = t ( )
3 2 1
J J J t J + + =

• At short times, polymer behaves as a glassy solid and is essentially time independent
– J(t) = J
U
~ 10
-9
Pa
-1
• At very long times, polymer behaves as a rubbery solid and is also time independent
(ignoring viscous flow)
– J(t) = J
R
~ 10
-5
Pa
-1
• At intermediate times, behavior is time dependent (i.e., viscoelastic)
– J
U
< J(t) < J
R
and increases with increasing time
• Assumes only 1 retardation time, t′
– At room temperature, t′ is small for rubbery polymer relative to experimental times
– At room temperature, t′ is large for glassy polymer relative to experimental times
Linear Viscoelasticity – Creep
Linear Viscoelasticity – Stress Relaxation
• Stress relaxation:
• Define stress relaxation modulus:
¸
¸
1
t
¸
¸
2
t
o
1
t
o
2
t
o
¸
t
2
t
1
( ) ( )
2
1 2
1
1 1
¸
o
¸
o t t
=
( )
( )
¸
o t
t G =
Shear 
( )
( )
c
o t
t E =
Tension 
t
1
t
2
t
1
t
2
t=0 t=0
( )
( )
|
|
.
|

\
|
=
t J
t G
1
• At short times, polymer behaves as a glassy solid and is time independent
– G(t) = G
U
~ 10
9
Pa
• At very long times, if viscous flow occurs, stress decays to zero. If no viscous flow,
polymer behaves as a rubbery solid (time independent) and stress decays to a finite
value related to relaxed modulus
– G(t) = G
R
~ 10
6
Pa
• At intermediate times, behavior is time dependent (i.e., viscoelastic)
– G
R
< G(t) < G
U
and decreases with increasing time
• Assumes only 1 relaxation time, t (t ≠ t′ but of same order of magnitude)
– At room temperature, t is small for rubbery polymer relative to experimental times
– At room temperature, t is large for glassy polymer relative to experimental times
Linear Viscoelasticity – Stress Relaxation
• Two main approaches:
– Rheological models
– Boltzmann Superposition
• Since we have looked at rheological models before, we will start here
Mathematical Treatment of Linear Viscoelasticity
2 1 2 1
c c c o o o + = = =
Mechanical Behavior of Materials: Engineering Methods for Deformation, Fracture, and Fatigue, Third Edition,
by Norman E. Dowling. ISBN 0-13-186312-6.
© 2007 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved.
q
M
E
M
Maxwell Model
( )
1 1
,c o ( )
2 2
,c o
E
V
q
V
( )
1 1
,c o
( )
2 2
,c o
o
2 1 2 1
o o o c c c + = = =
M M
M M
dt
d
E dt
d
dt
d
E
q
o o c
c
q o c o
+ =
= =
1
2
2 1 1
Voigt / Kelvin Model
dt
d
E
dt
d
E
V V
V V
c
q c o
c
q o c o
+ =
= =
2
2 1 1
Creep
Stress Relaxation
Mathematical Treatment of Linear Viscoelasticity
q
M
E
M
Maxwell Model
( )
1 1
,c o ( )
2 2
,c o
E
V
q
V
( )
1 1
,c o
( )
2 2
,c o
o
M M
dt
d
E dt
d
q
o o
c
c
+ = =
1

Voigt / Kelvin Model
dt
d
E
V V
c
q c o + =
M
dt
d
q
o
c
o
= =

0
c o
c
V
E
dt
d
= = 0
M M
dt
d
E q
o o
c + = =
1
0

( )
t
o o
t
t
÷
'
= exp
Relaxation time
( )
|
.
|

\
|
'
÷
÷ =
t
o
c
t
E
t
V
exp 1
Recovery (o = 0)
t
c c
'
÷
'
=
t
exp
Retardation
time

