Rheology of Polymers

Prof RD Sanderson
UNESCO Associated Centre
for Macromolecules & Materials
University of Stellenbosch, Stellenbosch
DMA
Dynamic Mechanical Analysis

!A Dynamic Mechanical Analyzer

(DMA) measures changes in
mechanical behaviour, such as
modulus, and damping, as a function
of temperature, time, frequency,
stress or combinations of these
parameters

Prof RD Sanderson,
University of Stellenbosch
How does DMA-DEA work?
! Simultaneous DMA-DEA results are
obtained using traditional DMA
parallel plates (or cup and plates) as
electrodes for the DEA

Prof RD Sanderson,
University of Stellenbosch
 What do DMA-DEA results
mean?
! Polymer viscosity is measured by DMA and
DEA in different ways, but both reflect the
same fundamental material property

The relationship between traditional DMA viscosity

(measured using parallel plates or cup and plates)
and DEA viscosity (derived from the dielectric loss
factor) is a function of polymer chain segment
mobility and free volume

Prof RD Sanderson,
University of Stellenbosch
 Faster and more accurate
results
! More can be obtained from Simultaneous DMA-
DEA
! Faster analysis because there is only a single
run
The sample has the same thermal and mechanical
history because the same sample and preparation is
used
Both mechanical and dielectric properties are
determined

Prof RD Sanderson,
University of Stellenbosch
 Analyze Many Sample Shapes
and Types

! In-process, process emulation, and laboratory bench

analysis can be performed using the multiple measuring
systems and geometries
Prepegs using parallel plates
Gels, pastes and viscous resins using the plate and tray
Solvent containing and saturated solvent systems using the
sintered parallel plate
Curing or samples with very low viscosities using the cup and
plate
Molecular transitions using the chip sensor (IC sensor)

Prof RD Sanderson,
University of Stellenbosch
Perform Many Types of Analysis
! Evaluate final products, emulate processes,
characterize basic mechanical properties using the
broad analytical capability offered by the multiple
modes of operation
Evaluate final products with a Youngs flexural modulus using
the Creep-Ramp (static stress scan) and the DEA
Test new formulations or new process parameters in-process
or in the laboratory using the Temp/Time scan mode and the
DEA. Emulate process conditions both in the laboratory and in
the process simultaneously using the Temp/Time scan mode
and the DEA

Prof RD Sanderson,
University of Stellenbosch
Perform Many Types of Analysis

! Characterize basic mechanical properties

such as elasticity (modulus) or damping
(tangent delta) using the Dynamic Stress
scan mode and the DEA
! Evaluate new incoming materials for
differences in molecular structure using
the Frequency scan mode and the DEA

Prof RD Sanderson,
University of Stellenbosch
 Completely Characterize Cure

! Evaluate the degree of cure advancement in

resins using the glass transition (Tg) of
uncured or staged resins
Optimize the flow into the mould, eliminate gas bubbles or
voids using the minimum viscosity
Optimize the forming, lay-up or working time using the
time between the minimum viscosity and the gel point
Define the end of working time and the point when the
modulus begins to increase using the gel point

Prof RD Sanderson,
University of Stellenbosch
 Completely Characterize Cure
! Determine the effects of storage or handling of the prepreg
using the modulus decrease due to stress relief
Optimize post bake operations using the cure rate after
vitrification
Assure fully cured products using by characterizing the
product until end of cure
Determine the maximum rate of modulus growth,
reaction order or reaction kinetics using the slope
calculations on the modulus
Find the best time to de-mould using the vitrification
point
Prof RD Sanderson,
University of Stellenbosch
 Summary

! Polymers are useful because of their

unique physical properties, but
their behaviour is difficult to predict
they are difficult to process
! Thermal Analysis is useful for describing
physical properties of polymer, it is used
to
optimize product processing
predict product behaviour

