Polymer viscoelasticity:

Dynamic Mechanical
Analysis (DMA)
Professor Maria L. Auad
E-mail: auad@auburn.edu
Phone: 334 844-5459
Office: 103 Textile Building
Rheology:
Rheos the flow; logos the word, the science => Rheology
Bingham 1920
Rheology is the science of flow and
deformation of matter
Rheology is the science of flow and deformation of matter. This definition was
suggested by E. Bingham in 1920 upon a suggestion from Markus Reiner. The
origins can be traced back to Heraklit and his famous expression panta
rei Everything flows
Linear viscoelasticity
During the latter half of the nineteenth century,
scientists began to note that a number of
materials showed time dependence in their
elastic response (silk, gum rubber, etc). After
the elastic period they continued deforming
( creep).
Today we call this time dependent response
VISCOLEASTICITY.
It is typical of all polymeric materials
Time dependent processes:
Viscoelasticity
The response of
polymeric liquids, such
as melts and solutions,
to an imposed stress may
resemble the behavior of
a solid or a liquid,
depending on the
situation.
S
C
t
stic characteri
De

=
n deformatio the of scale time
time material
Deborah Number
Pitch drop experiment
Started in 1927 by University of
Queensland Professor Thomas Parnell.
A drop of pitch falls every 9 years
Pitch can be shattered by a
hammer
Pitch drop experiment
apparatus
http://www.youtube.com/watch?v=CYofp3hWXGM
http://www.youtube.com/watch?v=tZdCGJTQh2w
Poly(ethylene oxide) high molecular
weight in water
A Demonst r at i on of Pol ymer
Vi sc oel ast i c i t y
Introduction to Viscoelasticity
Polymers may exhibit mechanical behavior characteristic
of either solid or a viscous liquid. The actual response
depends upon temperature, in relation to the Tg of the
polymer and to the time scale of the deformation.
Silly Putty: silicone rubber having low Tg
Polymer are Viscoelastic
Viscoleastic behavior may be characterized by a variety of
techniques that record the time dependent response of a polymeric
solid, melt, or solution to a periodic perturbation such as the
application of a sinusoidal strain or an electrical voltage.
Viscoelasticity
Viscoelastic
Ideally elastic behavior
Ideally viscous behavior
If we stretch a crystalline
solid, the energy is stored
in the chemical bonds
If we apply a shear stress
to a fluid, the energy is
dissipated in the flow
Viscoelastic behavior?
-Is silly putty a solid or a liquid?
-Why do some injection molded parts warp?
-What is the source of the die swell phenomena that is often observed in
extrusion processing?
-Expansion of a jet of an
8 wt% solution of
polyisobutylenein decalin
Under what circumstances am I justified in
ignoring viscoelastic effects?
S
t
r
e
s
s
Strain
increasing loading rate
ASTM standards
Stress vs. strain experiments: is the
deformation rate important?
Basics
Viscosity (Newtons Law)
Measure of materials resistance to flow
Modulus (Hookes Law)
Measure of materials resistance to deformation
on application of an external force
Viscosity
rate Shear
Stress
=
Modulus
Strain
Stress
=
Ideal Solid - Elastic
1678: Robert Hooke develop his True Theory of Elasticity
The power of any spring is in the same proportion with the
tension thereof.
o = G
Hookes Law of Elasticity
Hookes Law: Stress = Modulus Strain
Spring:
Mechanical Analogue of
Elastic Response
Ideal Liquid - Viscous
Ideal Liquid
1687: Isaac Newton addresses liquids and steady shearing flow in Principia
The resistance which arises from the lack of slipperiness of the parts of the
liquid, other things being equal, is proportional to the velocity with which the
parts of the liquid are separated from one another.
Dashpot:
Mechanical Analogue of
Viscous Response
Newtons Law of Viscosity
Newtons Law: stress = (coefficient of viscosity) shear-rate
q o

