DMA 2020 2 Days BNL

Dynamic Mechanical Analysis
(DMA)
2020
Els Verdonck
1
Contents
 Introduction to the technique, terminology,

viscoelastic behaviour
 Q800 & Discovery 850 instrument design
 Operation guidelines: modes of operation,
clamping configurations, experimental
considerations
 Calibration: clamps, instrument calibrations,
temperature calibration
 Applications
 Time Temperature Superposition (TTS)
2
An Introduction to DMA and
Viscoelastic Material Behaviour
3
DMA, Thermal Analysis and Rheology
 DMA is the general name given to an instrument that

mechanically deforms a sample and measures the
sample response. The deformation can be applied
sinusoidally, in a constant (or step) fashion, or under a
fixed rate. The response to the deformation can be
monitored as a function of temperature or time.
 Thermal Analysis is the measurement of some

characteristic of a substance as a function of
temperature or time.
 Rheology is the science of flow and deformation of

matter.
4
DMA : Correlation with Other Techniques
Liquids Gels Solids

Molten Polymers Soft Solids
DMA
DEA
Fluids Rheology
5
Importance of Dynamic Mechanical Analysis
 For many applications, mechanical properties and how

they change are considered the most important of all
properties of polymers.
‒ 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.
 For materials selection it’s important to have desirable

mechanical properties over the required temperature
range.
 Need to have an understanding of how the mechanical

behavior can be modified by the numerous structural
factors that can be varied (effect of fillers, orientation, etc)
and processing history (crystallinity).
6
DMA Results Can Correlate To…..
Stress
Strain
Stiffness
Damping factor
Transition temperatures
Modulus (E, G) / Compliance (J)
Processing Conditions
7
Measuring Viscoelastic Properties of Materials
A single polymer can exhibit an extremely wide range of

mechanical behavior dependent upon e.g. temperature
 Very hard and rigid solid
 Stiff to soft rubber
 Viscoelastic liquid DMA rheometer
Typical DMA Data
Glassy Region Rubbery Terminal

Plateau Region
Region
Transition
Region
Very hard and Stiff to Soft rubber Viscoelastic
rigid solid liquid
Temperature/Time/Frequency-1
8
Deformation of Solids and the Modulus
 All materials change in shape, volume, or both under the

influence of an applied stress.
 The Modulus measures the resistance to deformation of a

material when an external force is applied.
 Modulus = Stress/Strain
 We can define three kinds of Moduli for a material

 Young’s Modulus (Modulus of Elasticity) E
 Shear Modulus (Modulus of Rigidity) G
 Bulk Modulus B
9
The Three Moduli - Elastic Constants
Young’s Shear Bulk

Modulus Modulus Modulus
τ σ hyd
σ G= B=
E= γ ∆V / Vo
ε
Where Dashed lines indicate stressed state
σ = uniaxial tensile or compressive stress
τ = shear stress
σhyd = hydrostatic tensile or compressive stress
ε = normal strain
γ = shear strain
∆V/Vo = fractional volume expansion or contraction
10
Poisson's Ratio - The Fourth Elastic Constant
 Poisson's ratio, ν, is the ratio of transverse to axial strain

σ
 Axial strain:
Ly − Loy
εy =
Loy
 Transverse strain:
Ly Loy Lx − Lox
Lox εx =
Lox
Lx  Poisson’s Ratio:
εx
ν =−
σ
εy
11
Poisson's Ratio
 If the volume of the specimen remains

constant when deformed, ν = 0.5.
 Examples of constant volume materials:
liquids and ideal rubbers
 In general, there is an increase in volume

given by ∆V/V0 = (1 - 2ν)ε
where ∆V = increase in initial volume V0
caused by straining the sample
12
Comparison of Moduli and Poisson’s Ratio
Material E(GPa) ν G (GPa)

Steel 220 0.28 85.9
Copper 120 0.35 44.4
Glass 60 0.23 24.4
Granite 30 0.30 15.5
Polystyrene 3.4 0.33 1.28
Polyethylene 2.4 0.38 0.87
Natural Rubber 0.02 0.49 0.0067
Cowie, J.M.G., Polymers: Chemistry & Physics of Modern Materials, 2nd Edition,
Blackie academic & Professional, and imprint of Chapman & HallBishopbriggs, Glasgow, 1991p. 275
ISBN 0 7514 0134 X
13
Relationship Between Moduli and Poisson’s Ratio
for Elastic Isotropic Materials
 Elastic Isotropic materials are materials in which the

properties at a point are the same in all directions.
Some examples of isotropic materials are unoriented
amorphous polymers and annealed glasses.
 If any of the two elastic constants of a homogenous

isotropic material are known, the other two may be
calculated.
E = 2G (1 + ν) = 3B (1 + 2ν
ν)
14
Anisotropic Materials
 Anisotropic materials have different properties in

different directions.
Examples: fibers, wood, oriented amorphous polymers,
injection molded specimens, fiber-filled composites,
crystalline polymers in which the crystalline phase is not
randomly oriented.
 Anisotropic materials are really much more common

than isotropic ones.
 Have more than two independent moduli - generally a

minimum of 5 or 6.
 The number of independent moduli depends on the

symmetry in the system.
15
Basic Parameters and Units
 Stress = Force / Area [Pa]

σ = tensile stress, τ = shear stress
 Strain = Geometric Shape Change [dimensionless]
ε = tensile strain, γ = shear strain
 Strain or Shear Rate = Velocity Gradient or d(strain)/dt [1/s]
.
ε = tensile strain rate (dε/dt), = shear strain rate
 Modulus = Stress / Strain [Pa]
E = Young’s or Tensile Modulus, G = Shear Modulus
 Compliance = Strain / Stress [1/Pa]
Typically denoted J
 Viscosity = Stress / Strain Rate [Pa.s or Poise]
Denoted by η
16
Mechanical Analysis – Tensile Modulus
In classical mechanics, stress is applied to a material

to reach a strain, and a modulus is determined.
Stress, σ
Young’s
Modulus, E
Strain, ε
17
Elastic Behavior
Ideal Solid
1678: Robert Hooke develops his “True Theory of Elasticity”
“The power of any spring is in the same proportion
with the tension thereof.”
Hooke’s Law: σ E
Stress = Modulus • Strain Hooke’s Law of Elasticity
Spring:
Mechanical Analogue of ε Strain
Elastic Response
18
Hooke’s Law of Elasticity
 For an Elastic Solid, Stress and Strain

have a constant proportionality σ = E . ε
 If the material follows Hooke’s Law, the
deformation will be reversible when the
stress is removed
 The modulus of a Hookean solid will not
show any time dependence: the stress
depends on the strain, but not the strain
rate
Stress
Strain
19
Viscous Behavior
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.”
Newton’s Law: stress = (coefficient of viscosity) • strain rate
Dashpot: σ Ɛ
Mechanical Analogue of
Viscous Response Newton’s Law of Viscosity
20
Newton’s Law of Viscosity
 For a Viscous Liquid,

Stress is proportional to
Strain Rate dε/dt by a
coefficient of Viscosity η
Stress
η
σ = η . dε/dt
 The deformation of a
liquid is non-reversible
Strain Rate
21
Viscoelastic Behavior
Range of Material Behavior
Solid Like ---------- Liquid Like

Ideal Solid ----- Most Materials ----- Ideal Fluid
Purely Elastic ----- Viscoelastic ----- Purely Viscous
Viscoelasticity:
having both viscous and elastic properties
22
Mechanical Analysis – Tensile Modulus
 In tensile testing of
viscoelastic
materials, the rate of
extension will give
Stress, σ
different results
 the stress depends
on both the strain,
and the strain rate Strain, ε
 σ = E. ε + η . dε/dt
23
Viscoelastic Behavior
Viscoelastic Materials: Force depends on both Deformation and

Rate of Deformation and vice versa
Kelvin-Voigt Model (Basic Creep) Maxwell Model (Stress Relaxation)
.
σ = E.εε + η.ε
24
Time-Dependent Viscoelastic Behavior:
Solid and Liquid Properties of "Silly Putty"
At short times (high frequencies) At long times (low frequencies)
the response is solid-like the response is liquid-like
Silly Putty:
toy based
on silicone
polymer
T is short (< 1s) T is long (> 24 hours)

Deborah Number [De] = τ / Τ
25
The Deborah Number
Deborah Number, De - The ratio of a characteristic relaxation
time of a material (τ) to a characteristic time of the relevant
deformation process ( Τ ).
Deborah Number [De] = τ / Τ
High De Solid-like behavior

Low De Liquid-like behavior
Material can appear solid-like because:

1) the relevant deformation process is very fast or
2) it has a very long characteristic relaxation time
 Hookean elastic solid - τ is infinite
 Newtonian viscous liquid - τ is zero
26
Pitch Drop Experiment
 Short deformation time: pitch behaves like a

solid
Started in 1930
 Long deformation time: pitch behaves like a by Thomas Parnell in Australia
highly viscous liquid 9th drop fell in 2014
http://www.theatlantic.com/technology/archive/2013/07/the-3-most-exciting-words-in-science-right-now-the-pitch-dropped/277919/
27
Time and Temperature: Two Sides of the Same Coin
(E' or G') (E' or G')

(E" or G") (E" or G")
log Frequency Temperature
Principal effect of
changing temperature
is to rescale time
Time-Temperature Superposition (TTS)

log Time
28
Linear Viscoelasticity
If the deformation is small, or applied sufficiently slowly, the molecular

arrangements are never far from equilibrium. The mechanical
response is then just a reflection of dynamic processes at the
molecular level which go on constantly, even for a system at
equilibrium.
This is the domain of LINEAR VISCOELASTICITY.
The magnitudes of stress and strain are related linearly, and the
behavior is completely described by a single function of time.
Measuring linear viscoelastic properties helps us bridge the

gap between molecular structure and product performance.
29
LVR : Linear Viscoelastic Region
Linear Region: Non-linear Region:

Modulus independent Modulus is a function of strain
of strain
E' or G'
Stress
Constant γc = Critical Strain

Slope
Strain (amplitude)
30
Dynamic Mechanical Analysis
Oscillatory Testing
31
Dynamic Mechanical Testing
 An oscillatory (sinusoidal)
Deformation
deformation (stress or strain) is
applied to a sample.
Response
 The material response (strain
or stress) is measured.
 The phase angle δ, or phase

shift, between the deformation
Phase angle δ
and response is measured.
32
Dynamic Mechanical Testing: Response for
Classical Extremes
Purely Elastic Response Purely Viscous

(Hookean Solid) Response
(Newtonian Liquid)
δ = 0° δ = 90°
Stress Stress
Strain Strain
33
DMA Viscoelastic Parameters
Viscoelastic material response: 0° < δ < 90°
Phase angle δ
 The stress in a dynamic experiment is referred to as the complex stress σ*

 The complex stress can be separated into two components:
 An elastic stress in phase with the strain: σ' = σ*cosδ
σ' is the degree to which material behaves like an elastic solid
 A viscous stress in phase with the strain rate: σ" = σ*sinδ
σ" is the degree to which material behaves like an ideal liquid
34
DMA Viscoelastic Parameters:
The Complex, Elastic, & Viscous Modulus
The modulus of a material is defined as the ratio of the stress to the strain,
E = σ/εε. The complex, elastic, and viscous modulus are calculated as follows:
The Complex Modulus: Measure

of materials overall resistance to E* = σ*/ε = E' + iE"
deformation.
The Elastic (Storage) Modulus:
Measure of elasticity of material. E' = σ'/ ε =E*cosδ
The ability of the material to store
energy.
The Viscous (Loss) Modulus:
The ability of the material to
dissipate energy. Energy lost E" = σ"/ ε =E*sinδ
as heat.
35
Storage and Loss of a Viscoelastic Material
SUPER BALL LOSS
TENNIS
BALL X
STORAGE
36
DMA Viscoelastic Parameters: Damping, tan δ
E*
Dynamic measurement E"
represented as a vector
Phase angle δ
E'
The tangent of the phase angle is the ratio of the loss
modulus to the storage modulus.
tan δ = E"/E'
TAN DELTA (tan δ) is a measure of the damping ability
of the material, such as vibration damping.
37
Typical DMA Data
Glassy Region
Transition
Region
Rubbery
Plateau Terminal Region
Region
Viscoelastic
liquid
Very hard and
rigid solid
Stiff to Soft rubber
Storage Modulus (E' or G')

Loss Modulus (E" or G")
Temperature/Time/Frequency-1
38
Transient Testing
Stress Relaxation and Creep
39
Stress Relaxation Experiment
 Strain is applied to sample instantaneously (in principle)

and held constant with time.
 Stress is monitored as a function of time σ(t).

Strain
0
time
40
Deformation
0
time
Response for Classical Extremes
Elastic Viscous
Hookean Solid Newtonian Fluid
stress for t>0 is 0

stress for t>0
is constant
0 0
time time
41
Response of Viscoelastic Material
Stress decreases with time

starting at some high value
and decreasing to zero.
0
time
For small deformations (strains within the linear region)

the ratio of stress to strain is a function of time only.
This function is a material property known as the

STRESS RELAXATION MODULUS, E(t) or G(t)
E(t) = σ(t)/ε
42
Stress Relaxation – Material Response
Glassy Region
Transition
Region Rubbery
log Stress Relaxation Modulus
Plateau Terminal
Region Region
E(t) or G(t)
log time
43
Creep Recovery Experiment
 Stress is applied to sample instantaneously, t1, and held

constant for a specific period of time. The strain is
monitored as a function of time (γ(t) or ε(t)).
 The stress is reduced to zero, t2, and the strain is
monitored as a function of time (γ(t) or ε(t)).
creep
Stress
recovery
t1 t2
time
44
Deformation
t1 time t2
Response for Classical Extremes
Elastic (Hookean Solid) Viscous (Newtonian Liquid)
Strain for t>t1 is constant Strain rate for t>t1 is constant
Strain for t>t2 is zero Strain for t>t1 increases with time
Strain rate for t>t2 is 0
t1 time t2 t1 time t2
45
Creep Recovery Experiment:
Response of Viscoelastic Material
Creep σ> 0 Recovery σ = 0 (after steady state)
σ/η
Recoverable
Strain
t1 t2
time Recovery time
> 10 creep time
Strain rate decreases In the recovery zone, the viscoelastic
with time in the creep fluid recoils, eventually reaching an
zone, until finally equilibrium at some small total strain
reaching a steady state. relative to the strain at unloading.
Reference: Mark, J., et.al., Physical Properties of Polymers, American Chemical Society, 1984, p. 102.
46
Creep σ > 0 Recovery σ = 0 (after steady state)
σ/η
Less Elastic
More Elastic
Creep Zone Recovery Zone
t1 t2
time
47
log Creep Compliance, Jc
Creep: Material Response
Rubbery
Plateau
(strain/stress)
Region
Transition
Region
Glassy Region
Terminal Region
log time
48
The Instrument
49
DMA Q800
In 2018 the Q800 was

superseded by the DMA 850.
Theory of operation of the

instruments is similar.
There are differences in the

controller hardware and in the
software (TRIOS vs Advantage).
50
DISCOVERY SERIES DMA850
 Advanced drive mechanism for

unmatched stress and strain
performance
 Optimized frame mechanics for
measurements over a wider range of
frequencies
 High-speed electronics for fast signal
processing and data acquisition
 Separation of electronic box isolates
precision measurements from heat
and vibration for optimal data quality
 DirectStrain for superior strain control
 Saving of waveforms
 Mixing of modes
51
Measure Principle
 The Q800/Discovery 850 DMA is a

stress (force) controlled instrument.
Fixed
 It is composed of the following:
 A motor which applies the force Sample
(stress) to the sample.
 A displacement sensor that Displacement Sensor
measures strain (amplitude). Measures
deformation (Strain)
 When programming an experiment
the deformation is most of the time
input in the form of amplitude or
strain. Motor Applies
Force (Stress)
 The instrument then applies force (its

control parameter) until it measures
the requested amplitude or strain.
52
Measure Principle
 When programming an experiment the deformation is input in the form of

amplitude or strain.
 The instrument then applies force (its control parameter) until it measures
the requested amplitude or strain.
Minimum oscillation Check oscillation

Apply oscillation cycles
force displacement
NO Check
Adjust drive force if in
Range
YES
Calculate stiffness, damping, tan(δ)
53
Schematic of the Instrument
54
Q800 DMA & 850 : Key Design Elements
DRIVE
Air Bearing SHAFT
AIR BEARING
Air Bearing OPTICAL AIR BEARING

ENCODER SLIDE
Slide
Linear Optical
Encoder
Drive Motor Coil
Position Sensor DRIVE
Induction Motor MOTOR
[Controlled Force]
55
Innovative Technology
 Unique non-contact drive motor

 Air bearing -> low friction
 Optical encoder -> high displacement resolution
 Low mass clamps, high stiffness clamps and shaft
- rapid temperature equilibration
- able to measure the correct modulus of metals/composites
 Compliance calibration for almost every clamp
 Accuracy of moduli : sample shape is limiting factor
 Isothermal stability of ±0.1°C
 Temperature calibration with standards (e.g. Indium) for all
measuring geometries
 Temperature controlled submersion clamps & humidity chamber
 Stress/Strain controlled modes of operation
(Creep, Stress Relaxation, …)
 200 Hz on all deformations
56
Stress versus Strain Control
 Applying force/stress (very accurate)

 extremely linear motor
 motor is thermostatted to eliminate heat build-up (dimensional stability air bearing)
 force is calibrated over complete range (0.0001 - 18 N)
 calibrated with weights and electronically
 force resolution 0.00001 N
 no variation over time (very stable over long period)
 Measuring of displacement/strain
 with linear optical encoder:
large dynamic range (25 mm) and linearity compared to LVDT:
amplitude from 0.5 (Q800) or 0.005 (850) up to 10000 micron
 extremely high resolution (1 nm Q800 or 0.1 nm Discovery 850)
 based on diffraction patterns of light through gratings
 no temperature dependency
 no calibration needed (absolute value)
 Possibility to work in controlled strain mode
 very fast loop through hardware (like in rheology)
57
Modes of Operation
58
Modes Of Operation – Q800
 Multi-frequency Strain
 Multi-frequency Stress
Oscillation
 Multi-strain
 Multi-stress
 Creep Stress Control
 Stress Relaxation Strain Control
 Controlled force Stress & Rate Control
 Isostrain Strain Control
 Strain rate Rate Control
59
Discovery DMA850 – Modes of Operation
Test Mode Available Tests
Frequency Sweep
Strain Sweep
Oscillation Stress Sweep
Time Sweep
Temperature Sweep (Single, Multi-frequency TTS)
Temperature Ramp (Single, Multi-Frequency)
Fatigue Test
Stress Control Creep
Creep-Recovery
Creep TTS
IsoStress
Strain Control Stress Relaxation
Stress Relaxation TTS
IsoStrain
Rate Control Strain or Displacement Ramp
Stress or Force Ramp
Cfr table in the getting started manual: determine the mode for DMA 850 that is equivalent to the mode used for Q800
60
Modes of Operation
It might be convenient to use templates for unexperienced users
DMA850
Q800
available test depends upon
mode set in summary page
61
Q800 Modes Of Operation
 Multi-frequency Stress (Oscillation)