Prof RD Sanderson,
University of Stellenbosch
Application Examples
! Vicat and softening point determinations
! HDT and HDTUL determinations
! Modulus determinations
! Quality factor determinations
! Annealing
! Filler
! Orientation
Prof RD Sanderson,
University of Stellenbosch
The DMA 7e Can Perform
Many Tests
! Temperature Scan Mode
! Isothermal (Time) Scan Mode
! Frequency Scan Mode
! Dynamic Stress Scan Mode
! Static Stress Scan Mode (Creep Ramp)
! Creep Analysis
! Stress Relaxation (Recovery Analysis)
! Creep-Recovery Analysis
! Constant Length Analysis (Shrinkage Force)
! Constant Force Analysis (TMA)
Prof RD Sanderson,
University of Stellenbosch
DMA 7e Can Run Many Types of
Samples
! Measuring Systems are available to hold many
different types of samples in place for testing
Three Point Bending
Four Point Bending
Dual Cantilever
Single Cantilever
Film Extension
Fibre Extension
Parallel Plate
Cup and Plate
Plate and Tray
Sintered Plates
Prof RD Sanderson,
University of Stellenbosch
 Perform many different
types of tests
! Melt, Tg, alpha, beta and gamma transitions,
! recrystallization,
! cure,
! modulus,
! damping,
! shrinkage,
! heat deflection,
! brittle point tests and many more...

Prof RD Sanderson,
University of Stellenbosch
 Run many types of samples
! Plastic,
! automotive,
! construction,
! aerospace,
! business products,
! metal,
! ceramic,
! food,
! cosmetic,
! environmental,
! biological materials.
Prof RD Sanderson,
University of Stellenbosch
 The DMA 7e Analyzer
Includes
! Motor
Deforms the sample
! Displacement Measuring Device (LVDT)
Measures the deformation
! Measuring System
Holds the sample in place for testing
! Environmental System
Furnace, purge gas and cooling device

Prof RD Sanderson,
University of Stellenbosch
 Amplitude

! The maximum of an oscillatory

displacement
! 1/2 peak-to-peak sinusoidal
displacement

Prof RD Sanderson,
University of Stellenbosch
 Dynamic Strain

! Oscillatory displacement normalized

for original sample size
micrometers/micrometers (mm/mm)
no units

Prof RD Sanderson,
University of Stellenbosch
 Dynamic Force

! Themaximum force the analyzer

applies to the sample during an
oscillation
milliNewtons (mN)
! The DMA 73 can apply
0 to 6,500 mN dynamically

Prof RD Sanderson,
University of Stellenbosch
 Dynamic Stress

! Theapplied oscillatory force

normalized for sample area (geometry
and measuring system)
Newton per meter squared (N/m2)
Pascal (Pa)

Prof RD Sanderson,
University of Stellenbosch
 DMA Modes
! Time scan
! Temperature scan
! Frequency scan
! Dynamic force scan

Prof RD Sanderson,
University of Stellenbosch
 DMA Reports

! Tangent delta Vs. time

! Storage modulus Vs. time
! Storage modulus and tangent delta Vs.
temperature
! Storage modulus and complex
viscosity Vs. frequency
! Dynamic strain Vs. dynamic stress

Prof RD Sanderson,
University of Stellenbosch
 DMA Calculations

! Time stability
! Storage modulus
! Loss modulus
! Complex modulus
! Tangent delta
! Dynamic modulus

Prof RD Sanderson,
University of Stellenbosch
 Advanced Topics

! Multiplexing
! Time-temperature super positioning
! Molecular weight
! Molecular weight distribution

Prof RD Sanderson,
University of Stellenbosch
 Recovery Calculations
! When the sample has completely recovered from the
stress, strain reaches a steady state (a steady state
equilibrium is reached)
! The final value of the strain gives the elastic strain
recovery
! Since the stress is constant, the steady state
Equilibrium Modulus can be calculated
! But, obtaining the final strain is problematical

Prof RD Sanderson,
University of Stellenbosch
 What is Dielectric Analysis
(DEA)?

