Dynamic Mechanical Analysis (DMA)

Basics and Beyond

ε∗ ω= Σ(Δεβ/1+ιωτβ)

Dr. Lin Li
Thermal Analysis
PerkinElmer Inc.
April 2000
 The DMA lets you relate:
product properties

molecular structure
Material
Behavior

processing conditions
 DMA Structure in general
How the DMA works: Force Motor
 Constant inputs and outputs Coil
function as in the TMA Magnet

 A sine wave current is added

to the force coil Temperature Enclosure
 The resultant sine wave LVDT
voltage of the LVDT is
compared to the sine wave
force
Core Rod
 The amplitude of the LVDT is
Interchangeable
related to the storage modulus, Measuring System
E' via the spring constant, k. Furnace
 The phase lag, δ, is related to Heat Sink/Cooling System
the E" via the damping
constant, D.
 Outstanding Flexibility 1:
Multiple Geometries
Parallel Plate
Cup & Plate
Tray & Plate
Sintered Plates
3 pt. Bending
Compressive Shear 4 pt. Bending
AST M Flexure
Dual Cantilever
Single Cantilever
Extension Extension
Shear Sandwich
Coaxial Cylinder
Cup & Plate Flexure Paper Fold
 Why?
12 20 mm
11
10
9
Log E’

8
7
1 mm
6
5
4 5 mm 20 mm
3
 Stress Causes Strain...
Cauchy or
Engineering Strain
ε = ΔL/Lo
Henchy or
True Strain ε = ln (ΔL/Lo)
Lo L
Kinetic Theory
of Rubber Strain ε = 1/3{L/Lo-(Lo/L)2}
Kirchhoff Strain ε = 1/2{ (L/Lo)2-1}
Murnaghan Strain ε = 1/2{1-(Lo/L)2}
L-Lo = ΔL
The different definitions of tensile strain
become equivalent at very small deformations.
 The Elastic Limit: Hooke’s
Law

=
σ

slope = k

Strain increases
with increasing
Stress ε
 Real vs... Hookean Stress-
Strain Curves
Curve 1: DMACreep Recoveryin Parallel Plate
File info: Drssr90R.2Thu Apr 14 15:16:52 1994
Limiting
Sample Height:3.359 mmCreep Stress: 2600.0mN
Dresser 90 Durameter
Recovery Stress: 1.0mN
Modulus
1.4

1.2

Hookean
1.0
Behavior
7)

0.8

σ
Stress (Pa x 10

0.6

Slope 1642965.02 Pa/%

0.4

0.2

0.0 Slope 359171.32 Pa/%

Real behavior
4.0 8.0 12.0 16.0

Strain (%) KPM

TEMP1: 20.0 C TIME1: 5.3 min PERKIN-ELMER
7 Series ThermalAnalysis System
Thu Apr 14 16:34:38 1994 ε
 The Viscous Limit: Newtonian
Behavior

σ
slope = η

The speed at which the fluid flows

.
γ
through the holes (the strain rate)
increases with
stress!!!
 Viscosity Effects
• Newtonian behavior is linear and the
viscosity is independent of rate.
• Pseudoplastic fluids get thinner as shear
increases.
• Dilatant Fluids increase their viscosity as
shear rates increase.
τ • Plastic Fluids have a yield point with
pseudoplastic behavior.
• Thixotrophic and rheopectic fluids show
viscosity-time nonlinear behavior. For
example, the former shear thin and then
. reform its gel structure.
γ
 Polymers are Non-Newtonian
Fluids!!!
Zero Shear Plateau ~ ηo • At low shear rates, the
viscosity is controlled by
MW. The material shows
Linear Newtonian behavior
Dependence • Viscosity shows a linear
η

on Rate dependence on rate above

Log

the ηo region.
• At high rates, the material
can no longer shear thin and
Infinite Shear Plateau ~ η a second plateau is reached.
∞
.
Log γ
 Analyzing a Stress-Strain
Curve failure (ε , σ ) Β Β
linear
region nonlinear region

σ
yield point (εy, σy) The area under
the curve to this line
is the energy needed
to break the material
Young’s modulus (E)
dσ σ L
E = =
dε ε L

ε
Under Continuos Loads: Creep
Recovery
• Applying a constant
load for long times
and removing it from a
sample.
• Allows one to see the
distortion under
constant load and also
how well it recovers.
 Creep is a fundamental
engineering test.
• Creep is used as a Curve 1: DMA Creep Recovery
in 3 Point Bending
File info: cr_ptfe-5 Wed Jun 29 15:31:18 1988
Sample Height:3.300 mmCreep Stress: 1.50e+06Pa Recovery Stress: 6.25e+02Pa

basic test for design.