Multi-frequency Strain (Oscillation)
 Isotherm, or temperature ramp, or temperature steps
 Time, temperature & frequency dependence of Storage &

Loss Modulus, Tan Delta
 To compare materials (Modulus & transition temperatures)
 Thermoset curing behaviour
 Projection of performance under load using TTS
62
Time Sweep
Deformation  The material response is

monitored at a constant
frequency, amplitude and
temperature.
Time
Instrument Mode
Multi-Frequency
Method  USES
Equilibrate at x°C
 Cure Studies
Isotherm for y min
Frequency  Degradation
Single
Amplitude
In linear viscoelastic region
63
Epoxy Curing on Glass Braid
Clamp: Dual cantilever

Sample: Epoxy coated on
glass braid and wrapped in
aluminium foil
Dynamic time sweep
Temperature: 35°C
Frequency: 1 Hz
Amplitude: 10 µm
64
Frequency Sweep
Deformation  The material response to

increasing frequency
(rate of deformation) is
monitored at a constant
Time amplitude and
temperature.
Instrument mode
Multi-frequency
Method
 USES
 High and Low Rate(short and
long time) modulus properties.
Frequency Sweep
 Polymer melt processing
Frequency
(shear sandwich).
Program table up to 50 values,
 Extend range with TTS
cover multiple decades, usually from high to low
Amplitude
Single, only in linear viscoelastic region.
65
Frequency Sweep: Material Response
Transition
Rubbery Region
Terminal Plateau
Region Region
Glassy Region

log Frequency (Hz)
66
Happy & Unhappy Balls
Happy & Unhappy Balls

8 0
10 10
Modulus is the same
tan δ is very different
107
tan_delta (
Unhappy ball
)
[dyn/cm²]
[]
-1
10
E' (
)
106
Happy ball
5 -2
10 10
0 1
10-1 10 10
102
Freq [rad/s]
67
Temperature Ramp
 A linear heating rate is

applied. The material
response is monitored at
a constant frequency and time between
data points
constant amplitude of m = ramp rate
deformation. Data is (°C/min)
taken at user defined

Denotes Oscillatory
time intervals. Measurement
time (min)
68
Dynamic Temperature Ramp: Material Response
Glassy Region
Transition
Region Rubbery Plateau
Region Terminal Region

Temperature
69
Temperature Step & Hold /
Single Frequency or Multi-Frequency
 A step and hold Soak

Time
temperature profile is
Step Size
applied. The material
response is monitored Oscillatory
Measurement
at one, or over a range
of frequencies, at Time
constant amplitude of
deformation. Soak
Time
Step Oscillatory
Size Measurement
Time
70
Q800 Modes of Operation
 DMA Multi-strain (Oscillation)

 Evaluation of Linear Viscoelastic Region (LVR)
 “Mullins”-effect in elastomers
(modulus decreases as strain increases and remains low on subsequent runs, if
sufficient time is allowed the modulus returns to its initial level)
 DMA Multi-stress (Oscillation)

 Stress fatigue
 Stress-dependent LVR
71
Strain Sweep
Deformation  The material response to

increasing deformation
amplitude is monitored at
a constant frequency and
temperature.
Time
Instrument mode
Multi-Strain
Method  USES
Equilibrate at x°C  Identify Linear Viscoelastic Region
 Resilience
Strain sweep
Frequency
Single only
Amplitude
Program table up to 28 values
72
Dynamic Strain Sweep: Material Response
Linear Region: Non-linear Region:

Modulus independent Modulus is a function of strain
of strain
E' or G'
Stress

Slope
Strain (amplitude)
73
Multi-Stress Mode
 Sinusoidal application of preset peak forces instead of amplitudes

 Allows the user to setup a Force Table.
 Can be used to evaluate stress-dependent LVR.
74
 DMA Creep (Stress Control)

 Creep Compliance J(t), material sag (elongation)
under load
 DMA Stress Relaxation (Strain Control)
 Stress relaxation modulus E(t), tightness of gasket
seals & force fit parts with time
75
Programming Stress Relaxation on a Q800
Increment temperature in steps
76
Determining Strain For Stress Relaxation
Experiment
 If linear viscoelastic information is the goal, such as generation of a
family of curves for TTS, then the strain should be in the linear
viscoelastic region. The stress relaxation modulus will be
independent of applied strain in the linear region. A good starting
point is 0.1 to 1% strain.
 If the goal is to measure the stress as it relaxes under a specified

load (strain), then the question is "what is the range of strain that I
can apply on the sample?" This must be calculated. Help file lists the
calculations for strain (search on equations, choose calculations
based on clamp type).
77
DMA: Stress Relaxation on PP
78
Programming Creep on a DMA850
79
Determining Stress For Creep Experiment
 If you are doing creep and are interested in viscoelastic

information (creep and recoverable compliance), then you need
to conduct the test at a stress within the linear viscoelastic
region of the material. A good starting point is 500-1000 Pa.
 If you want to know the dimension change with time under a

specified load (stress) and temperature, a common question is
"what is the maximum/minimum stress that I can apply to the
sample?". This must be calculated. Help file lists the
calculations for stress.
80
DMA: Creep-Recovery Test on PET Film
S am p le: P E T Film Creep at 75°C File: C:\TA \D ata\DMA \P e tcreep

S ize : 1 0.549 0 x 6 .2 500 x 0.07 00 m m DMA O pe rator: A pplica tions L abo ratory
Metho d: C ree p R un D ate: 1 1-S e p-97 1 0:41
Co m m en t: S tress
0.4
 

 

 
0.3  




Strain (%)
0.2
0.1






 
       
0.0 
4 6 8 10 12 14 16 18 20 22
Time (min) Universal V2.6B TA Instrum ents
81
Creep Behavior in Each Viscoelastic Zone
J
4.5000E-7 1.0000E-5
4.0000E-7
8.0000E-6
3.5000E-7 1.5000E-3
compliance (m^2/N)
Glassy
compliance (m^2/N)
3.0000E-7
6.0000E-6 1.2500E-3
2.5000E-7
T
70°C g
compliance (m^2/N)
2.0000E-7 4.0000E-6 1.0000E-3
1.5000E-7
1.0000E-7 2.0000E-6
7.5000E-4
Plateau
5.0000E-8
0
0
0
110°C
50.00 100.0 150.0 200.0 250.0
5.0000E-4
150°C
0 50.00 100.0 150.0 200.0 250.0
time (s)
t time (s)
2.5000E-4
1.000E7 1.000E7 10.00 0

0 50.00 100.0 150.0 200.0 250.0
time (s)
1000000 1000000
0.12000
1.000 0.10000
100000 100000
compliance (m^2/N)
0.080000
Flow
tan(delta)
G'' (Pa)
G' (Pa)
0.060000
0.040000
190°C
10000 10000
0.020000
0.1000
0
0 50.00 100.0 150.0 200.0 250.0
time (s)
1000 1000
100.0 100.0 0.01000

25.0 50.0 75.0 100.0 125.0 150.0 175.0 200.0 225.0 250.0
temperature (Deg C)
82
 DMA Controlled force

 Stress/strain (force ramp) (Rate Control)
 Temperature ramp (fixed static force) (Stress Control)
 DMA Isostrain (Strain Control)

 Temperature ramp (fixed strain)
 DMA Strain rate (Rate Control)

 Strain ramp (%/min) or
Displacement ramp (μm/min)
83

 Force ramp (Rate Control)
 DMA Strain rate (Rate Control)

 Strain ramp (%/min) or displacement ramp (μm/min)
 Stress/strain curves for films & fibres

 Static modulus
 Evaluation of LVR
 Yield point
84
DMA Force Ramp Test on Solids
Deformation
 Force is applied to
material at a constant
m = force rate
rate. Resultant strain is
(N/min)
monitored with time.
USES
time (min.)
 "Static" modulus
 Determine linear region
Instrument mode
for tensioning clamps DMA Controlled Force
Method
Ramp force a N/min until b N
85
Force Ramp Helps Establish Parameters
Stress
Force
86
Ramped Force Experiment Polyethylene Film
(5 mm Length)
4
Controlled Force - Tension: Film
Sample
3 Broke
Static Force (N)
Drawing Stiffening
Yielding
Linear Region
0
0 5 10 15 20 25 30
Dimension Change (mm)
87
Strain-Rate Mode
 This mode lets the user set a rate of strain to apply, just like an
Instron Universal Testing Machine.
 This enables the user to perform the ever-popular ASTM D-790
and ASTM D-638 for evaluating the Flexural modulus and
Tensile modulus, respectively.
6 
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The PE sample in the 

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example was stretched 

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Displacement (µm)
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 
at a programmed rate of Stress (MPa) 

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500 microns/min.  
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0 2 4 6 8 10
Universal V3.4C TA Instruments
Time (min)
88
Polysaccharide Film Stress-Strain Test
Linear rate
time
Strain hardening
Geometry: Tension
Temperature: 37°C
Rate: 10 µm/s
89

 Temperature ramp (fixed static force) (Stress Control)
 DMA Isostrain
 Temperature ramp (fixed strain) (Strain Control)
 To measure Tg
 Measure softening point according to DTUL or HDT
TA307 & TA308
 Shrinkage and shrinkage force
 Processing orientation effects in films
 Thermal expansion coefficient CTE (?):
consider CTE of clamps !
Note: TMA is the dedicated technique to measure CTE,
uses quartz clamps (low expansion)
90
Constant Force Mode - Powder Softening Profile
Powder in cup, alu foil on top of it, TMA-like probe