V
V
E
q
t =
'
M
M
E
q
t =
Fig. 5.6
Mechanical Behavior of Materials: Engineering Methods for Deformation, Fracture, and Fatigue, Third Edition,
by Norman E. Dowling. ISBN 0-13-186312-6.
© 2007 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved.
Removal of Strain After Stress Relaxation
• Standard Linear Solid (Zener) model combines capabilities
of both Maxwell and Voigt models
– Stress-strain equations of the form:
– Creep:
– Stress relaxation:
Standard Linear Solid Model
dt
d
b b
dt
d
a a
c
c
o
o
1 0 1 0
+ = +
( ) ( ) ( ) | |
R
t
E E E E E t
t
c c c o
÷
'
+ ÷
'
+
'
+ = exp
2 1 1 2 1 
2
2
E
q
t =
'
Mechanical Behavior of Materials: Engineering Methods for Deformation, Fracture, and Fatigue, Third Edition,
by Norman E. Dowling. ISBN 0-13-186312-6.
© 2007 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved.
dt
d
E E E
E E
dt
d o t
o
c
t c
1 2 1
2 1
'
+
+
=
'
+
o
c
t c
'
+
=
'
+
2 1
2 1
E E
E E
dt
d
dt
d
E E E
E E o t
o c
1 2 1
2 1
'
+
+
=
R
R
E E E
2
2 1
2
q q
t =
+
=
( )
(
¸
(

¸

'
÷
÷ + =
t
o o
c
t
E E
t exp 1
2 1

Mechanical Behavior of Materials: Engineering Methods for Deformation, Fracture, and Fatigue, Third Edition,
by Norman E. Dowling. ISBN 0-13-186312-6.
© 2007 Pearson Education, Inc., Upper Saddle River, NJ. All rights reserved.
Standard Linear Solid Model (2)
• Creep-recovery
• Stress relaxation
• Isochronous stress-strain
response
R
R
R
R
• Boltzmann Superposition is useful for expressing
viscoelastic behavior in a mathematical fashion
– Expand beyond constant stresses and strains
– Cyclic behavior
– Relating J(t) and G(t)
• Consider creep response as a function of the entire loading
history:
Boltzmann Superposition
o
t
¸
t
t=0 t
1
t
2
o
1
o
2
( )
( )

2 1 2
1 1
o ¸
o ¸
t t J
t J
÷ =
=
( ) ( )
( ) ( )
}
· ÷
÷ =
+ ÷ + = + + =
t
T
T
d t J
t t J t J
t o t ¸
o o ¸ ¸ ¸  
2 1 1 2 1
– Creep-recovery is then a special case
Apply stress, then apply equal and opposite stress
¸
t t=0 t
1
( ) ( )( )
( ) ( ) ( ) | |
1 1
1 1 2 1 1
o ¸
o ¸ o ¸
t t J t J t
t t J t J
÷ ÷ = ÷
÷ ÷ = =
• In general, assuming that the polymer is stress free at t = 0
– ¸(0) = o(0) = 0
• Strain response is then states as a convolution integral:
• In a complementary fashion, we can represent stress-
relaxation behavior as:
• It can then be shown that G(t) and J(t) are related by
– Exact formal relationships between various viscoelastic functions
are often expressed using Fourier or Laplace transforms
Boltzmann Superposition
( ) ( )
( )
}
÷ =
t
d
d
d
t J t
0
t
t
t o
t ¸
( ) ( )
( )
}
÷ =
t
d
d
d
t G t
0
t
t
t ¸
t o
( ) ( ) t d t J G
t
= ÷
}
0
t t t
• Boltzmann Superposition Principle is an integral
representation of linear viscoelasticity
• We can instead represent linear viscoelasticity in
differential form
• If we only use 1-2 terms on each side, we get equations
such as those we had for various rheological models using
Hookean springs and Newtonian dashpots
Generalized Rheological Models
  + + + = + + +
2
2
2 1 0
2
2
2 1 0
dt
d
b
dt
d
b b
dt
d
a
dt
d
a a
c c
c
o o
o
• If we expand our models to consider an infinite number of
– Maxwell elements in parallel for stress relaxation (¸ = constant)
– Voigt elements in series for creep (o = constant)
– g(t) is the relaxation time spectrum for the material and j(t) is the
retardation time spectrum for the material
• Recall integral representations for general loading:
Rheological Models and Boltzmann Superposition
( ) ( )
( )
}
÷ =
t
d
d
d
t J t
0
t
t
t o
t ¸ ( ) ( )
( )
}
÷ =
t
d
d
d
t G t
0
t
t
t ¸
t o
( ) ( )
}
·
÷
+ =
0
exp t
t
t ¸ ¸ o d
t
g G t
R
( ) ( )
} (
¸
(