PTFE - CREEP/RELAXATION # 1 PTFE - CREEP/RELAXATION AT -5C:cr_ptfe-5
Strain (%)
# 2 Force (mN)

2500.0

• By looking at both
2250.0
0.0025

2000.0

0.0020 1750.0

the creep and

Force (mN)
1500.0

Strain (%)
1250.0
0.0015

recovery parts of the

1000.0

750.0
0.0010

500.0

curve, we can begin 0.0005

250.0

0.0

to examine how
-250.0
0.0000
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0

Time (minutes) DMA7 APPLICATIONS LAB

TEMP1: -15.0 C TIME1: 7.0 min PERKIN-ELMER
7 Series ThermalAnalysis System

polymers relax.
Thu Apr 28 20:32:20 1994
 Dynamic Stress
Force (dynamic)

Force

F (static) Stress =FA

Time
Phase angle = δ
material response

Stress Amplitude = k

Strain =yo/y
Time
Why? Let’s bounce a ball.

E” ~ energy loss in
internal motion

E’ ~ elastic
response
All this is calculated from δ and
k:
• From k, we calculate E’ (storage modulus)
• From δ, we calculate E’’ (loss modulus)
• then:
Tan δ = E”/E’
E* = E’ + iE” = SQRT(E’2 + E”2)
G* = E*/2(1+ν)
η = 3G*/ω
 To apply this to materials...
Dyna mic Stress Scan Since each part of the ramp
has a sine wave stress
associated with it, we get:
tan δ
E*, E’, E”
η
σο σ ε for each data point!!

ε ο
 For example, DSS Curves
Curve 1: DMA AC Stress Scanin Parallel Plate
Curve 1: DMAAC Stress Scanin Parallel Plate
File info: Drssr70DssThu Apr 14 16:44:41 1994
File info: Drssr70DssThu Apr 14 16:44:41 1994
Frequency: 1.00 Hz Stress Rate: 250.0mN/min
Frequency: 1.00 Hz Stress Rate: 250.0mN/min
Dresser 70 Durameter Tension: 110.000%
Dresser 70 Durameter Tension: 110.000% # 1 Dresser 70 Durameter:Drssr70Dss
7
Complex Viscosity (Pas x 10 )
5.5
# 2 Dresser 90 Durameter:Drssr90dss
5.5 7
Complex Viscosity (Pa s x 10 )
5.0

5.0
4.5

4.5
6)

4.0

7)
3.5 4.0

s x 10
Dynamic Stress (Pa x 10

3.0 3.5

3.0

Viscosity (Pa
2.5

2.0 2.5

1.5 2.0

1.0 Slope 6297938.16 Pa/% 1.5

0.5
1.0
Slope 1274361.04 Pa/%
0.0
0.2 0.4 0.6 0.8 1.0
0.2 0.4 0.6 0.8 1.0
Strain (%) KPM
TEMP1: 10.5 C TIME1: -1.2 min PERKIN-ELMER Strain (%) KPM
7 Series ThermalAnalysis System TEMP1: 10.5 C TIME1: -1.2 min PERKIN-ELMER
Thu Apr 14 16:59:58 1994 7 Series ThermalAnalysis System
Thu Apr 28 20:28:00 1994
 Now, let’s induce temperature
as a variable.
• We can heat the material
under minimal load at a