100
Controlled Force experiment
3°C/Min Heating - 2 N Static Load
Expansion
0
107.19°C
Displacement (µm)
-100 165.42°C
-200 48.62°C
173.44°C(I)
-300 178.65°C
0 20 40 60 80
-400
-100 -50 0 50 100 150 200
Temperature (°C)
91
Iso-Force Temp Ramp: Measure Length Shrinkage
Film sample is held at a constant

force; shrinkage is measured
Hold force at 0.05N

Temperature : ambient to 120˚C
Ramp rate: 3˚C/min
92
Iso-Strain Temp Ramp: Measure Shrinking Force
Strain = 0.05%
Film sample is held at a constant

length; shrinkage force is measured
93
Effect of Orientation on Thermal Expansion of
Extruded Film
200
0
Displacement (µm)
Hold force at 0.01N

Temperature : ambient to 250˚C
Ramp rate: 3˚C/min
-200 Transverse Direction
Machine Direction
-400
0 50 100 150 200 250
Temperature (°C)
94
Discovery DMA 850 – Modes of Operation
Mix and match any combination of available tests types

(not possible on Q800)
Additional controls (conditioning step):

 Equilibrate or Jump or Initial Temp to a set temperature, set Soak time at
target temperature
 Set or Increment Relative Humidity levels, set Soak time at target RH
 Set or Increment a Force/Stress, Displacement/Strain
 Loop and repeat previous steps
 Refill GCA
 Data storage On/Off, set data sampling intervals
 Other: Control Motor State, Set external events, PID Tuning
95
Discovery DMA 850: Direct Strain Mode
 Native strain control mode like RSA-G2

Made possible by RSA-G2 electronics
 Traditional strain control uses an iterative combination
of controlled stress driving to a target displacement
Minimum Apply oscillation Check oscillation
oscillation force cycles displacement *
NO Check
Adjust drive force if in
Range
 In direct strain mode the motor directly commands a YES
target displacement and achieves it on the first try Calculate stiffness,

damping, tan(δ)
without iterating
 Ideal for challenging test conditions
- Fast ramp rates/ slow test frequency
- Quickly changing sample
- Soft samples at high frequencies
 Not recommended for high stiffness samples
96
Oscillation Strain Control Modes
 DMA 850 closes the loop around sample displacement, whereas Q800
used motor displacement (* in previous slide)
 For most samples, Sample displacement = Motor displacement
 EXCEPT extreme cases  high stiffness samples with compliance
effects: Sample displacement = Motor displacement – Compliance
850:
can be changed
from sample to
motor
97
DMA 850: Usage of Oscillation Modes
Oscillation Mode of Operation Recommended Usage & Comments
Mode
Oscillation Iterative control of  Default mode for DMA 850
Strain – oscillation displacement  Suitable for 95%+ of applications - from low to high
Sample at sample stiffness samples
Oscillation Iterative control of  High stiffness samples (> 16N total force, significant
Strain – oscillation displacement compliance) ONLY IF difference in oscillation displacement
Motor at motor (equal to (sample vs drive) is noticeable
sample displacement if  No difference for 99%+ of samples, similar data in both
modes
compliance is  Q800 only controlled motor displacement, and used
insignificant) compliance-corrected sample displacement to calculate
E*, E’, E”, etc.
DirectStrain Direct, real-time control  Consistent point timing with quickly changing sample (fast
of sample displacement ramp rates/ slow test frequency)
(similar to RSA-G2)  Low stiffness (soft) samples at high frequencies
 Not recommended for high stiffness samples
Oscillation Direct, real-time control  No feedback loop

Stress of sample force/stress  100X improvement over Q800
98
DMA Clamps
99
What Samples Can DMA Measure?
By changing the clamp, a wide range of different materials can be

tested: solid bars, elastomers, soft foams, thin films and fibers
Elastomers
Films
Fibers Gels
Solid Polymers
Foams Composites ( Polymer Melts )
consider a rheometer
100
DMA Clamps and Geometries
Shear Sandwich Bending or Cantilever Compression
Tension
Motor Applies Force
Strain Read by
Optical Encoder.
101
DMA Tension : Specialty Fibre
102
DMA Tension : Thin Film – Mk II
103
Tension Clamp Faces
The clamp consists of an upper fixed clamp and lower movable clamp. Both the
top and bottom clamp have rotating dual surfaces clamp faces.
The second clamp face has two thin

The smooth (or flat) surface
ridged surfaces at the top and bottom.
is intended for clamping of
This ridged clamp face is intended for
low modulus or soft samples.
clamping stiffer, high modulus
materials.
104
DMA Tension : Film/Fibre Mk III
 Redesigned clamp faces for easy and

uniform sample loading
 Visual guides for sampling alignment
 Test film and fiber samples with a
single clamp
 Smooth and grooved clamp faces for
the widest range of sample types
105
Thin Film Clamp - Submersion
Up to 80°C (Q800)
150°C (Discovery 850)
106
DMA : Tension Mode
Stationary
Clamp
Sample
(film, fiber, or thin sheet)
Movable clamp
 Best mode for evaluation of thin films and fibers (bundle or single filaments)
 Small samples of high modulus materials can be measured
 TMA-like constant force & force ramp measurements (mini-tensile tester)
107
DMA – Single and Dual Cantilever Clamp
DMA 850:
use torque wrench (10 in.lb) to
install fixed clamp. This
ensures that the nuts are not
torqued, which may risk
damaging the mounting posts.
All DMA:
use torque wrench to clamp
the sample.
108
Dual Cantilever Clamp
Sample
Movable Stationary
clamp Clamp
 Good general purpose mode (thermoplastics above Tg, elastomers)

 Highly damped materials can be measured
 Best mode for evaluating the cure of supported material
 Caution when running samples with reasonable dimension change
 Sample clamping torque is important
109
Single Cantilever Clamp
Sample
Stationary
Clamp
Movable
clamp
 Best general purpose mode (thermoplastics)

 Preferred mode over dual cantilever for most neat thermoplastics
(unreinforced) except elastomers
 Sample clamping torque is important
 Use back part of clamp (sample close to thermocouple)
110
Powder Holder for Dual Cantilever
111
DMA - 3 Point Bend
Submersion 3PB
available too
112
3PB
Sample
Stationary Fulcrum
Moveable Force
Clamp
 Best mode for measuring medium to high modulus materials

 Conforms with ASTM standard test method for bending
 Purest deformation mode since clamping effects are
eliminated
113
20 or 50 mm Low Friction 3 Point Bend Clamp
114
DMA – Shear Sandwich
115
Shear Sandwich
Movable
Clamp
Stationary
Clamp
Sample
 Square sample configuration, provides pure shear deformation

(do not compress on clamping)
 Provides Shear Moduli: G*, G', G" & G(t)
 Good for evaluating highly damped soft solids such as gels and
adhesives & elastomers > Tg
 Can be used for high viscosity melts and resins (be very careful !)
116
DMA – Compression (Old)
117
DMA – Compression (New)
 Self-aligning compression
clamp for quick, easy setup
 Upper plate is mounted to a
ball-joint that has free
motion to tip and tilt
 Cfr TA Tech Tips:
compression clamp
installation & calibration for
the DMA850
118
Compression Clamp - Submersion
119
Compression
Movable Clamp
Sample
Stationary clamp
 Good mode for low to medium modulus materials (gels, elastomers)

 Materials must provide restoring force (support necessary static load)
 Make sure the clamp is in the down position before closing the furnace !
120
DMA - Penetration
 Only works with static force, no

dynamic force.
 Not recommended for thermal
expansion coefficient (CTE)
determination.
Macro
TMA-like probes
Hemispherical Penetration
Expansion
121
Clamp Selection - Rigid Samples
 Rigid (Glassy, Crystalline) Samples
 Rectangular or cylindrical sample desired:

necessary for quantitative Young’s modulus
L/T > 10: otherwise mixed mode of deformation and modulus will
be too low
 Use Dual/Single Cantilever or Three Point Bend Clamps
 Smooth edges for better gripping of samples
 Pellets/thermoset resins - form into bars or films
 Unusual shapes - cut into rectangular bars or run as formed for
qualitative information
 Films and Fibers
 Use Tension Film or Specialty Fiber clamps
122
Clamp Selection - Elastomers
 For sub-Tg information use dual/single cantilever clamp.
 To characterize through Tg and above, use single cantilever.

If sample is sufficiently thin (low stiffness) then tension can be
used.
 Shear sandwich clamp

Can be used to characterize material above Tg
Can be used for curing (Vulcanizing) a rubber
123
Clamp Selection - Coatings and Resins
 Coatings
Only qualitative data from supported samples
Transitions of coatings on substrates are best observed in
bending
Tension clamps can be used for free standing samples
 Resins
Use fiberglass braid, metal mesh or metal shims as support
for cure characterization in dual cantilever
Use 8 mm dual cantilever clamps for low stiffness samples
124
DMA-RH Accessory
 Easier mounting on
the Discovery 850
 Discovery 850
available with RH
accessory only, no
standard furnace
required
125
DMA-RH Specifications
Temperature Range 5°C–120°C

Temperature Accuracy ±0.5°C
Maximum + or -1°C/min
Heating/Cooling Rate
over entire temperature range
Humidity Range See humidity range chart
5-90%RH: ±3% RH
Humidity Accuracy
>90%RH: ±5% RH
+ or - 2% RH/min
Humidity Ramp Rate
(fixed*)
*Alternative pseudo-linear RH
ramp rates can be achieved
through Step-Iso control
126
DMA-RH Clamps
 RH chamber is compatible with most clamps

 Clamps which expose the sample’s surface area are
recommended
 985018.901 special clamp kit for RH accessory, includes:
 Small 3PB (10 mm)
 Penetration
 Compression (only 15 mm diameter, not 40 mm)
127
DMA Calibrations
128
Help Menu Q800
 Browse the Contents list or

search using the Index tab.
For help topics on your laptop browse to:

C:\Program Files(x86)\TA
Instruments\Thermal
Advantage\Qseries\Help\QDMA\qdma.htm
129
Help Menu DMA 850
130
Instructional Videos
 From www.tainstruments.com click on Support

 Select Tech Tips and choose a video
131
DMA Q800 Chart of Calibration Procedures
Mass
Clamp Zero
Compliance
Position
Electronics Clamp Mass

Balance Compliance
Instrument Force
Weight 0.005 Steel
Dynamic 0.010 Steel
0.020 Steel
Temperature (optional) 0.030 Steel
(other steel)
All calibrations are ‘wizard’ driven. Analyze Data
Go to ‘Calibrate’ and pick the appropriate calibration
132
Discovery DMA 850 Calibrations
 Clamp
 Position (Automatic)
 Installation Stability
Verification
 Force Calibration
 Phase Calibration
 Temperature Offset
(Optional)
133
DMA Clamp Calibration Details
 Clamp Calibration needs to be done initially for every clamp the first
time you use that clamp. The calibration is stored in the software for
that specific clamp.
 Experiment will not run without clamp calibration.
 There are three clamp calibrations:

 Mass
 Zero
 Compliance
 Not all calibrations need to be performed on all clamps.
 Recommended to redo zero and compliance cal every time you

change the clamp.
134
DMA Clamp Calibration Chart
Clamp Mass Zero Compliance

Dual/Single Cantilever  
3-Point Bending  
Tension Film   
Compression/Penetration   
Shear Sandwich 
Speciality Fibre  
135
DMA Clamp MASS Calibration
 Only calibration performed on all clamp types.
 Mass Calibration is performed FIRST when clamp is changed.
 Weighs the clamp and compensates for its mass to ensure accuracy
of force measurements.
 Mass calibration takes 5 minutes to run
 MASS CALIBRATION CHECK: Release (float) the clamp by

pressing the FLOAT/LOCK key on the module. Manually position
the clamp in the middle of its range and release it. The clamp
should maintain its position or SLOWLY drift up or down. If the
clamp RAPIDLY sinks or rises, perform mass calibration. If
condition persists for penetration and compression clamps, after
mass calibration, perform position calibration.
136
DMA Clamp ZERO Calibration
 Determines the point of zero sample length for accurate

measurements of sample length (tension) or thickness
(compression)
 Zero calibration is performed SECOND, after clamp mass

calibration.
 COMPRESSION/PENETRATION CLAMPS: The Gauge Block

Size window will appear. Leave all entries at ZERO and select
OK. Gauge block size must be zero for calibration.
 FILM/FIBER TENSION CLAMPS: Clamp Kit comes with an

OFFSET GAUGE. Measure the length of the offset gauge and
mount the gauge in the clamp. Enter the length of the offset
gauge block and select OK.
137
DMA Clamp COMPLIANCE Calibration
 Measures the flexibility (compliance) of the clamp and calibrates the

instrument to ensure quantitative modulus and damping measurements on
stiff samples.
 Compliance calibration is performed LAST, after zero calibration.
 COMPRESSION/PENETRATION CLAMPS: Enter ZERO for all dimensions

on the Compliance Sample Calibration window and select OK. Sample size
must be zero for calibration.
 TPB & SINGLE/DUAL CANT.: Accessory Kit comes with a Precision Steel
Compliance sample (52mm x 12.7mm x 3mm). Measure the width, and
thickness of the compliance sample and mount in the clamp. If you are
using Dual Cantilever or Three Point Bending, use the appropriate length
between the clamps. If you are using Single Cantilever, you will need to
measure the sample test length between the inside clamp faces (≈17.5mm)
using the telescoping gauge provided. Enter the length of the compliance
sample, select OK.
138
DMA Clamp COMPLIANCE Calibration
 TENSION FILM: A Precision Steel Compliance sample (30 mm x 6.4 mm x

0.1 mm Part# 984331.901) is provided.
 After calibrating the mass and zero for the clamp, press the SCROLL soft
key on the module display until LENGTH is displayed (MAKE SURE YOU
DO NOT USE POSITION).
 Float the drive shaft and manually set the length to approximately 15 mm.
 Measure the width, and thickness of the compliance sample and mount in
the clamp. MANUALLY ENTER THE LENGTH DISPLAYED ON THE
MODULE. DO NOT HIT THE MEASURE KEY ON THE MODULE TO GET
THE LENGTH FOR THE CALIBRATION.
 Finish calibration.
 Details in this procedure are specific for the Q800 !
For the 850 just follow the wizard.
139
DMA Clamp Calibration Report (Q800)
 REPORT returns the values for the currently installed clamp
 Notes
 Turn air bearings on for 20 min before mass calibration
 Mass can change with residue on clamps
 Clamp Compliance should be ≤ 1.0 µm/N
140
DMA Clamp Typical Compliance
 Clamp
 Single Cantilever ≤ 0.8

 Dual Cantilever ≤ 0.2
 Three Point Bending ≤ 0.6
 Tension Film ≤ 0.5
 Compression ≤ 0.6
 Tension Fiber N/A
 Shear Sandwich N/A
Note
Compliance of 0.5 µm/N means stiffness of 2.106 N/m
141
Discovery DMA 850 Clamp Calibration
 Mass calibration much faster than

on Q800
 Clamp zero calibration is called
Clamp offset calibration
 Procedure for clamp compliance
calibration for film more
straightforward than on Q800
142
Position Calibration
 Calibrates the absolute position of the drive shaft (and slide) as read by the
Optical Encoder
 Perform when DMA is moved, reset, or powered down with floating clamp
(often happens due to power failure during test). To prevent re-calibration,
make certain "Stop" is pressed before shutting off or resetting instrument.
Set method end condition for the clamps to "lock" if power tends to go out.
 To Perform Calibration on Q800

 Remove both fixed and moveable clamps
 Select Position from the Calibrate menu.
 Calibration takes about 7 minutes
143
DISCOVERY DMA850 POSITION CALIBRATION
 Automatically performed at  If position calibration is

instrument startup after the unsuccessful, TRIOS will
frame has warmed up automatically popup the
 Drops the motor to the lowest calibration when it connects
position, establishes zero to the instrument
reference position  then  No separate option to do
motor sweeps entire 25 mm position calibration from
travel range TRIOS
 Shipping clamp, samples, and  Touchscreen allows user to
certain clamps have to be do position calibration at any
removed for successful time
calibration
144
DMA Position Calibration Check
 Penetration and Compression Clamps: Manually position the clamp in the

middle of its range of travel and release it. The clamp should maintain its
position or slowly drift up or down. If the clamp rapidly sinks or rises, and
the clamp mass has already been calibrated, the clamp position requires
calibration.
 For all other clamps: Press the SCROLL button on the DMA module until
position is on the display. Manually move the clamp to the top of the travel.
The position signal on the instrument display should read between -0.5 to
1.0 mm. Move the clamp to the bottom of the travel. The position signal
should read between 24.5 to 25.5 mm. If the upper or lower limit are not in
the specified limits, calibrate position.
145
Q800 Instrument Calibrations
 Three instrument calibrations

 Electronics
 Force
 Dynamic
 Instrument calibrations need to be performed when the DMA
is moved, or when the feed hose for the air cool or GCA is
removed or installed
 Electronics Calibration
 Performed to calibrate the electronics
on the analog board.
 Takes approximately 10 minutes.
 Install shipping bracket to perform Electronics calibration
146
 Measures the moving mass of instrument and calibrates
motor force response
 Two steps:
1. Balance:
measures the amount of force needed to hold the position
of the drive shaft.
2. Weight:
measures the amount of force needed to hold the position
of the drive shaft when a weight (typically 100 g) has
been added.
 Takes approximately 7 minutes
 Calibrate if the drive shaft is changed.
147
 Dynamic Calibration
 Multi-step process - measures samples of known stiffness and
loss to determine the dynamic performance over wide range of
force and frequency.
 Perform calibration when the instrument is moved or when poor
frequency performance is observed.
 Be very attentive how to load the samples, especially the thin
ones, should not be bend !
148
Q800 Instrument Calibration Report
Calibrate,
report
 Note:
 Dynamic fails above 0.1 The lower the residual value, the better the
calibration. The residual values should by preference be < 0.01 (< 0.05
for dynamic).
 If instrument does not report a calibration failure then all values are OK.
It is typical for the values to change slightly with time.
149
Discovery DMA 850 Instrument Calibrations
 Installation Stability
Verification
 Phase Calibration
150
DISCOVERY DMA850 INSTALLATION STABILITY VERIFICATION
Done by service engineer at installation

 Verifies stability of DMA 850’s installation
 Ensures all four feet are in contact with the table/bench surface
 Performed without any clamp or sample
 The installation stability verification performs a time sweep test
at a fixed oscillation displacement and high frequency. A real
time readout of the residual phase angle is displayed in TRIOS
and on the instrument's touchscreen and will reach a maximum
value at the optimum position.
 User manually adjusts one foot (typically front right) to maximize
the value of the residual angle
 Mainly required for high frequency testing
 Perform when instrument is moved
151
DISCOVERY DMA850 FORCE CALIBRATION
 All DMA 850’s are factory

calibrated using multiple weights
over the entire range of travel
 User only needs to calibrate
force using a known 1 kg weight
 Step 1: Empty drive shaft (tare)
Step 2: Mass of tool holder
Step 3: Mass of 1 kg weight
 All mass and force calibration
performed at 12.5 mm
Otherwise thermocouple could
be damaged if tool drops
152
DISCOVERY DMA850 PHASE CALIBRATION
 Replaces Q800’s dynamic

calibration, uses first principles
 Step 1: No clamp or sample
Step 2: Dual Cantilever –
Mass Calibration
Step 3: Cantilever –
Compliance Calibration
Step 4: 0.003” Steel shim
 Entire calibration takes around
15-20 minutes – much faster
than Q800
153
DMA Confidence Check -
Expected Results For Polycarbonate
 Single Cantilever, 20-30 micrometer amplitude, 1 Hz

frequency, torque to 10 using torque wrench
 Storage Modulus at Room Temperature

E' = 2.35 GPa (2350 MPa) +/- 5%
 Tan Delta at Room Temperature

Tan δ < 0.01
 Transition Temperature
Tan δ peak from 155-160°C @ 1Hz, 3°C/min
E" peak will be about 5°C lower
154
Influence of Incorrect Sample Dimensions on E’
130
125
120
115
110
Modulus (%)
105
100
95
90
85
80
1.45 1.5 1.55 1.6 1.65 1.7 1.75
Thickness (mm)
155
DMA Temperature Calibration
156
 Note: Thermocouple position and sample or thermocouple

shields can effect temperature results from a temperature
ramp. So calibrate in same conditions as you’ll measure.
Sample
shield
Thermo-
couple
shield
Thermocouple
157
 No real consistency in literature !