¸

÷
÷ + =
t
U
d
t
j J t
0
exp 1 t
t
t o o ¸
( ) ( )
( )
}
÷ + =
t
U
d
d
d
t J J t
0
t
t
t o
t o ¸ ( ) ( )
( )
}
÷ + =
t
R
d
d
d
t G G t
0
t
t
t ¸
t ¸ o

Empirical Representations of
Linear Viscoelasticity
• Vogle-Fulcher-Tammann (VFT)
– Relates variation of average relaxation time with T
• Kohlrausch-Williams-Watts (KWW)
– Distribution of relaxation times described by stretched exponential
– | – describes shape of distribution of relaxation times
 | =1 – simple exponential term gives single relaxation time
 | =0 – no relaxation
 Decreasing | indicates broadening of the distribution of relaxation times
• Relaxation behavior for bulk polymers is well described by VFT and KWW
|
|
.
|

\
|
÷
=
0
0
exp
T T
B
avg
t t
( )
|
t
| |
|
.
|

\
|
=
t
t exp
0
 t
0
= microscopic relaxation time
 B = activation parameter related to fragility
 T
0
~ T
g
- 50K
Dynamic Mechanical Response of Linear
Viscoelastic Materials
• If we apply an oscillatory strain to a
material and measure the stress
response (or vice versa)
– Elastic material – stress and strain will
always be in phase
No hysteresis – all energy stored
– Viscoelastic material – stress will lag strain
by a phase angle, o
Some energy stored, some energy lost
• The modulus, G or E, and compliance, J
or D, are characterized by a storage
component and a loss component and
will be functions of frequency, e
( ) o e o o
e ¸ ¸
+ =
=
t
t
a
a
sin
sin
o
¸
o
¸
t
t
o
Hysteresis = energy loss
Storage and Loss Modulus
( ) ( ) | | o e o o e ¸ ¸ + = = t i t i
a a
exp exp
o, ¸
o
o
a
¸
a
et
o o o cos
a
=
'
o o o sin
a
=
' '
( ) t t t
a a a
e o o e o o o e o o cos sin sin cos sin + = + =
t t e o e o cos sin
' '
+
'
=
in-phase
component
out-of-phase
component
a
a
a
a
a
a
G
G
G
¸
o o
¸
o
¸
o o
¸
o
¸
o
sin
cos
*
=
' '
=
' '
=
'
=
'
= • Complex Modulus 
• Storage Modulus 
• Loss Modulus 
( ) G i G i e G
a
a
i
a
a
' '
+
'
= + = = = o o
¸
o
¸
o
¸
o
o
sin cos
*
o
o
o
tan
cos
sin
*
*
= =
'
' '
G
G
G
G
Loss tangent
G
*
G″
G′
o
Complex Compliance
( ) ( ) | | o e o o e ¸ ¸ + = = t i t i
a a
exp exp
a
a
a
a
J
J
J
o
o ¸
o
o ¸
o
¸
sin
cos
*
=
' '
=
'
=
• Complex Compliance 
• Storage Compliance 
• Loss Compliance 
( ) J i J i e J
a
a
i
a
a
' '
÷
'
= ÷ = = =
÷
o o
o
¸
o
¸
o
¸
o
sin cos
*
J
J
J
J
'
' '
= =
o
o
o
cos
sin
tan
*
*
D i D D
' '
÷
'
=
*
E i E E
' '
+
'
=
*
• For axial stress-strain behavior
*
*
1
G
J =
*
*
1
D
E =
Dynamic Mechanical Response of Linear
Viscoelastic Materials
• Log-log plots of storage modulus and compliance
with frequency have similar look to quasi-static
modulus and compliance vs. time
– Rubbery and glassy behavior independent of
frequency
 Glassy behavior at high frequencies
 Rubbery behavior at low frequencies
 Values correspond to “unrelaxed” and “relaxed”
values, respectively
– Storage modulus and compliance are strong
functions of frequency in viscoelastic region
• Additional information from loss components
– Very small relative to storage components in
glassy and rubbery regions
 tan o ~ o
– Loss becomes significant in viscoelastic region
where loss modulus, loss compliance, and tan o
all have maximum values
– We can calculate energy dissipated as
G dt
dt
d
d U
a
' '
= = = A
} }
2
0
2