=
Elasticity
(Solids)
Viscous Flow
(Liquids)
dt
dc
q o * =
Viscoelasticity
Most materials behave such that they have a combination of
viscous and elastic responses under stress or deformation.
Materials behave in the linear manner, as described by
Hooke and Newton, only on a small scale in stress or
deformation.
Most Materials
Ideal Solid Ideal Liquid
Time-Dependent Viscoelastic Behavior:
Solid and Liquid Properties of "Silly Putty"
T is short [< 1s]
T is long [24 hours]
Deformation of Solids and the Modulus
All materials change in shape, volume, or both under the
influence of an applied stress.
We can define three kinds of Moduli for a material
Youngs Modulus (Modulus of Elasticity) E
Shear Modulus (Modulus of Rigidity) G
Bulk Modulus B
Shear
Modulus
Youngs
Modulus
o
c
E =
t

G =
Storage and Loss of a Viscoelastic Material
SUPER BALL
TENNIS
BALL
X
STORAGE
LOSS
Viscoelastic Spectrum for a Typical Amorphous
Polymer
Terminal Region
Rubbery
Plateau
Region
Transition
Region
Glassy Region
Loss Modulus (E" or G")
Storage Modulus (E' or G')
Very hard and
rigid solid
Stiff to Soft rubber
Viscoelastic
liquid
Temperature
Deformation
Response
Phase angleo
An oscillatory (sinusoidal)
deformation (stress or strain)
is applied to a sample.
The material response
(strain or stress) is measured.
The phase angleo, or phase
shift, between the deformation
and response is measured.
Dynamic Mechanical Testing
Stress
Strain
o = 0
o = 90
Purely Elastic Response
(Hookean Solid)
Purely Viscous
Response
(Newtonian Liquid)
Stress
Strain
Dynamic Mechanical Testing:
Response for Classical Extremes
Phase angle 0< o < 90
Strain
Stress
Dynamic Mechanical Testing:
Viscoelastic Material Response
Transition from Solid to Liquid
soft
0 20 40 60 80 100
-1
0
1
phase o
Solid
Strain
Stress
Viscoelastic Solid
S
t
r
a
i
n
;

S
t
r
e
s
s
Time
0 20 40 60 80 100
-1
0
1
phase o
Liquid
Strain
Stress
Viscoelastic Fluid
S
t
r
a
i
n
;