! Dielectricanalysis (DEA) is the study of

relative mobility of charged sites in a
polymer
! Charged sites in a polymer are typically
ions and dipoles

Prof RD Sanderson,
University of Stellenbosch
 How does DEA work?

! The mobility of charged sites is

measured by applying an oscillating
electrical voltage to the sample and
measuring the current
! The resulting oscillating current
amplitude and time delay are used to
characterize the electrical properties of
the sample
Prof RD Sanderson,
University of Stellenbosch
 Why do I need DMA-DEA?

! More can be obtained from the simultaneous

techniques than the individual techniques
! DMA-DEA can be used for most thermosets,
hot melt adhesives and curing elastomers
Results from DMA-DEA can be used to increase product
quality and reduce manufacturing costs
Since DEA is also an in-process technique, this information
can be applied to a wide variety of processing environments

Prof RD Sanderson,
University of Stellenbosch
 Two Analyzed Combined

! Combine the best in Dielectrics with the

best in Thermal Analysis and get the best
of both techniques
Dynamic Mechanical Analyzer (DMA 7e)
from Perkin-Elmer
Eumetric System III Microdielectrometer
(DEA) from Micromet Instruments, Inc.
! Simultaneous DMA-DEA
Prof RD Sanderson,
University of Stellenbosch
 How does DMA-DEA work?

! Simultaneous DMA-DEA results are

obtained using traditional DMA parallel
plates (or cup and plates) as electrodes
for the DEA

Prof RD Sanderson,
University of Stellenbosch
 What do DMA-DEA results
mean?

! Polymer viscosity is measured by DMA and

DEA in different ways, but both reflect the
same fundamental material property
The relationship between traditional DMA
viscosity (measured using parallel plates or cup
and plates) and DEA viscosity (derived from the
dielectric loss factor) is a function of polymer
chain segment mobility and free volume

Prof RD Sanderson,
University of Stellenbosch
 Faster and more accurate
results
! More can be obtained from Simultaneous
DMA-DEA
Faster analysis because there is only a single run
The sample has the same thermal and mechanical
history because the same sample and preparation
is used
Both mechanical and dielectric properties are
determined

Prof RD Sanderson,
University of Stellenbosch
 Analyze Many Sample Shapes
and Types
! In-process, process emulation, and laboratory bench
analysis can be performed using the multiple
measuring systems and geometries
Prepegs using parallel plates
Gels, pastes and viscous resins using the plate and tray
Solvent containing and saturated solvent systems using the
sintered parallel plate
Curing or samples with very low viscosities using the cup
and plate
Molecular transitions using the chip sensor (IC sensor)

Prof RD Sanderson,
University of Stellenbosch
 Perform Many Types of
Analysis
! Evaluate final products, emulate processes,
characterize basic mechanical properties using the
broad analytical capability offered by the multiple
modes of operationn
Evaluate final products with a Youngs flexural modulus using
the Creep-Ramp (static stress scan) and the DEA
Test new formulations or new process parameters in-process
or in the laboratory using the Temp/Time scan mode and the
DEA. Emulate process conditions both in the laboratory and in
the process simultaneously using the Temp/Time scan mode
and the DEA

Prof RD Sanderson,
University of Stellenbosch
 Perform Many Types of
Analysis
! Characterize basic mechanical properties
such as elasticity (modulus) or damping
(tangent delta) using the Dynamic Stress
scan mode and the DEA
! Evaluate new incoming materials for
differences in molecular structure using
the Frequency scan mode and the DEA

Prof RD Sanderson,
University of Stellenbosch
 Completely Characterize
Cure
! Evaluate the degree of cure advancement in resins
using the glass transition (Tg) of uncured or staged
resins
Optimize the flow into the mould, eliminate gas bubbles or
voids using the minimum viscosity
Optimize the forming, lay-up or working time using the time
between the minimum viscosity and the gel point
Define the end of working time and the point when the
modulus begins to increase using the gel point

