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 Elasticity resistance to flow (damping) ability to revert back to original shape
Viscoelastic Response
Stress
E 1

Elastic vs viscoelastic response

Elastic Response
Stress

Strain

Strain

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) Loss tangent (tan )

Energy converted to heat during deformation Visco of viscoelastic Applied
Stress

= phase lag between applied stress and measured strain Tan = E/E

Strain

time

Transition Temperatures
Glass Transition Temperature (Tg)
Definition: Transition from bond stretching to long range molecular motion Helps dictate mechanical properties of material at different temperatures
glassy rubbery

Melting Temperature (Tm)

Definition: point at which heat vibration is enough to break bonds in crystal lattice Polymer must be semicrystalline to have a Tm

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

Tg indicated by major change in curves
Large drop in log E curve Peak in Tan curve

Tm indicated by drop in log E curve beyond Tg

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 Aliphatic Isocyanate Increase E Increase Tg Higher E Lower E
Hard Segment Domains

Increase hard segment content

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 Tg because less energy Soft Segment is needed for motion Matrix

Outline
DMA introduction DMA of segmented polyurethanes

Testing Example
Test parameters Results

Testing Example - DMA of PESU

Poly(ester urethane)

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

DMA of PESU
PESU Storage Modulus
10000 1000

Tg-SS ~ -30C

log E' (MPa)

100 10 1 0.1 -90

-60

-30

30

60

90

120

150

Temperature (C)

Our DMA
TA Instruments RSA3 Uses direct drive linear motor to apply cyclic deformation Full temperature range:
-150C to 600C
LN2 cooler

LN2 cooling system Compression tests on soft materials

Gels, elastomers

Furnace

www.tainstruments.com

Cyclic tensile tests on thin films

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 Tg, Tm, 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