S
t
r
e
s
s
Time
stiff
What does change?
Solids and Melts testing
Glass
Transition
Plateau
Flow
(atomic groups)
(main chain)
(chain segments)
(polymer chain)
Time Temperature
Melts testing
Solids testing
Structure and Properties of
Polymers and Fibers
Viscoleastic materials simultaneously exhibit a combination of Elastic and
Viscous behavior
Viscoleasticity refers to time and temperature dependence of
mechanical behavior
Vicoelasticity
Region 1- Glassy Region
Polymer is glassy and frequently brittle (PS), (PMMA).
The youngs modulus is constant over a wide range of polymers.
Modulus ~ 3 10
9
Pa.
The molecular motion are largely restricted to vibration and short rotational
motion. Why?
Region 2 Glass transition region (Tg)
Glass rubber transition (Tg): the amorphous portion of a polymer soften.
The Tg is a type of second order transition.
Typically the modulus drops a factor of about 1000 in a 20-30 C range.
The behavior of polymers in this region is described as leathery.
Often Tg is defined as the temperature where the thermal expansion coefficient
undergoes a discontinuity. This transition could be also measured with a DSC
The basis for the glass transition is the onset of coordinate molecular motion in
the polymer chain. At low temperatures, only vibrational motions are possible,
and the polymer is hard and glassy.
Table 8.4 Glass transition parameters (9,15)
Polymer Tg, C Number of Chain Atoms Involved
Poly(dimethyl siloxane) -127 40
Poly(ethylene glycol) -41 30
Polystyrene +100 40100
Polyisoprene -73 3040
Structure and Properties of
Polymers and Fibers
Region 3- The rubbery Plateau Region
After the glass transition, the modulus become almost constant in the
rubbery plateau (~2 10
6
Pa).
In the rubbery plateau, polymer exhibit a long-range rubber elasticity, which
means that the elastomers can be stretched.
There are two important classes here:
The polymer is linear: the modulus will drop of slowly. The width of the
plateau is governed primarily by the molecular weight of the polymer. The
higher the molecular weight the longer the plateau.
Structure and Properties of
Polymers and Fibers
The polymer is crosslinked: the doted line is followed and a constant modulus
is observed.
The equation for the modulus is: E=3nRT
Where n is de number of active chains in the network.
The modulus increase with T!!!! Why?
Structure and Properties of
Polymers and Fibers
In general, the rapid, coordinate molecular motion in this region is governed
by principles of reptation and diffusion.
When the elastomer is stretched, the chains deform with a series of rapid
motions(this is for amorphous polymers). The model must be altered for
crosslinked systems, since the chain ends are bound at the crosslinks.
If the polymer is semi crystalline the
dashed line is followed . The height
of the plateau is governed by the
degree of crystallinity.
This is so because:
a) The crystalline region behaves as
a filler phase
b) Crystalline region behaves as a
type of physical crosslink, tying
chains together.
The crystalline plateau extends until
the melting point Tm.
Structure and Properties of
Polymers and Fibers
Region 4 Rubber flow region
In this region the polymer is marked by both:
a) Rubber elasticity
b) Flow properties.
They depend on time scale of experiments.
At short times (time~0)
The physical entanglements are not able
to relax, and the material behaves
rubbery
At longer times (time>>>)
The increased molecular motion imparted
by the high temperature permits
chains to move in coordinate manner.
Example Silly Putty (bounces at t~0
and flows at t>>>)
Region 4 does not occur for crosslinked polymers . In this case, region 3
remains in effect up to the decomposition temperature of the polymer
Structure and Properties of
Polymers and Fibers
Region 5 Liquid Flow region
The polymer flows readily, often behaving like molasses.
In this region we can apply the equation for liquids
q = t/ (d/dt ) Newton Law
The increased energy allotted to the chains permits them to reptate out
through entanglements rapidly and flow as individuals molecules.
Injection or extrusion process!!
Modulus versus temperature
Structure and Properties of
Polymers and Fibers
Polymer behavior
Modes of Deformation
Bending
Compressive
Rectangular
Torsion
Tensile
Linear
Rotational
Torsional
Shear
Dynamic Mechanical Analyzer
(DMA)
Rotational Rheometer
Clamps (on RSA III)
S/D Cantilever
Tension-Film
Shear-Sandwich
Compression 3-Point Bending
Immersion
Accessories
Bending Tension Shear - Other
Three point bending
& dual cantilever
Both, dual cantilever
and three point bending
can accomodate samples
with different sample
length up to a maximum
of 45 i.e. 52mm.
Material: 316SST.
Used to test solid bars of stiff
materials, such as composites,
ceramics, glassy and semi-
crystalline polymers.
Accessories
Bending Tension Shear - Other
Film-Fibre
Used to test thin films, such as
magnetic recording tape,
packaging films, individual
fibers and bundles up to a
length of 35mm.
Compression
Used for dynamic compressive
or creep testing of foams,
elastomers, gels and other soft
solids. Plates of 8, 15, 25mm
diameter.
Material: 316SST.
Accessories
Bending Tension Shear - Other
Shear sandwich
Used to test materials, such as polymer melts,
dough, and other soft solids in shear. The shear
surface is 15 mm square and can accommodate
samples of 0.5, 1.0 and 1.5mm thickness.
Optional glass windows are
available for UV curing studies
or simultaneous optical
measurements
light
Accessories
Contact lens fixture
Bending Tension Shear - Other
This fixture is used to test
contact lens material in
bending for internal strains that
cause defected lenses
Material: 316SST.
DMA Clamping Guide
Sample Clamp Sample Dimensions
High modulus metals;
polymer composites;
thermoplastics or
thermosets; brittle solids
(ceramics)
3-point Bend
Cantilever
Torsion
L/T>10 if possible
Elastomers
Cantilever
Shear Sandwich
Tension
L/T>10
only for T>Tg
T<2 mm W<5 mm
Films/Fibers Tension L 10-20 mm
T<2 mm
Foam
Soft Rubber
Compression T>Tg
Structure -Property Applications
DMA
Glass transition
Secondary transitions
Crystallinity
Molecular weight/cross-linking
Phase separation (polymer blends, copolymers,...)
Composites
Aging (physical and chemical)
Curing of networks
Orientation
Effect of additives
Polymer Structure
The mechanical properties of a polymer are a
consequence of
Chemical Composition of the Polymer
Dictates where changes in mechanical properties
occur
Physical Molecular Structure of the Polymer
Dictates how changes in mechanical properties
will occur
A DMA can be used to measure the mechanical
properties of a polymer material and relate them to
differences in composition and molecular structure
(chemical and physical differences).
Structure and Properties of
Polymers and Fibers
Temperature Sweep-DMA-
Polycarbonate
145.98C
0.5
1.0
1.5
T
a
n

