Dynamic Mechanical

Analysis
Dave Dempsey
September 4, 2009
Outline
DMA introduction
Viscoelasticity
DMA overview
Transition Temperatures
Polymer structure effects
DMA of segmented polyurethanes
Testing example
Viscoelasticity
Viscoelastic materials exhibit characteristics
of both viscous and elastic materials
Viscosity resistance to flow (damping)
Elasticity ability to revert back to original
shape
Elastic vs viscoelastic response
E
1
Stress
Strain
Elastic
Response
Stress
Strain
Viscoelastic
Response
DMA Overview
Small cyclic deformation applied
Study material responses to:
Stress
Temperature
Frequency
Storage modulus (E) elastic property
Loss modulus (E) viscous property
Loss tangent (tan )
DMA Overview
Complex dynamic modulus (E)
E = E + iE
Storage modulus (E)
Energy stored elastically during deformation
Related to elastic modulus of solids
Elastic of viscoelastic
Loss modulus (E)
Energy converted to heat during deformation
Visco of viscoelastic
Loss tangent (tan )
= phase lag between applied stress
and measured strain
Tan = E/E

Applied
Stress
Strain
time
Transition Temperatures
Glass Transition Temperature (T
g
)
Definition: Transition from bond stretching to long range
molecular motion
Helps dictate mechanical properties of material at
different temperatures
glassy rubbery
Melting Temperature (T
m
)
Definition: point at which heat vibration is enough to
break bonds in crystal lattice
Polymer must be semicrystalline to have a T
m
DMA Procedure
Cut sample with known geometry
Load sample into clamp inside DMA furnace
Set start temperature, finish temperature, and
step
Apply same cyclic strain through entire
temperature range
DMA records material response to deformation
and determines: E, E, Tan
Identify transition temperatures based on
noticeable changes in curves
Identifying Transition
Temperatures
T
g
indicated by major change in curves
Large drop in log E curve
Peak in Tan curve
T
m
indicated by drop in log E curve beyond T
g
Second large drop in log E curve (for homopolymers)
Gradual decline in melting region for amorphous
Polymer Structure Effects
Motion Restriction
Crosslink Density
Replaces melting transition with rubber plateau
Increased density higher plateau
Crystallinity
Elastic response between glass and melt transitions
Increased crystallinity increased elastic response
Molecular Weight
Elastic response in melting transition
Increased MW increased elastic response
Polymer Structure Effects
Outline
DMA introduction
DMA of segmented
polyurethanes
Hard segment effects
Soft segment effects
Testing example
Hard Segment Effects
Hard Segment Type
Aromatic Isocyanate Higher E
Aliphatic Isocyanate Lower E
Increase hard segment content
Increase E
Increase T
g
Hard Segment
Domains
Soft Segment Effects
Increase in soft segment length
Increases degree of crystallinity
Causes increase in E
Increase in MW:
Increases phase separation because of increase in
mobility
Decrease in T
g
because less energy
is needed for motion
Soft Segment
Matrix
Outline
DMA introduction
DMA of segmented polyurethanes
Testing Example
Test parameters
Results
Testing Example - DMA of PESU
Cut samples of known size (10mm x 5mm x 0.3mm)
Testing Parameters
2% Strain
Frequency = 1Hz
T = -90C to 150C
T = 5C/min
Analyzed plots:
Log E vs T
Log E vs T
Tan vs T
TA Instruments Q800
Poly(ester urethane)
DMA of PESU
PESU Storage Modulus
0.1
1
10
100
1000
10000
-90 -60 -30 0 30 60 90 120 150
Temperature (C)
l
o
g

E
'

(
M
P
a
)
T
g-SS
~ -30C
Our DMA
TA Instruments RSA3
Uses direct drive linear
motor to apply cyclic
deformation
Full temperature range:
-150C to 600C
LN
2
cooling system
Compression tests on soft
materials
Gels, elastomers
Cyclic tensile tests on thin
films
www.tainstruments.com
LN
2
cooler
Furnace
Summary
DMA can determine both elastic (E) and viscous
(E) properties of polymers
Major temperature transitions can be found with
resultant E, E, and tan curves
T
g
, T
m
, and resultant mechanical responses
dependent on polymer structure
Mechanical response of segmented polyurethanes
dependent on both hard and soft segments
Demonstrated DMA procedure with a temperature
sweep of PESU in tensile mode
Acknowledgements
Dr. Elizabeth Cosgriff-Hernandez
Dr. Melissa Grunlan
Dr. H. J. Sue
Hugh Benhardt
Paul Turner
Bobby Moglia
Mary Beth Browning
Nick Sears
Thomas Wilems
Tyler Touchet
Ahmed Haque