Free Volume
calibrated rate.
• This allows the material
to change with
temperature.
• These changes can be
described in terms of free
volume or relaxation
times.
 Thermomechanical Analysis as
a starting Point.
Curve 1: TMAin Penetration
File info: Tgflex Tue Oct 10 16:21:08 1995
Sample Height:4.180 mmDC Force: 100.0 mN
Tg by flex # 1 Tg by flex:Tgflex
Penetration (mm)
7.0

6.5

6.0
Onset 106.92 C
5.5

5.0

4.5
Penetration (mm)

4.0

3.5

3.0

2.5

2.0

1.5

1.0

0.5

0.0
50.0 75.0 100.0 125.0 150.0 175.0

Temperature (C)
TEMP1: 30.0 C TIME1: 0.0 min RATE1: 10.0 C/min PERKIN-ELMER
TEMP2: 150.0 C
7 Series Thermal Analysis System
Sun Nov 26 20:10:47 1995
 TMA - It’s all free volume.
Curve 1: TMA in Expansion
File info: cte Tue Oct 10 16:46:51 1995
Sample Height: 1.742 mm DC Force: 10.0 mN
cte # 1 cte :cte
Expansion (mm)

2.10

2.05
Free
2.00
Volume
Expansion (mm)

1.95

1.90 -2
Cx 2.195 x 10 /C

1.85

1.80
Occupied
Volume
1.75
Tg
-5 Onset 105.53 C
1.70 Cx 2.948 x 10 /C

70.0 80.0 90.0 100.0 110.0

Temperature ( C)
TEMP1: 30.0 C TIME1: 0.0 min RATE1: 10.0 C/min PERKIN-ELMER
TEMP2: 150.0 C
7 Series Thermal Analysis System
Sun Nov 26 20:08:09 1995
 And it’s not just Tg.
Curve 1: TMA in Extension
File info: menard005 Tue Feb 21 12:28:20 1995
Sample Height: 12.017 mm DC Force: 0.0 mN
FIBER E # 1 FIBER E:menard005
Extension (mm)
12.20

12.18

12.16

12.14

12.12
Extension (mm)

12.10

12.08

12.06

12.04

12.02

12.00

11.98

0.0 50.0 100.0 150.0 200.0 250.0

He/20psi/H/Chiller Temperature ( C) Tech.Support Lab/K.Menard

TEMP1: 30.0 C TIME1: 0.0 min RATE1: 5.0 C/min PERKIN-ELMER
TEMP2: 250.0 C
7 Series Thermal Analysis System
Tue Feb 21 12:29:39 1995

(the traditional way to do heat set)

 Time Temperature Scans at a
Fixed Frequency
• hold frequency constant and vary
temperature or time at temperature
• allows detection of transitions in material
• allows one to study cures
• most sensitive method for finding Tg
• can also get changes in dimension (TMA)
while collecting DMA data
• Best probe of polymer relaxations as function
of temperature
Idealized Multi-Event DMA Scan
(6) γ (5)
Β (4)
Tg - glass transition (3) α

E’
Rubbery Plateau (2)
Tm - melting (1)

Temperature
(6) (5) (4) (3) (2) (1)
local bend side gradual large chain
motions and groups main scale slippage
stretch chain chain
 In more detail...
Log Modulus (Pa)
11 F
E
10 D Crystalline Polymer
9 C
8 Crystal-crystal slip
7
6 Cross-linked
B
5
Glassy Rubbery A
4
3 Temperature
F E D C B A
Secondary Hookean Second Primary Highly Visco Elastic
Deformation Dispersion Behavior Transition Transition Flow
(gamma) (beta) (alpha) (rubbery) (melt)

Molecular Localized Bend & Side Main Main Chain Large Chain
Motion Motion Stretch Groups Chain Scale Mobility Slipping
Bonds Gradual

Unstrained
State
Strained Increasing
State
R. Seymour, 1971
 Common changes show as:
MW MWD Crosslink Density Crystallinity

E’
tan δ
 Tg are easily seen, as in PET Film
Curve 1: DMA Temp/Time Scan in Extension
File info: demofilm Wed Oct 11 17:06:48 1995
Frequency: 1.00 Hz Amplitude: 21.949u
pet film Tension: 110.000% #1 pet film:demofilm
tan
9
#2 Storage Modulus (Pa x 10 )
1.6