D
e
l
t
a
0
100
200
300
400
500
L
o
s
s

M
o
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(
M
P
a
)
0
500
1000
1500
2000
2500
S
t
o
r
a
g
e

M
o
d
u
l
u
s

(
M
P
a
)
20 40 60 80 100 120 140 160 180
Temperature (C)
Sample: P olycarbonate
Size: 17.5000 x 11.8500 x 1.6200 mm
Method: ramp 3C/min
Comment: Amplitude 30m
DMA
File: C:\TA\Data\DMA\Dma-pc.001
Operator: Apps. Lab
Run Date: 02-J an-1997 17:03
Instrument: 2980 DMA V1.0F
Universal V4.1D TA Instruments
The Glass Transition
The glass transition is associated with the onset of
long-range cooperative segmental mobility in the
amorphous phase, in either an amorphous or
semicrystalline polymer.
In general, any factor that affects segmental
mobility will affect T
g
. This includes factors that
influence the nature of the moving segment, chain
stiffness or steric hindrance, and those that
influence the free volume available for segmental
motion.
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second
Edition, Volume I., Academic Press, Brooklyn, New York, P. 508.
The Importance of the Glass Transition Measurement
Below the glass transition temperature, many amorphous
polymers are hard, rigid glasses
modulus is > 10
9
Pa
In the glassy region, thermal energy is insufficient to
surmount the potential barriers for translational and
rotational motions of segments of the polymer molecules.
The chain segments are frozen in fixed positions.
Above Tg, the amorphous polymer is soft and flexible.
modulus in this rubbery region is about 10
5
or 10
6
Pa.
Because of the four orders of magnitude change in modulus
between the glassy and rubbery state, the T
g
can be
considered the most important material characteristic of a
polymer.
Nielsen, Lawrence E., Mechanical Properties of Polymers and Composites, Marcel Dekker, Inc., New York, 1974, p. 19.
Thermoset Additive: Glass
Transition Measurement
Structure and Properties of
Polymers and Fibers
Epoxy Sample
Secondary Transitions
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second
Edition, Volume I., Academic Press, Brooklyn, New York, P. 487.
Glass Transition - Cooperative motion among a large number of
chain segments, including those from neighboring polymer chains
Secondary Transitions
Local Main-Chain Motion - intramolecular rotational motion of
main chain segments four to six atoms in length
Side groupmotion with some cooperative motion from the main
chain
Internal motion within a side group without interference from side
group.
Motion of or within a small molecule or diluent dissolved in the
polymer (eg. plasticizer.)
Advanced solids testing - DMA
-150 -100 -50 0 50 100 150
10
6
10
7
10
8
10
9
0.01
0.1
1
Injection molded ABS part
G' ABS unannealed
G' ABS annealed
M
o
d
u
l
u
s

G
'

[
P
a
]
Temperature T [C]
tan o ABS unannealed
tan o ABS annealed
L
o
s
s

t
a
n

o

Modulus, Glass transition, -transition
T
g
T

Modulus
At T
g
the
relaxation of
the polymer
backbone is in
phase with the
input strain
Increased
energy
dissipation is
reponsible for
the maximum
of tan o
Primary and Secondary Transition in PET Film

119.44C
-55.49C
0.05
0.10
0.15
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T
a
n

D
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t
a

10
100
1000
10000
[




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100
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[




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S
t
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a
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)

-150 -100 -50 0 50 100 150 200 250

Temperature (C)
Sample: PET Film in Machine Direction
Size: 8.1880 x 5.5000 x 0.0200 mm
Method: 3C/min ramp
Comment: 1Hz; 3C/min from -140 to 150C, 15 microns,
DMA
File: A:\Petmd.001
Operator: RRU
Run Date: 27-J an-99 13:56
Universal V2.5D TA Instruments
PBT - Polybutylene terepthtalate in Torsion
Temperature Ramp at 3C/min.
Frequency = 1 Hz
Strain = 0.025%
G
G
tan o
|- transition
-95C
o- transition
T
g
= 58.3C
250.0 -200.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0
temperature (Deg C)
1.000E10
10000
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'