Prof RD Sanderson,
University of Stellenbosch
Completely Characterize Cure
! Determine the effects of storage or handling of the
prepreg using the modulus decrease due to stress
relief
Optimize post bake operations using the cure rate after
vitrification
Assure fully cured products using by characterizing the
product until end of cure
Determine the maximum rate of modulus growth, reaction
order or reaction kinetics using the slope calculations on the
modulus
Find the best time to de-mould using the vitrification point

Prof RD Sanderson,
University of Stellenbosch
Parallel Plates Chip Sensor
Sinusoidal
! Oscillatory
DMA Analyzer Operation
DMA 7e Cut-
Away Diagram
DMA 7e Operation
DMA 7e Force, Displacement,
Amplitude and Phase Lag
 DMA 7e
Theory of Operation
! Force motor applies a
sinusoidal force to the
sample
! The resultatant sine wave
response of the sample is
measured using an LVDT
! The amplitude of the
response is used to calculate
the STORAGE MODULUS (E)
! The phase lag of the
response is used to calculate
the LOSS MODULUS (E)
! Other curves are derived
from these results (e.g. TAN
DELTA is E/E, etc).
 DMA 7e Storage Modulus
10
10
Tm
Storage Modulus

9
10

8
10

7
10
Tg
DSC
6
10
Hard and Elastic and
Fluid
Brittle Deformable
5
10

Temperature
 DMA 7e Temperature Scan
Log Modulus (Pa) 11 F
E
10 D

9 C

8
7
Cross-linked
6 B
5
A
Glassy Rubbery
4
3 Temperature

F E D C B A
Secondary Hookean Second P r im a r y
Deformation Highly Visco Elastic Flow
Dispersion Behavior Transition Transition
( ga m m a ) ( b e ta ) (alpha) (rubbery) ( m e l t)

Molecular Bend & Side Main Main Chain Large Chain

Localized
Motion Stretch Groups Chain Scale Mobility Slipping
Motion
Bonds Gradual

Unstrained
State

Strained
State Increasing

R. Seymou r, 1971
 DMA 7e
Dynamic Stress Scan Mode
 DMA 7e
Frequency Scan Mode
 DMA 7 Temperature Scan Mode
Curve 1: DMA Temp/Time Scan in 3 Point Bending
File info: temp5 Tue Feb 13 19:27:31 1990
Frequency: 10.00 Hz Strain: 0.050%
GLASS-
GLASS-EPOXY COMPOSITE Tension: 120.000% GLASS-
GLASS-EPOXY COMPOSITE

2.0 4.0

1.8 3.5

1.6
3.0

)
1.4
)
10

-1
2.5
Modulus (Pa x 10

(x 10
1.2
2.0

delta
1.0

tan
1.5
0.8

1.0
0.6

0.4 0.5

0.2 0.0
0.0 50.0 100.0 150.0 200.0 250.0 300.0

Temperature ( C) APPLICATION LABORAORY

TEMP1: 50.0 C TIME1: 0.0 min RATE1: 2.0 C/min PERKIN-
PERKIN-ELMER
TEMP2: 225.0 C
7 Series Thermal Analysis System
Tue Aug 30 12:49:11 1994
Youngs Modulus Comparison of Samples

5.0 10
A 3.121 x 10 B
1.490 x 10 10
4.5

4.0 G
F
9
7

9 2.998 x 10
3.577 x 10
3.5
Static Stress (Pa x 10 )

9
E 3.471 x 10
3.0
2.992 x 10 9
D
2.5 C
2.256 x 10 9

2.0

1.5

1.0

0.5

0.0
0.0 0.2 0.4 0.6 0.8 1.0

Static Strain (%)