 Choose procedure that best suits your needs
 Two types of calibration
 Absolute temperature calibration
 Dynamic temperature calibration
(thermal lag)
158
 Prior to any temperature calibration:

Reset or Clear temperature table to zero !
After typing in measured correction(s): Apply or Send
Q800
DMA 850
159
Absolute Temperature Calibration
 Help File
 Sample thermocouple accuracy compared with an
external thermocouple under isothermal conditions.
 DMA should be at ambient temperature with

furnace open, for at least 1 hour
1- Measure ambient temperature with reliable
external thermometer
2 - Note temperature reading of DMA
 Enter in temperature table:
Correct temperature = reading 1
Observed temperature = reading 2
160
Absolute Temperature Calibration: More Scientific
 ASTM E1867-06
 Sample thermocouple corrected by measuring
melting point of two recognised standard reference
materials.
 Load the standards in a polymer tube or wrap them
into polymer tape to protect the clamps/instrument.
e.g. indium wire in PTFE tube
 Run under the same heating rate conditions as you
will run the samples.
 Select the standards in the temperature range of
interest for the sample.
161
Dynamic Temperature Calibration (Thermal Lag)
 Using a polymer (Tg), e.g. PC
 Step 1: With the absolute temperature calibration (isothermal) in place
Run Polycarbonate using stepwise isothermal method through Tg region. This will give
true temperature range of Tg (no thermal lag). Measure Tg temperature as peak in
Loss modulus (E”).
 Step 2: With the temperature table reset to zero
Run fresh polycarbonate at dynamic heating rate to be used to run samples. Again
measure the Tg temperature as the peak in Loss Modulus (E”).
 Input true equilibrium Tg temperature (test 1) into calibration table as Correct

temperature and the Tg temperature from the dynamic heating experiment (test 2) as
Observed temperature.
162
Dynamic Temperature Calibration
Methodology for stepwise isothermal experiment

(indicated temperature region is for PC)
1. Equilibrate at 130°C
2. Isotherm 5 minutes
3. Frequency sweep
4. Increment temperature by 1°C (or smaller)
5. Repeat segment 2 until 170°C
 Put the instrument into Multi-frequency strain mode

 Set the frequency in the frequency table to 1 Hz
 Torque the sample in the clamps to 10
 Set the amplitude to 50 microns or the strain to 0.07%.
163
Dynamic Temperature Calibration
 Use the thermocouple shield and the geometry

shield if you will be using it for your sample runs.
 If a different heating rate is required for your sample

the dynamic run (step 2) should be repeated at the
required rate.
 The compensation for thermal lag can be significant.
 After this calibration the ambient temperature

reading is expected to be unusual high or low.
 Choose a polymer with a transition in the same

temperature range as your sample.
164
What about the different clamps ?
 Polymer Tg’s
 Cantilever
 3-Point Bending (caution with pure amorphous materials)
 Thin Film
 Melting Points
 Cantilever (metal wire in polymer tube or between 2 wood splints
e.g. coffee stirrers)
 Thin Film (wire or foil format with protective foil wrapped around)
 Compression (protect clamp with aluminium foil)
 Penetration (protect clamp with aluminium foil)
 Modulus Equivalence
 Shear Sandwich
165
DMA-RH Calibration
 Temperature and humidity are calibrated at the factory

through a software routine which uses an external
RH/temperature probe.
 Verification of RH by using sample in metal mesh ?
e.g. deliquescent salt (but can be corrosive)
166
Measurement Principles
167
Measure principles of DMA
 An example of a typical measurement over a wide temperature range
Stiffness, K Force/amplitude in N/m
Measured strain
(programmed) Stress (Instrument
Control Variable)
Temperature
 The measured amplitude (strain) is constant throughout the test.

 The controlled force variable changes as the stiffness of the sample
changes to keep the amplitude constant
168
 Force & Amplitude

 The DMA is stress or FORCE controlled. This means that the
motor can apply any force within the range of its specification.
 The DMA uses an optical encoder to measure displacement.
This means that the amplitude/strain selected must be within
the minimum & maximum limits of the optical encoder.
 The force range of the DMA is
 0.0001 N to 18 N
 The amplitudes that can be applied in a dynamic
experiment are from
 ± 0.5μm (Q800) or ± 0.005μm (DMA 850) to 10,000 μm
169
 Recommended starting Amplitudes for Dynamic Experiments
Clamp Type Amplitude, µm
Tension Film or Fiber 15 to 25
Compression 10 to 20
Three Point Bend 25 to 40
Dual/Single Cantilever 10 to 50
Shear Sandwich 10 to 20
Specialty Fiber 15 to 25
 If the amplitude requested does not require at least 0.0001 N force, the
measurement will be out of specification. In such cases increase the amplitude
in increments of 5-10 μm. Do not exceed the Linear Viscoelastic Region (no
creep/permanent deformation of the sample should occur).
 A higher amplitude will generally provide less noise in the result.
170
 If the amplitude/strain requested requires more than 18 N force the

measurements will most likely be ok. When the Q800 is driving at
the full 18 N the module will display “Force Limit”.
 The sample is so stiff that the full 18 N of force is insufficient to
displace the sample to the requested amplitude/strain.
 Options to reduce the force at this amplitude/strain:
 Reduce the sample stiffness (tension/cantilever/3PB)
 Increase sample length or span length
 Reduce sample thickness or width (Cross section area)
 Reduce the measurement frequency
 Reduce the Amplitude/strain
The measurement is not valid if the measured amplitude is below
the 0.5 μm limit of dynamic displacement.
171
 “Force limit” scenario
S tiffn ess, K
M a x . F o rce
M easu red strain

(p ro g ram m ed ) S tress(In stru m en t
C o n tro l Variab le)
Te m p e ra tu re
 Force remains at 18 N until the request amplitude is achieved. As

sample stiffness drops on heating, the instrument will at some
point be able to achieve the programmed amplitude/strain.
172
Measure principles of Q800 DMA
Minimum force limit is reached:

0.001
Stiffness, K
Min. Force limit

Reached. Strain
begins to increase.
Measured strain
Stress (Instrument
(programmed)
Control Variable)
Temperature
173
Measure principles of Discovery 850 DMA
Auto Ranging Control
 Standard – 2 user
parameters
 Minimum oscillation force
 Maximum oscillation
displacement
 Enhanced – 2 additional
user parameters
 Maximum oscillation force
 Minimum oscillation
displacement
174
Measure principles of Discovery 850 DMA
Auto Ranging Control
175
 Sample Stiffness and Modulus calculations

 Very important to consider sample geometry – Sample
length, width (or diameter) and thickness.
 Simply because a sample can be loaded into a geometry
it does not necessarily mean that it can be tested
effectively.
 To understand why, it is important to realise the difference
between Sample Modulus and Sample Stiffness.
 The fundamental measurement of the DMA is sample
stiffness K.
 Sample stiffness is defined as the force applied to the
sample (in Newton N) divided by the amplitude of
deformation (in micrometer μm).
 The stiffness of a material is an extrinsic property that is
dependant on its geometry (physical dimensions).
176
 The Modulus of a material is an intrinsic property,

independent of its geometry.
 As an example consider Aluminium in two physical forms:
 Aluminium foil – very easy to bend, twist and fold by hand
– low stiffness.
 A one inch thick Aluminium bar – very difficult to deform
by hand – high stiffness.
 Both are the same material but by changing the physical
dimensions the amount of force required to deform them
changes: stiffness changes.
 However, the Modulus of both the Al foil and the Al bar are
the same.
177
 Two materials of different Modulus can have the same

stiffness through adjustment of their physical dimensions:
decreasing sample thickness will reduce stiffness
T h ick a n d T h in T h ick a n d T h in
S a m p le s C a n H a v e S a m p les T h a t H a v e
T h e S a m e S tiffn e ss T h e S a m e M o d u lu s
F = 1 N F = 1 N
x = 10 m m x = 10 m m
H ig h M o d u lu s L o w S tiffn e s s S a m p le
M a ter ia l
F = 1 N F = 1 N
x = 2 mm
x = 10 m m
H ig h S tiffn es s S a m p le
L o w M o d u lu s M a te ria l
178
 After the instrument makes the fundamental measurement

of stiffness, the materials modulus is then calculated.
 Dynamic Experiments (Properties measured at frequency)
 Raw signals measured are:
 Force
 Amplitude of deformation
 Phase angle
 Instrument calibration factors are then applied to the raw
signals.
 Force and Amplitude are used to calculate the complex
stiffness K*
 Complex Stiffness K* used with the phase angle to
calculate Storage & Loss Stiffness, K’ & K”.
179
 Tan delta is calculated as the ratio of K” to K’.