(
P
a
)
1.000E10
10000
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'
'

(
P
a
)
10.00
1.000E-3
0.01000
0.1000
1.000
t
a
n
(
d
e
l
t
a
)
PC - Polycarbonate in Torsion
200.0 -200.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0
temperature (Deg C)
1.000E10
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'

(
P
a
)
1.000E10
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'
'

(
P
a
)
10.00
1.000E-3
0.01000
0.1000
1.000
t
a
n
(
d
e
l
t
a
)
Temperature Ramp at 3C/min.
Frequency = 1 Hz
Strain = 0.025%
G
G
tan o
|- transition
-94.4C
o- transition
T
g
= 154.1C
LDPE: Primary and Secondary Transitions

96.33C
-118.12C
-10.55C
0.05
0.10
0.15
0.20
0.25
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[




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S
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a
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e

M
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(
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)

-150 -100 -50 0 50 100 150

Temperature (C)
Sample: Polyethylene in Tension
Size: 8.4740 x 5.7500 x 1.0000 mm
Comment: 15 microns, 120% Autostrain, -150C to 100C
DMA
File: F:...\DMADATA\Peten.tr1
Operator: RRU
Run Date: 18-J an-99 16:10
Universal V2.5D TA Instruments
Tm
Large scale cooperative Motion:
Disruption of crystalline structure
| -Relaxation
An amorphous phase relaxation
A local-mode, simple, non-cooperative
relaxation process
o -Relaxation
Originates in amorphous phase
Related to glass transition
Zytel - Nylon in Torsion
Temperature Ramp at 3C/min.
Frequency = 1 Hz
Strain = 0.025%
G
G
tan o
- transition
-140.3C
o- transition
T
g
= 81.6C
250.0 -200.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0
temperature (Deg C)
1.000E10
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'

(
P
a
)
1.000E10
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'
'

(
P
a
)
10.00
1.000E-3
0.01000
0.1000
1.000
t
a
n
(
d
e
l
t
a
)
Melt Peak
210C
|- transition
-70.8C
Degradation
Amorphous and Crystalline Structure in
Polymers
Random Chain
100% Amorphous
Fringed Micelle
Crystalline
Effect of % Crystallinity
x x x x x x x x
x
x
x
x
x
x
x
x
x
x
x
x
x
x x
x
x
x
x
x
20 40 60 80 100 120 140 160
0.01
0.1
1.0
Temperature (C)
T
a
n

o
0.1
0.5
1.0
5
10
x x x x
x x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
x
20 40 60 80 100 120 140 160
0.01
0.1
1.0
Temperature (C)
T
a
n

o
0.1
0.5
1.0
5
10
AMORPHOUS PET
CRYSTALLINE PET
Effect of Branching on Polymer Properties -
Polyethylene Example
HDPE
LLDPE
LDPE
Cowie, J .M.G., Polymers: Chemistry & Physics of Modern Materials, 2nd Edition,
Blackie academic & Professional, and imprint of Chapman & HallBishopbriggs, Glasgow, 1991p. 342-345
ISBN 0 7514 0134 X
Structurally regular chain with few branch points.
Polymer chains can pack efficiently resulting in a highly
crystalline material with high density
Highly branched with much lower crystalline content
and density compared to HDPE
Can be produced to have a chain with a controlled number
of short chain branches yielding densities intermediate between
HDPE and LDPE.
Property LDPE LLDPE HDPE
Melting Point (K) 383 393-403 >403
Density (g/cm
3
) 0.92 0.92 - 0.94 0.94 - 0.97
Film Tensile 24 37 43
strength (Mpa)
Effect of % Crystallinity on
Modulus
The major effect of the crystallite in a sample is to act as a crosslink in the
polymer matrix. This makes the polymer behave as though it was a crosslinked
network, but as the crystallite anchoring points are thermally labile, they
disintegrate as the temperature approaches the melting temperature, and the
material undergoes a progressive change in structure until beyond T
m
, when it is
molten
0% Crystallinity
(100% Amorphous)
25%
40%
65%
M.
P.
Temperature
The Main Points
1. Crystallinity only affects the
mechanical response in the
temperature range T
g
to T
m
, and
below T
g
the effect on the modulus
is small.
2. The Modulus of a semi-
crystalline polymer is directly
proportional to the degree of
crystallinity, and remains
independent of temperature if the
amount of crystalline order
remains unchanged.
PET Bottle Resin - Polyethylene
terepthalate -1
st
. Run
Temperature Ramp at 3C/min.
Frequency = 1 Hz
Strain = 0.025%
G
G
tan o
|- transition
-56.62C
o- transition
T
g
= 88.0C
250.0 -200.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0
temperature (Deg C)
1.000E10
1.000E6
1.000E7
1.000E8
1.000E9
G
'