3.5
1.4

1.2 3.0

)
9
1.0

Modulus (Pa x 10
2.5

0.8
tan

Onset 83.29 C 2.0

0.6
1.5

0.4
1.0
Onset 107.82 C
0.2

0.5
0.0
Onset 79.35 C
0.0
-100.0 0.0 100.0 200.0 300.0

Temperature ( C)
TEMP1: -100.0 C TIME1: 0.0 min RATE1: 10.0 C/min PERKIN-ELMER
TEMP2: 250.0 C
7 Series Thermal Analysis System
Sun Nov 26 21:02:11 1995
 or in PP fishing line.
Curve 1: DMA Temp/Time Scan in Extension
File info: 1116942 Wed Nov 16 13:20:39 1994
Frequency: 1.00 Hz Dynamic Stress: 200.0mN
fishing line Static Stress: 300.0mN # 1 fishing line:1116942
-1
tan (x 10 )
9
# 2 Storage Modulus (Pa x 10 )

8.0
2.5

7.0

2.0

)
9
6.0
)

Modulus (Pa x 10
-1

5.0
1.5
(x 10

4.0
tan

1.0
3.0

0.5 2.0

1.0
0.0
0.0

-100.0 -50.0 0.0 50.0 100.0 150.0 200.0

Temperature ( C)
TEMP1: -130.0 C TIME1: 0.0 min RATE1: 10.0 C/min PERKIN-ELMER
TEMP2: 270.0 C
7 Series Thermal Analysis System
Sun Nov 26 21:24:35 1995

Sample prep can be minimal if only temperatures are needed.

Transitions are clearly seen in
highly crosslinked samples
Curve 1: DMA Temp/Time Scan in 3 Point Bending
File info: afriedli.1 Thu Feb 17 12:14:11 1994
Frequency: 1.00 Hz Dynamic Stress: 800.0mN
epoxyresin Static Stress: 1000.0mN #1 epoxyresin:afriedli.1
9
Storage Modulus (Pa x 10 )
#2 tan 1.0

4.5 0.9

4.0 0.8

3.5 0.7
)
9

3.0 0.6
Modulus (Pa x 10

tan
2.5 0.5

2.0 0.4

1.5 0.3

1.0 0.2

0.5 0.1

0.0 0.0
0.0 50.0 100.0 150.0 200.0 250.0
heavy xlink Temperature ( C) km
TEMP1: 30.0 C TIME1: 0.0 min RATE1: 10.0 C/min PERKIN-ELMER
TEMP2: 250.0 C
7 Series Thermal Analysis System
Thu Jun 23 13:45:10 1994

This Tg is undetectable in the DSC !!!!!!

 as well as in blends.
Curve 1: DMA Temp/Time Scan in 3 Point Bending
File info: sbr14 Thu Feb 15 10:45:19 1990
Frequency: 1.00 Hz Dynamic Stress: 2.00e+05Pa
STYRENE BUTADIENE RUBBE Tension: 110.000% #1 STYRENE BUTADIENE RUBBER:sbr14
Storage Modulus (Pa) L
#2 tan 1.0

0.9

10 9 0.8

0.7
Modulus (Pa)

0.6

tan
10 8
0.5

0.4

0.3
10 7

0.2

0.1

10 6 0.0
-150.0 -100.0 -50.0 0.0 50.0 100.0 150.0 200.0

K66:22T914 Temperature ( C) APPLICATION LABORATORY

TEMP1: -180.0 C TIME1: 0.0 min RATE1: 5.0 C/min PERKIN-ELMER
TEMP2: 250.0 C
7 Series Thermal Analysis System
Sun Nov 26 20:54:43 1995
 It’s not always so simple:
For example, crystal-crystals slips can cause α∗ transitions
Curve 1: DMA Temp/Time Scan in 3 Point Bending
File info: AMPfrPP.1 Wed Oct 27 13:49:06 1993
Frequency: 1.00 Hz Dynamic Stress: 950.0mN
LeBrun samples Static Stress: 1000.0mN #1 LeBrun samples:AMPfrPP.1
9
Storage Modulus (Pa x 10 )
-1
#2 tan (x 10 ) 3.0