397018
 DMA 7e Creep Recovery
Curve 1: DMA Creep Recovery in 3 Point Bending
File info: creppvc1 Mon Jul 11 23:54:56 1988
Sample Height: 3.061 mm Creep Stress: 2.00e+06Pa Recovery Stress: 1.00e+01Pa
POLY(VINYL CHLORIDE) POLY(VINYL CHLORIDE)

2500.0

2250.0
0.025
2000.0

1750.0 0.020

Strain (%)
Force (mN)

1500.0

0.015
1250.0

1000.0
0.010
750.0

500.0
0.005

250.0

0.0 0.000
0.0 4.0 8.0 12.0 16.0 20.0

At 30 C Time (minutes) PE DMA7 R&D LAB

TEMP1: 30.0 C TIME1: 20.5 min PERKIN-ELMER
7 Series Thermal Analysis System
Tue Aug 30 13:01:32 1994
 DMA 7e
Creep-Recovery Mode
 DMA 7e
Creep Ramp Mode
 DMA 7e
Creep Ramp
Curve 1: DMA Creep Recovery in Extension
File info: PET002 Thu Mar 10 13:30:57 1994
Sample Height: 6.162 mm Creep Stress: 6428.0mN Recovery Stress: 1.0mN
PET

1.3

1.2

1.1

1.0
Slope 7010474.97 Pa/%
0.9
)
8

0.8
Stress (Pa x 10

0.7

0.6

0.5

0.4

0.3
Slope 2.355e+7 Pa/%
0.2

0.1

0.0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
RERUN AFTER INITIAL SCAN Strain (%)
TEMP1: 25.0 C TIME1: 13.0 min PERKIN-ELMER
7 Series Thermal Analysis System
Tue Aug 30 13:10:19 1994
 DMA 7e
Dynamic Stress Scan
Curve 1: DMA AC Stress Scan in 3 Point Bending
File info: ssceramg2 Sat Sep 16 19:38:40 1989
Frequency: 1.00 Hz Stress Rate: 10.0mN/min
CERAMIC STRESS SCAN SLO Tension: 110.000%

7.0

6.0
)
5

5.0
Dynamic Stress (Pa x 10

4.0

3.0

2.0

1.0

0.0
0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07

Strain (%) J.S.MAYER

TEMP1: 22.3 C TIME1: 34.4 min PERKIN-ELMER
7 Series Thermal Analysis System
Tue Aug 30 12:57:53 1994
 DMA 7e
Tangent Delta
 DMA 7e
Frequency Scan Mode
Curve 1: DMA Frequency Scan in Parallel Plate
File info: f6Rheo1c1d Fri Jan 18 14:52:01 1991
Strain: 0.100% Tension: 0.000%
POLY(DIMETHYLSILOXANE) POLY(DIMETHYLSILOXANE)

10 7 10 7

10 6 10 6

s)
Modulus (Pa)

Viscosity (Pa
10 5 10 5

10 4 10 4

10 3 10 3
10 -3 10 -2 10 -1 10 0 10 1 10 2
LOT 1441C Frequency (Hz) APPLICATION LABORATORY
TEMP1: 26.7 C TIME1: 66.3 min PERKIN-ELMER
7 Series Thermal Analysis System
Tue Aug 30 12:53:58 1994
Quatra Functional Phenolic Film
Effect of Rubber Formulation

A A+B B+C C
Cable Insulation
DMA 7e Temperature Scan of a
Typical Epoxy-Glass Composite
Semi-crystalline polymer
DMA is used to describe mechanical properties
like hardness, brittleness, elasticity, and viscosity

11
Very
Hard
Hard
10
Pliable

8 Soft

7
Log Modulus, (Pa) Cross-linked
6 Very
Soft

Glassy Rubbery
4

3 Flowing

Temperature ( oC)

340901
 Thank
Thank you.
you.

Prof RD Sanderson,
University of Stellenbosch