 Storage and Loss Moduli are then calculated by multiplying
the raw stiffness measurements by the appropriate geometric
factors, GF.
 Transient Experiments
 Stress relaxation & Creep
 Controlled force (Stress) and Controlled Rate (Strain)
 Instrument measures the raw signals of force and
amplitude of deformation. Stress and strain are
derived from these raw signals and normalised for the
geometry factor GF.
180
 The sample modulus is calculated in the DMA by multiplying the

measured sample stiffness, Ks, by the geometry factor, GF.
Modulus = Ks x GF
 The measurable stiffness range of the instrument is a fixed quantity
between 100 to 10,000,000 N/m. The measurable modulus range
for a given sample size can be determined by solving the equation
at the minimum and maximum stiffness values.
 Since the modulus of the material is an intrinsic property, i.e.

independent of the sample dimensions, it can be seen that the
sample dimensions must be selected to yield stiffness values within
the allowable measurable range of the instrument.
Ks = Modulus/GF
181
 The stiffness range of the DMA instrument is

100 N/m to 10,000,000 N/m (102 to 107 N/m)
 If sample stiffness is above or below this range then the
samples size will need to be changed or the clamp type
changed
 Note that clamp stiffness is typically slightly lower e.g.

ca 2.106 N/m for film clamp. Ideally sample stiffness
should be an order of magnitude lower for highly
quantitative modulus results
182
Guidelines for changing Sample Stiffness
Clamp Type To Increase Stiffness…… To Decrease Stiffness…….
Tension Film Decrease length or increase width. If Increase length or decrease width. If
possible increase thickness. possible decrease thickness.
Tension Fiber Decrease length or increase diameter if Increase length or decrease diameter if
possible. possible.
Dual/Single Cantilever Decrease length or increase width. If Increase length or decrease width, if
possible increase thickness. Possible decrease thickness.
Note: L/T > 10 Note: L/T > 10
Three Point Bending Decrease length or increase width. If Increase length or decrease width. If
possible increase thickness. possible decrease thickness.
Compression – circular sample Decrease thickness or Increase Increase thickness or decrease

diameter. diameter.
Shear Sandwich Decrease thickness or Increase length Increase thickness or decrease length
and width. and width.
183
 The geometry factor (GF) equations and operating windows can be

used to help you determine both the optimum sample size for a
sample under test, and the modulus range for a particular sample
size.
Operating Window for Tension Film Clamp
M o d u lu s (P a )
13
10
12
10
1 0 11
}
10
10 M o d u lu s
10
9 R ange
8
10
107
6
10
G e o m e t ry F a c to r = L /A = 1 0
5
10
4
10
1 0 -1 100 10
1
102 103 104 105
G e o m e tr y F a c to r (1 /m m )
184
Measure principles of Q800 DMA
 To use the operating window, calculate the geometry factor

using the dimensions of the sample to be tested. Strike a
vertical line at the calculated geometry factor. The maximum
and minimum modulus will be where the vertical line crosses
at the upper and lower limits of the geometry window.
 For Tension Film Clamp: GF = L/A where L is the length and
A is the cross sectional area
185
Operating Window Film & Fiber
Modulus (Pa)
13
10
12
10
11
10
10
10 L
Film GF =
A
9
10
8
10 L L = Sample Length
Fiber GF =
ρ A = Cross Sectional Area
7
10
= width x thickness = W x T
6
10 ρ = Fiber Linear Density
10 mm long 20 mm long
5 5 mm wide 4 mm wide 20 mm long
10 0.2 mm thick 0.1 mm thick 0.1 mm diameter
4
10
-1 0 2 3 4
10 10 10
1
10 10 10 10
5
Geometry Factor (1/mm)

186
Operating Window Dual Cantilever
Modulus (Pa)
13
10
12
10
11
10
10 1  L3 L 
10 GF = + S(1 + ν)
9
F 192I 2A 
10
8
10 I = Geometric (Inertial) Moment
7 = 1/12 T3W for rectangular samples
10
ν = Poisson's Ratio
10
6 S = Shearing Factor
F = Clamping Factor
5
10
16 mm long 35 mm long 35 mm long 8 mm long
10 mm wide 12.5 mm wide 12.5 mm wide 12.5 mm wide
4 3.2 mm thick
10 4 mm thick 1.75 mm thick 0.1 mm thick
3
10
-1 0 1 2 3 4 5
10 10 10 10 10 10 10
187
Operating Window Single Cantilever
13
10
12
10
11
10
10
10
1  L3 L
GF = + 2S(1 + ν)
F 12I A 
9
10
8
10
7
10
6
10
5
10 17.5 mm long 17.5 mm long 17.5 mm long
12.5 mm wide 12.5 mm wide 12.5 mm wide
3.2 mm thick 1.75 mm thick 0.5 mm thick
4
10
3
10
-1 0 1 2 3 4 5
10 10 10 10 10 10 10
188
Operating Window 3PB
Modulus (Pa)
13
10
12
10
11
10
10
10  L3 L 
GF =  48I + S(1 + ν )
9
2A 
10
8
10 No F
7
10
6
10
20 mm long 50 mm long
5 50 mm long 12.5 mm wide
12.5 mm wide
10 2.5 mm thick
12.5 mm wide 1 mm thick
3.2 mm thick
4
10
0 1 2 3 4 5
10 10 10 10 10 10
189
Operating Window Shear Sandwich
Modulus (Pa)
10
10
9
10
8
10
7
10
6
10 3 T
GF =
10
5 10 A
4
10
3
10
each piece each piece
2 mm thick 4 mm thick
2
10 10 mm square 5 mm square
1
10
-3 -2 -1 0
10 10 10 10
190
Operating Window Compression
Modulus (Pa)
10
10
10
9 Fe = Compressibility Correction
(a strong function of sample size and Poisson's ratio)
8
10
7
10
6
10
T
5
G F = Fe
10 A
4
10
3
10
1 mm thick
2 2 mm thick 6 mm thick
40 mm diameter
10 20 mm diameter 10 mm diameter
1
10
-4 -3 -2 -1 0
10 10 10 10 10
191
Clamp Selection
Sample Clamp Sample Dimensions

High modulus metals or 3-Point Bend L/T > 10 if possible
composites Dual Cantilever
Single Cantilever
Unreinforced thermoplastics Single Cantilever L/T > 10 if possible
or thermosets
Brittle solids (ceramics) 3-Point Bend L/T > 10 if possible
Dual Cantilever
Elastomers Dual Cantilever L/T > 20 for T < Tg
Single Cantilever L/T > 10 for T < Tg
Shear Sandwich only for T > Tg
Tension T < 2 mm W < 5mm
Films/Fibers Tension L = 10 to 20 mm
T < 2 mm
Supported Systems 8 mm Dual Cantilever Minimum sample (foil
protection of clamps)
If length/thickness > 10, GF is simplified, dropped shear contribution
192
Preparation of Solid Test Specimen
 Uniform and well-defined

dimensions are extremely
important for accurate
modulus measurements !
193
Hints for Preparing Solid Samples
 Films
 Use parallel blade cutter or razor blade to cut parallel edges – cut
5 to 8 mm wide.
 Make sure to cut films in same direction, machine or transverse,
for comparisons.
 Uneven film thickness can be problematic since aspect ratio is
extreme
 Fibers
 Thicker single fibers, e.g. carpet fibers are easily run.
 Prepare bundles out of thinner fibers. Try to twist uniformly.
194
Alignment in Tension Mode
 Buckling during loading causes serious errors

as buckled areas do not “feel” the force or
deformation
 Buckling can be the result of non-uniform
stretching, or crooked loading of a film.
 Observe film from the side while oscillating to
verify goodness of load.
Force  If sample is buckling, reload a new sample.
If sample buckles during
oscillation, modulus
is artificially low.
ideal inclined sagging variable thickness

195
Preparing Samples – The Importance of Shape
Shape: Molded samples are often not flat. May lead to poor contact
in Cantilever and Three Point Bend Clamps. Sand samples smooth.
Cantilever Bending or 3PB Molded
sample
Not OK !
Need Smooth surfaces
for good contact
196
Sample twist along length can cause problems with accurate modulus
measurements. Need to make sure the sample aligns to the clamp.
Three Point Bending  Alternative: low friction 3 pt bend clamp

 Rocking action eliminates artifacts due to
twist in the sample
 Rolling action eliminates friction
 “Rock-n-Roll” Clamp!
Force
Sample twists rather
than bending. Modulus
is artificially low.
197
Modulus Comparison: 3 Pt Bend Clamp Original
vs. Low Friction
 Sample: PC; 50mm x 12.45mm x 4.41mm @ 10Hz
2500
2442.MPa
-4% off Theoretical Value of 2350
2000 1934.MPa
Storage Modulus (MPa)
18% off Theoretical Value of 2350
1500
1000
––––––– Original 50mm 3 Pt Bend Clamp

––––––– Low Friction 50mm 3 Pt Bend
500
2 4 6 8 10 12 14 16 18 20 22 24 26 28
Amplitude (µm)
198
 Foams, elastomers, and gels can

be difficult to cut flat and parallel.
Need to get good contact over
entire surface of compression
clamps.
 Don’t try to compensate for poor
sample contact with too much
static force.
Not OK !
199
Some Sample Prep Tools
Cork Borer
Good for stiff foams and

sheets of rubber
984486.901
film cutting kit
200
DMA 850 New Motor Modes
 Conventional (Q800)
‘frictionless’ float and
lock modes
 850: Unlocked mode for
easier positioning when
loading samples
 850: Directly position
drive at a specific
location (e.g. to set
sample length for film)
or apply a preload force
201
Sub-ambient Clamping procedure
 Clamping should by preference be performed at the

start temperature. Use the following method
procedure :
– Motor drive OFF
– Initial Temperature –100°C
open furnace and tighten clamps further
– Motor drive ON
– Isotherm 15 minutes (depends on sample)
– Ramp 3°C/min to 200°C
202
Sub-ambient Clamping procedure
 The Go to Temperature option allows the user to go to a sub-

ambient temperature without starting the run so that the sample
could be retightened in the clamp. Allowable Temperatures –150°C
to 20°C
 The Measure after Equilibrate option allows samples to be re-

measured after Equilibrate method segment.
203
Q800 Instrument Preference Settings &
DMA 850 Clamp Settings
204
Use of Thermocouple Screen for GCA
 The Thermocouple Screen is important for experiments that start at sub-

ambient temperatures with GCA. If you use it during measurements also
use it during temperature calibration.
205
Use of Mesh Screens for Cantilever & Tension Clamps
For GCA
cooler
206
Sub-Ambient Heating Rate Noise : Test @ 3°C/min
 The data in the plot below contains no smoothing !