¸
o ¸ o
e
t
Rheological Models Applied to Dynamic
Mechanical Response
q
M
G
M
Maxwell Model
M M
dt
d
G dt
d
q
o o
¸
¸
+ = =
1

G
V
q
V
o
Voigt / Kelvin Model
dt
d
G
V V
¸
q ¸ o + =
V
V
E
q
t =
' M
M
G
q
t =
¸
¸
• Doesn’t capture
rubbery part of
storage modulus
• Predicts tan o is
inversely
proportional to e
G′
G″
et
o
t e
et
t e
t e
1
tan
1 1
2 2 2 2
2 2
=
'
' '
=
+
=
' '
+
=
'
G
G
G
G G G
M
M
et o
et
=
'
' '
=
=
' '
=
'
G
G
G G G G
V V
tan
• Dynamic oscillation with SLS model
gives:
– Gives much better representation of
tan o
Goes to zero for both low and high
frequencies
Time constants control peak location
– As frequency gets small, storage
modulus goes to constant value (not
zero)
Standard Linear Solid Model
2
2
E
q
t =
'
dt
d
E E E
E E
dt
d o t
o
c
t c
1 2 1
2 1
'
+
+
=
'
+
( )
( )
( )
R
R
R
R
R
R
R
R
E
E
E E
E E
E
E E
E E
E
t t
t t
o
t t e
t t e
o
t e
t t e
t e
t t e
'
÷
'
= ÷
'
+
÷
'
=
'
' '
=
(
¸
(