2.5 2.5

2.0

)
)

-1
9

2.0
Modulus (Pa x 10

(x 10
1.5
1.5

tan
Tg or 1.0

1.0
Alpha
Tα* 0.5

0.5
0.0

-150.0 -100.0 -50.0 0.0 50.0 100.0

AMP Flame Retardant Polypropylene Temperature ( C) KPM
TEMP1: -160.0 C TIME1: 0.0 min RATE1: 5.0 C/min PERKIN-ELMER
TEMP2: 300.0 C
7 Series Thermal Analysis System
Sun Nov 26 20:58:36 1995
 Higher Order Transitions
affect toughness
Curve 1: DMA Temp/Time Scan in 3 Point Bending
File info: AMP66gp.1 Tue Oct 26 16:05:29 1993
Frequency: 1.00 Hz Dynamic Stress: 190.0mN
LeBrun samples Static Stress: 200.0mN LeBrun samples

4.0
5.5

5.0 3.5

4.5

4.0 Good Impact Strength 3.0

)
)

-1
9

3.5 2.5

(x 10
Modulus (Pa x 10

3.0

β Transitions 2.0

tan
2.5
1.5
2.0
Tg
1.5 Poor 1.0

1.0
0.5
0.5

0.0 0.0
-150.0 -100.0 -50.0 0.0 50.0 100.0 150.0

AMP good part 20% glass filled Nylon 6/6 Temperature ( C) KPM
TEMP1: -160.0 C TIME1: 0.0 min RATE1: 5.0 C/min PERKIN-ELMER
TEMP2: 300.0 C
7 Series Thermal Analysis System
Sat Oct 15 14:32:54 1994

Impact was good if Tg/Tβ was 3 or less.

...and also define operating
range.
Curve 1: DMA Temp/Time Scan in 3 Point Bending
File info: gamma_1 Thu Jun 30 02:17:24 1988
Frequency: 7.00 Hz Dynamic Stress: 1.86e+06Pa
EPOXY PC BOARD AT 7 Hz Static Stress: 1.86e+06Pa # 1 EPOXY PC BOARD AT 7 Hz:gamma_1
10
Storage Modulus (Pa x 10 )
1.1 -1
-> # 2 tan (x 10 )

1.0 Beta 5.0

4.5
0.9
Tg 4.0
0.8

)
3.5
)
10

-1
0.7
3.0

(x 10
Modulus (Pa x 10

0.6
Operating 2.5

tan
0.5

0.4
range 2.0

1.5

0.3
1.0

0.2 0.5

0.1 0.0

0.0
-100.0 0.0 100.0 200.0

Temperature ( C) PE DMA7 R&D LAB

TEMP1: -180.0 C TIME1: 0.0 min RATE1: 10.0 C/min PERKIN-ELMER
TEMP2: 300.0 C
7 Series Thermal Analysis System
Sun Nov 26 20:13:53 1995
 It can get complex...
Curve 1: DMA Temp/Time Scan in Extension
File info: T2n4ptg Fri Jan 18 18:14:51 1991
Frequency: 1.00 Hz Dynamic Stress: 1.00e+07Pa
NYLON MONOFILAMENT Static Stress: 1.05e+07Pa #1 NYLON MONOFILAMENT:T2n4ptg
Storage Modulus (Pa) L
2 -1 4.0
#2 tan (x 10 )

3.5
10 10
9
8 3.0
7

)
6

-1
5 2.5
Modulus (Pa)

(x 10
4

3 2.0

tan
2 1.5

Tg or Tα 1.0
10 9
9
8
7
Stress 0.5

6
5 Tβ Relief 0.0
-200.0 Tγ
-150.0 -100.0 -50.0 0.0 50.0 100.0 150.0 200.0
iNITIAL RUN Temperature ( C) B.Cassel
TEMP1: -180.0 C TIME1: 0.0 min RATE1: 4.0 C/min PERKIN-ELMER
TEMP2: 0.0 C
TEMP3: 150.0 C
TIME2: 0.0 min RATE2: 2.0 C/min
7 Series Thermal Analysis System
Sun Nov 26 20:59:14 1995
 Curing of Thermosets