(
P
a
)
1.000E10
1.000E6
1.000E7
1.000E8
1.000E9
G
'
'

(
P
a
)
0.4000
0
0.05000
0.1000
0.1500
0.2000
0.2500
0.3000
0.3500
t
a
n
(
d
e
l
t
a
)
Cold
Crystallization
PET Bottle Resin - Polyethylene terepthalate
PET After Temperature
Ramp Scan
(Cold Crystallization)
Pressed PET
Bottle Resin
250.0 -200.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0
temperature (Deg C)
1.000E10
10000
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'

(
P
a
)
1.000E10
10000
1.000E5
1.000E6
1.000E7
1.000E8
1.000E9
G
'
'

(
P
a
)
2.250
0
0.2500
0.5000
0.7500
1.000
1.250
1.500
1.750
2.000
t
a
n
(
d
e
l
t
a
)
PET Bottle Resin - Repeat Run After Cold
Crystallization 2
nd
. run
Temperature Ramp at 3C/min.
Frequency = 1 Hz
Strain = 0.025%
G
G
tan o
o- transition
T
g
= 103C
Melt
T
m
= 240C
PET Bottle Resin - Comparison
of G
Temperature Ramp at 3C/min.
Frequency = 1 Hz
Strain = 0.025%
250.0 -150.0 -100.0 -50.0 0 50.0 100.0 150.0 200.0
temperature (Deg C)
1.000E10
1.000E6
1.000E7
1.000E8
1.000E9
G
'

(
P
a
)
Cold
Crystallization
Repeat Run After Cold
Crystallization
Initial Scan on Pressed
Resin
Aging Affects Modulus, Damping and Glass
Transition of Elastomer in Tension
Temperature (C)
S
t
o
r
a
g
e

M
o
d
u
l
u
s

(
G
P
a
)
As-Received
Aged 7 days @ 150C
Molecular Structure - Effect of Molecular
Weight
Molecular Weight has practically no effect on the
modulus below T
g
.
Tg and the drop in modulus are also nearly
independent of MW if the MW is high enough for
applications where mechanical strength becomes
important
With the exception of low molecular weight (below
M
c
where there are no entanglements), the rubbery
plateau region above T
g
is strongly dependent on
MW. In the absence of true crosslinks, the behavior
is determined by entanglements. The length of the
rubbery plateau is a function of the number of
entanglements per molecule.
Nielsen, Lawrence E., Mechanical Properties of Polymers and Composites, Marcel Dekker, Inc., New York, 1974, p. 51-52.
Molecular Structure - Effect of Molecular
Weight
Rubbery
Plateau
Region
Transition
Region
Glassy Region
Temperature
MW has practically
no effect on the
modulus below Tg
Low
MW
Med.
MW
High
MW
Molecular Structure - Crosslinking
Linear polymers can
be chemically or
physically joined at
points to other chains
along their length to
create a crosslinked
structure.
Chemically
crosslinked systems
are typically known
as thermosetting
polymers because
the crosslinking
agent is heat
activated.
Ward, I.M., Hadley, D.W., An Introduction to the Mechanical Properties of Solid Polymers, J ohn Wiley & Sons Ltd., New York, 1993, p.2.
Effect of Crosslinking on T
g
Introducing crosslinks into a polymer will
proportionally increase the density. As the density of
the sample increases, molecular motion in the sample
is restricted causing an rise in the glass transition
temperature.
For low values of crosslink density, T
g
can be found to
increase linearly with the number of crosslinks.
For high crosslink density the T
g
is broad and not well
defined.
Cowie, J .M.G., Polymers: Chemistry & Physics of Modern Materials, 2nd Edition,
Blackie academic & Professional, and imprint of Chapman & HallBishopbriggs, Glasgow, 1991 p.262
ISBN 0 7514 0134 X
Effect of Crosslinking
120
160
300
1500
9000
30,000
M = MW between
crosslinks
c
Temperature
Effect of Plasticizer
Plasticizers are generally low molecular weight organic
additives which are used to soften rigid polymers
Plasticizers are typically added to a polymer for two
reasons:
1. To lower the T
g
to make a rigid polymer
become soft and rubbery.
2. To make the polymer easier to process.
Plasticizers make it easier for a polymer to change
molecular conformation.
Therefore plasticizers will have the effect of:
1. Lowering the glass transition temperature
and
2. Broadening the tan o peak
Effect of Plasticizer on Vinyl
Flooring
Moisture affects performance
100 110 120 130 140 150
10
8
10
9
10
10
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
Dry sample
Moist sample
Nylon: Moisture effect on DMA trace
M
o
d
u
l
u
s