¸

+
÷
'
+
=
' '
(
¸
(

¸

+
'
+
+
=
'
2
tan
1
tan
1 1
1
max
2
2 2
2 1
2 1
2 2
2
2 1
2 1
R
R
E E E
2
2 1
2
q q
t =
+
=
¸
Measuring Mechanical Response of Linear
Viscoelastic Materials
• Many techniques have been
developed
– Transient (creep and stress relaxation)
– Low frequency vibration / free oscillation
– High frequency vibration / resonance
– Forced-vibration, non-resonance
– Wave propagation
• To capture widest range of behavior,
need to capture data over a wide
range of frequency / time and
temperature
– Often requires using a combination of
techniques
Longer times (lower frequencies) correspond to higher temperatures
Shorter times (higher frequencies) correspond to lower temperatures
– This concept allows data to be captured over ranges of time or
frequency as a function of temperature and shifted to form a
master curve
• More general concept is the Deborah number
– If observation time short
Polymer appears “cold”
– If observation time long
Polymer appears “warm”
Time-Temperature Superposition Principle
• Linear viscoelasticity
– Under conditions of infinitesimal
strains, time and temperature are
often shown to have equivalent effects
on polymer mechanical behavior
Time-Temperature Superposition
• Data taken over a range of temperature can be shifted horizontally
to form a master curve
– Shift factors, a
T
, based on the assumption that changing temperature is the
same as applying a factor to the time scale
– Pick reference temperature, T
0
, and shift one way for T > T
0
, other way for T < T
0
.
a
T
= f(T)
( )
0 2
0 1
log
T T C
T T C
a
T
÷ +
÷
=
Williams-Landel-Ferry
(WLF) Equation
Other Temperature and Rate Effects
• Yield / flow behavior (e.g., strain softening / hardening)
generally temperature and rate dependent
– Also can be affected by hydrostatic stresses (pressure)
• Ductile-to-brittle transition is a function of
– Rate and temperature (and pressure)
– Test geometry (stress state)
– Polymer structure
Often linked to sub-T
g
transitions related to local chain motion
 Rapidly change with rate / frequency
Time for a Break!
Course Wrap-up and Review for
Final
Objectives for Chapters 5-7
• Chapter 5 – Stress-Strain Relationships and Behavior
– Explore 3D stress-strain relationships for linear elastic deformation in isotropic
materials, analyzing the interdependence of stresses or strains imposed in
more than one direction
 Also studied simple rheological models and some extensions of 3-D stress-strain
relationships to anisotropic materials
• Chapter 6 – Review of Complex and Principal States of Stress and
Strain
– For plane stress, develop the equations for transformation of axes, and apply
to determine principal normal and shear stresses, including graphical
representation by Mohr’s circle; extend to generalized plane stress
– Explore 3D states of stress with emphasis on determining principal normal and
shear stresses, principal axes, and maximum shear stress
– Review complex states of strain using analysis procedures that are analogous
to those for stress
• Chapter 7 – Yielding and Fracture under Combined Stresses
– Develop and employ 3 basic criteria for predicting failure under multiaxial
stresses: maximum normal fracture criterion, maximum shear stress yield
criterion, and octahedral shear stress yield criterion
– Explore fracture of brittle materials under multiaxial stresses in tension or
compression, where either of two modes of fracture may occur (tension or
shear) with the degree of compression affecting the shear mode
Objectives for Chapters 12, 13, & 15
• Chapter 12 – Plastic Deformation Behavior and Models for Materials
– Become familiar with the basic forms of stress-strain relationships, including fitting data
to these relationships and representing them with spring and slider rheological models
– Use deformation plasticity theory to explore the effects of multiaxial states of stress on
stress-strain behavior
– Analyze unloading and cyclic loading behavior for rheological models and for real
materials, including cyclic stress-strain curves
• Chapter 13 –Stress-Strain Analysis of Plastically Deforming Members
– Perform elasto-plastic stress-strain analysis for simple cases of bending and torsion,
considering various forms of stress-strain curves
– Use Neuber’s rule to estimate stresses and strains at notches where there is local
plastic deformation
– Extend the analysis of bending, torsion, and notched members to unloading, residual
stress and strain determination, and cyclic loading
• Chapter 15 – Time-Dependent Behavior: Creep and Damping
– Explore time-dependent behavior and physical mechanisms for creep and damping
– Apply time-temperature parameters to estimate creep-rupture life, and extend creep
analysis to multiaxial stress states
– Extend analysis of elastic and time-dependent deformation of metals and ceramics to
polymeric materials
Final Exam
• Start at 6:00 pm (Dec 9)
• Closed book
• No computers, no cell phones allowed, no cheating
– Calculator okay
• 2-pages of formulas (front and back)
– I will give you any formulas from Appendix A (or any other special
formula) that you would need
• Check your Drexel email for results, final grade
Chapter 5
G
xy
xy
t
¸ =
G
yz
yz
t
¸ =
G
zx
zx
t
¸ =
( ) T T T
T
A = ÷ = o o c
0
Contraints in a mechanical loading situation
Chapter 6
• Principal stresses and strains, Mohr’s Circle
• Plane stress, generalized plane stress, plane strain
Chapter 7
• Failure criteria – fracture vs. yield
• Effective stresses and safety factors
( )
S o S
S
X o o =
o ÷ o o ÷ o o ÷ o = o
/
, , MAX
1 3 3 2 2 1
Chapter 12 – Part 1
• Plastic deformation mechanisms
and critical resolved shear stress
(including temperature effects from
Chapter 15)
• Representing stress-strain curves
with rheological models, Ramberg-
Osgood eq.
• Deformation plasticity theory
– Generalized Poisson’s Ratio
– Effective stress-strain curve
• Focus on equations for elastic,
perfectly plastic and Ramberg-
Osgood
f a CRSS
t t t + =
n
p e
H E
/ 1
,
|
.
|

\
|
+ = + =
o o
c c c c
Chapter 12 – Part 2
• Unloading and cyclic loading
– Bauschinger effect, cyclic hardening, cyclic softening,
cyclic stress-strain curves
– Using rheological models and stress-strain curve
models
Focus on equations for elastic, perfectly plastic, elastic, linear
hardening and Ramberg Osgood
pa
a
a
E
c
o
c + =
n
a a
a
H E
'
|
.
|

\
|
'
+ =
/ 1
o o
c
Chapter 13
• Plasticity in beams and at notches
– Beams – focus on elastical perfectly plastic behavior
– Notches – Neuber rule, elastical perfectly plastic, and
Ramberg-Osgood
• Residual stresses and strains
t
k k k =
c o
Neuber’s Rule
( )
E
S k
t
2
= oc

Chapter 15
• Creep deformation mechanisms / maps
• Strain rate and viscosity,
• Isochronous stress-strain curves
• Differences between plasticity based creep
and linear viscoelastic creep
• Time-temperature parameters (SD, LM)
• Linear viscoelasticity concepts
shear
strain
rates