• can be studied at constant temperature or by a

temperature ramp
• can get minimum viscosity, gelation point (time),
vitrification point, and activation energies from
DMA curve
• can adapt instrument to do simultaneous DEA-
DMA to follow cure to completion
• cure studies are not limited to polymeric systems
but include food products like cakes and cookies
 Analysis of a Cure by DMA
E’-E” Crossover ~ gelation point
10 8

10 7
106 Pa ~ Solidity
10 6
Modulus

10 5 vitrification point
E”
10 4

Curing
10 3

10 2 E’ Minimum Viscosity (time, length,

Melting
10 1 temperature )
η∗
10 0
50.0 70.0 90.0 110.0 130.0 150.0

Τ
 QC can often be done by
simply fingerprinting the resin.

3.5

3.0

2.5
note the different slopes and
η∗ 2.0 the different curve shapes
1.5
bad
1.0

0.5

0.0
good
25.0 50.0 75.0 100.0 125.0 150.0
 Postcure studies allow process
optimization:
1 hour Postcure time vs... Tg and E’
1.0 0 hours 2 hours 200
180
3 - 8 hours
160
140
120
0.5

Property
100
E'@50 ( E 9 P A )
tan δ

80
60 E' ONSET
40 T A N D PE A K
20
T A N D ONSET
0.0 0
0 2 4 6 8
150 175 200
TIME IN HOURS
Temperature
 Frequency Scans

• hold temperature constant and vary frequency

• allows one to look at trends in material
• can estimate changes in MW and MWD
• looks at both tack-like and peel-like behavior
• can use data for Time Temperature Superposition
to extend frequency range or predict age life.
 Frequency determines the type
of response
10 7 10 7

More More
Liquid solid
10 6 like like 10 6

s)
Modulus (Pa)

Viscosity (Pa
10 5 10 5

10 4 10 4

Flow dominates Elastic dominates

10 3 10 3

10 -2 10 -1 10 0 10 1
Frequency (Hz)
For example, two hot melt adhesives...
show affect of rate (peel vs.... tack)
10 8 10 8

10 7 10 7
bad
η∗ E’’
10 6 10 6

10 5 10 5

10 4 10 4
good
10 3 10 3

10 2 10 2
10 -4 10 -3 10 -2 10 -1 10 0 10 1

Τ
 Creep can look at distortion
under load,
Curve 1: DMA Creep Recovery in 3 Point Bending
File info: cr_ptfe-5 Wed Jun 29 15:31:18 1988
Sample Height: 3.300 mm Creep Stress: 1.50e+06Pa Recovery Stress: 6.25e+02Pa
PTFE - CREEP/RELAXATION #1 PTFE - CREEP/RELAXATION AT -5C:cr_ptfe-5
Strain (%)
#2 Force (mN)

2500.0

2250.0
0.0025

2000.0

0.0020 1750.0

Force (mN)
1500.0
Strain (%)

1250.0
0.0015
1000.0

750.0
0.0010

500.0

250.0
0.0005

0.0

-250.0
0.0000
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0

Time (minutes) DMA7 APPLICATIONS LAB

TEMP1: -15.0 C TIME1: 7.0 min PERKIN-ELMER
7 Series Thermal Analysis System
Thu Apr 28 20:32:20 1994
 cyclic application of loads,
Differences can be seen in good and bad samples and get more apparent with
several cycles. Here the bad material is not flowing enough to fill the pores and
form a mechanical bond.
55.0
50.0
45.0 Good
% Strain

40.0
35.0
30.0
25.0
20.0
15.0
10.0
5.0 Bad
0.0 6.0
0.0 1.0 2.0 3.0 4.0 5.0

Time in minutes
and with varying temperatures.
Curve 1: DMA Creep Recovery in Parallel Plate
File info: DR90D2.1 Fri Jul 23 12:23:50 1993
Sample Height: 2.836 mm Creep Stress: 2600.0mN Recovery Stress: 1.0mN
Dresser 90 D # 1 Dresser 90 D:DR90D2.1
Strain (%)
#2 Force (mN)
24.0
#3 T ( C) 2750.0
P
22.0 2500.0