E
'
;

E
'
'

[
P
a
]
Temperature T [
o
C]

L
o
s
s

t
a
n

o
Fibers made
from moist
pellets show:
- Higher
modulus in the
transition
region (cross
linking)
- Lower glass
transition tan d
peak
(increased
crystallinity)
Moisture enhances crosslinking
reactions and crystallization kinetics
Effect of Filler on Modulus
20 40
60 80 100 120 140 160
TEMP. (C)
60% mica
40% mica
60% asbestos
40% asbestos
20% mica
20% asbestos
20% calcium carbonate
polystyrene control
Nielson, L. E., Wall, R. A., and Richmond, P. G., Soc. Plastics Eng. J., 11, 22 (1966)

Morphology
Composition, Processing, and Interphase determine the
morphology of blends.
droplets
laminar
fibers
droplets in drops
Co-continuous phase
Blending of Amorphous Polymers
Blending may produce a polymer whose
modulus-temperature curve shows two
transition regions
If the polymers blended are completely
compatible, then the blend behaves like
an ordinary amorphous polymer with a
single transition region and an
intermediate glass transition temperature.
Tobolsky, A.V., Properties and Structure of Polymers, J ohn Wiley & Sons, Inc., New York, 1967, p.81.
Compatibility and in-compatibility
Properties of immiscible blends (mostly ductility and
toughness) are often less attractive than those of either
components, due to incompatibility at the interface
Dispersion poor, because interfacial tension favors
coalescence
Stress transfer poor, because poor adhesion ate the
interface
Energy take up by the continuous phase cannot be
dissipated in the rubbery phase
Solution compatibilization
Compatibilization and co-polymerization
A compatibilizer improves the adhesion of two
phases and stabalizes the morphology
Compatibilizers can be:
Bock copolymers tie two phases
together => better energy transfer
Compounds, which lower the
surface energy at the phase
boundary => facilitates creating
new surface and provides better
dispersion
Immicible Blends PS/SB
-50 0 50 100 150
0.01
0.10
1.0
10
Temperature (C)
L
o
g
a
r
i
t
h
m
i
c

d
e
c
r
e
m
e
n
t
S
h
e
a
r

m
o
d
u
l
u
s
,

G

10
9
10
8
10
7
10
6
10
5
Polymer Blend - Aerospace
Coating
Temperature (C)
100 % Polymer A
100%
Polymer B
Polymer Blend
A +B
Polymer A
Polymer Blend: A +B
Polymer B
E
l
a
s
t
i
c

M
o
d
u
l
u
s
Polymer Blend - Aerospace Coating

89.77C
76.19C
46.46C
-0.5
0.0
0.5
1.0
1.5
T
a
n

D
e
l
t
a
-25 0 25 50 75 100 125
Temperature (C)
Polymer A
Polymer Blend: A +B
Polymer B
Universal V2.5D TA Instruments
100 % Polymer A
100%
Polymer B
Polymer Blend
A +B