20.0 2250.0

18.0 2000.0

16.0 1750.0

Force (mN)
Strain (%)

14.0 1500.0

12.0 1250.0

10.0 1000.0

8.0 750.0

6.0 500.0

250.0
4.0
0.0
2.0
-250.0
0.0
0.0 25.0 50.0 75.0 100.0 125.0

Time (minutes) KPM

TEMP1: -50.0 C TIME1: 11.0 min RATE1: 10.0 C/min PERKIN-ELMER
TEMP2: 0.0 C
TEMP3: 50.0 C
TIME2:
TIME3:
15.0
15.0
min
min
RATE2: 10.0 C/min
RATE3: 10.0 C/min
7 Series Thermal Analysis System
TEMP4: 100.0 C TIME4: 75.0 min Sun Nov 26 20:41:31 1995
 And you can tabulate this stuff
graphically...
• The time to 1/e
percent recovery is
the relaxation.
τ • This is a measure
of how quickly a
material recovers.
(There is a lot more
1/T to this subject.)
 Stress Relaxation
• By exploiting the special Experiment Starts
controls of the DMA-7e,
we can run stress

Position
relaxation experiments.
σ
• These look at how the
force change for a
sample kept at a set
Time
distortion as a function of
time or temperature. Sample would be distorted to y length and held.
Don’t forget the DMA-7e also does
Stress Scans
• can do either static or dynamic ramps
• static scans calculate Young’s modulus and
stress-strain curves
• dynamic scans give material response to
increasing oscillatory forces:
– get complex viscosity and modulus for each data point
– can look at changes in elasticity (E’) and lag (phase angle) with
increasing stress
• Both methods are fast tests for QC applications
after the material has been fully characterized by
other DMA modes.
Specialized Testing is Possible...
The design of the DMA-7e makes it possible to
do:
Time-Temperature Superposition (TTS)
DEA/DMA
Tests in Solution
Microscopic DMA
Photo DMA
DMA-?
 PP fibers in solvent
200.0

175.0

150.0
air
Force in mN

125.0

100.0 xylene water

75.0

50.0
iso-octane
25.0

0.0
20.0 40.0 60.0 80.0 100.0

Temperature in C
 To Review, DMA ties together...
m olecular structure product properties
Molecular weight Dimensional Stability
MW Distribution Impact properties
Chain Branching Long term behavior
Material
Cross linking Environmental resistance
Behavior
Entanglements Temperature performance
Phases Adhesion
Crystallinity Tack
Free Volume Peel
Localized motion
processing conditions
Relaxation Mechanisms
Stress
Strain
Temperature
Heat History
Frequency
Pressure
Heat set
 Conclusions
• DMA allows you to preform a wide range of
tests from sensitive probes of molecular
structure to model studies.
• the DMA-7e allows operation as six different
instruments to maximize flexibility.
• Data can be overlayed with DSC, TGA, TMA,
and DTA for easier analysis.
 References: Books
• Menard, DMA: Introduction to the Technique, Its Applications and Theory,
CRC Press, 1999.
• Brostow et a., Failure of Plastics, Hanser, 1986.
• Ferry, Viscoelastic Properties of Polymers, Wiley, 1980.
• Gordon et al., Computer Programs for Rheologists, Hanser, 1995.
• Gol'dman, Prediction of Deformation Properties of Polymeric and Composite
Materials,, ACS, 1994.
• Mascosko, Rheology, VCH, 1993.
• Matsouka, Relaxation Phenomena in Polymers, Hanser, 1993.
• McCrum et al, Anelastic and Dielectric Properties of Polymeric Solids, Dover,
1992 (reprint of 1967 edition).
• Nielsen et al., Mechanical Properties of Polymers and Composites, Dekker,
1994.
• Sperling, Introduction to Physical Polymer Science, Academic Press, 1994.
• Ward et al., Introduction to Mechanical Properties of Solid Polymers, Wiley,
1993.