8
6
Deriv. Temperature (°C/min)
Note that the curves

4 are shifted along the
y-axis !
0
––––––– No Screens
––––––– 100 Mesh Screen
––––––– Thermocouple Screen
––––––– 100 Mesh & Thermocouple Screens
-2
-150 -100 -50 0 50 100 150
Temperature (°C)
207
Screens for the ACS Cooler Only
 Do not use the thermocouple screen in this case !

 Do not use above 400°C (metal band = Al)
208
Static Force (Preload Force)
The static force is the force initially placed on the sample when
the measure button is pressed. The purpose of the static force
depends on the type of clamp installed.
 Tension film or fiber

Applied to remove the buckle from a sample in tension so an
accurate length measurement can be made. Typically 0.01 – 0.05
Newton. For thin samples (<50 μm) best to use the higher end of
this range to ensure sample flatness in the clamps.
 Compression
Applied to keep upper plate in contact with sample so an accurate
thickness measurement can be made. Typically 0.001 – 0.05
Newton. The less stiff the sample the lower the static force should
be.
 Three point bending
Applied to keep center fulcrum in contact with sample prior to
starting dynamic oscillation.
Typically 0.1 - 1 Newton.
209
Tensioning Clamps Require Offset Force During Oscillation !
Force/Time Curves
A
0
OF
A
A = Oscillatory force amplitude
OF = Offset force
Clamps with offset force

Clamps without offset force: (tensioning clamps)
Single Cantilever Tension Film
Dual Cantilever Tension: Fiber
Shear Sandwich 3-Point Bend
Compression
Penetration (TMA option)
210
Offset Force on DMA
 Constant static force OR  Force track
211
Offset = Static Force (No Force Track)
Static force when used without force track is simply the static
force that is maintained on the sample for the duration of the
test. There are no recommended starting values for static force
when used alone. Important requirement:
 the static force used must exceed the dynamic force
generated at all amplitudes and frequencies in the test
chosen. Considerations must be made here when choosing
the start temperature. A static force that is higher than the
dynamic force at ambient temperature may be insufficient at
a sub-ambient start temperature.
 Can be used with highly crystalline or cross-linked materials
(stiffness does not change a lot as a function of temperature).
212
Offset = Force Track
Force track is a feature that will keep the static load at a user
defined proportion greater than the dynamic load required to
drive the selected amplitude (strain).
As a sample is heated or cooled through a wide range of
temperatures, the stiffness of the sample may vary greatly,
especially for unfilled thermoplastic polymers.
When the sample is at its stiffest, the static load is required to
be high in order to drive the dynamic amplitude on the
sample. If the high load were maintained for the entire test, as
the sample softens, it may creep significantly.
However, as the sample softens, the force required to drive
the dynamic amplitude decreases, and therefore the static
load that is required to drive the amplitude also decreases.
Force track acts to reduce the static force as the sample
softens to minimize the risk of creep during the scan.
213
Force Track
 Static Force tracks Dynamic Force throughout temperature ramp
214
Static Force and Force Track
 Recommended values for static force and force track for the
tensioning clamps. Minimizing the force track and sample
amplitude/strain will reduce the risk of creep as the sample softens.
Clamp Type Static Force Force Track
Tension Film 0.01-0.05 N 120 to 150%

Tension Fiber 0.001 N 120%
Compression 0.001 to 0.05 N 125%
Three Point Bending 0.1 - 1 N 125 to 150%
Thermoplastic Sample
Three Point Bending 0.1 - 1 N 150 to 200% *
Stiff Thermoset Sample
* Can use constant static force as an alternative to Force Track.

Make sure static force > dynamic force through out the entire experiment.
215
Choosing Frequency
 The frequency range of the Q800 DMA is 0.01 (Q800) or 0.001

Hz (Discovery 850) to 200 Hz. This is the frequency range the
instrument’s motor is capable of driving, however, the upper
frequency that can be applied to a sample is dependent on the
stiffness of the sample. The higher the sample stiffness the easier
it will be to drive the sample at higher frequencies.
 Do not work above sample resonant frequency (e.g. composite
70-100 Hz, unfilled TP 10-30 Hz).
 Single Frequency Temperature Ramp Scan
 If you do not know at what frequency you are interested in
running a test, and want to run a typical temperature ramp
test for determining the location of transitions in a material,
the recommended starting frequency is 1 Hz. A frequency
of 1 Hz is a “benchmarked” standard scan.
216
Choosing Frequency
 Data Collection rate

 The limiting factor in selecting a frequency for a test is the
data collection rate. The lower the frequency, the longer it
will take to collect data. This can cause very big voids in
data points over a wide temperature range if the
frequency selected is too low (and/or the ramp rate is too
high). When running a temperature ramp scan at a single
frequency, the data will be collected according to:
 First data point in the scan: t = 7/F, where
F = frequency in Hz
 Second through last data points: t = 3/F
Note these values are based on 4 equilibrate cycles and a
further 3 cycles (default settings) to generate a single data
point. The number of equilibrate and measure cycles can be
adjusted by the operator.
217
Q800 Instrument Preference Settings
218
Choosing Frequency
 Multi-Frequency Temperature Ramp Scan

If you intend to run multiple frequencies during a temperature ramp
you should run only two or three frequencies in a single scan. The
minimum frequency in a ramp scan should be no lower than 1 Hz.
This is because when running multiple frequencies each data point
at each frequency will be taken at a time of 7/F.
 For example, running a temperature ramp at 3°C/min and at
frequencies of 1 Hz, 3 Hz and 10 Hz. The total time required
to scan through all three frequencies will be:
t = 7/1 + 7/3 + 7/10 = 7 + 2.3 + 0.7 = 10 seconds
This translates to a data point approximately every 0.5°C
(20 seconds = 1°C temperature rise) at each frequency in
the sweep. This generates more than enough data points
to define the transitions smoothly.
219
Note : Data Collection Period is Related to
Digital Signal Processor (Q800)
Frequency Range (Hz) Measurement period
0.01 - 0.99 100 sec
1.0 - 10.0 10 sec
10.1 - 50.0 5 sec
50.1 - 100.0 2 sec
100.0 - 200.0 1 sec
The measurement period is optimized (reduced) for the following "nice" frequencies:
Frequency (Hz) Measurement period

dd.0 1 sec
dd.5 2 sec
dd.2, dd.4, dd.6, dd.8 5 sec
0.d0 10 sec
0.d5 20 sec
0.d2, 0.d4, 0.d6, 0.d8 50 sec
220
Discovery DMA 850 Oscillation Data Acquisition
 Frequency based correlation table,

Standard is typically 3 s/pt at frequencies
> 1 Hz (3X)
Example with “Standard”:
1 Hz  3 s  3 cycles
5 Hz  3 s  15 cycles
10 Hz  3 s  30 cycles
0.1 Hz  3 cycles  30 s
 Fast  Typically 1 s/pt at most
frequencies (1X)
 Enhanced  Typically 6 s/pt (6X)
221
Choosing Heating Rate
 Temperature Ramp Rate

The recommended temperature ramp rate for DMA
experiments is from 1°C/min to 5°C/min. The temperature
ramp rate in a DMA experiment should not exceed 5°C/min.
The choice of ramp rate will depend on the sample size, the
frequency or frequencies of interest, and the desired degree
of accuracy in transitions. When designing a test consider
the following:
 The faster the heating rate, the more the sample will lag
the programmed temperature and transitions will be
pushed to higher temperatures. Slower heating rates (1 to
3°C/min) will give more accurate transition temperatures.
If the absolute temperature of the transition is desired,
then a step and hold temperature profile should be used.
222
Choosing Heating Rate
 Large, thick samples, such as those used in three point bending

and cantilever-bending clamps will lag the heating rate more than
thin samples, such as films and fibers.
 The lower the frequency, the less often data will be acquired.
Low frequencies (<0.5 Hz) and fast heating rates (5°C/min.) are
not good combinations. Make sure data will be acquired at
reasonable time intervals for the ramp rate selected.
A recommended combination for a single-frequency temperature
ramp is a frequency of 1 Hz and ramp rate of 3°C/min.
223
Voids in Data
10
To plot every data point:

• Graph, options
• Symbols: custom symbol list, spacing = every point
 
 
 
 







Storage Modulus (GPa)







 No data collection as
1 

 no stable data in



transition region at

Clamp 3-Point Bending



high heating rate


Size 50.0000 10.3500 2.0000 mm
Freq 1.00 Hz 

Ramp 10.00 °C/min to 175.00 °C 






0.1
80 90 100 110 120 130 140 150 160
Temperature (°C) Universal V4.5A TA Instruments
224
Voids in Data versus Instrument Preference
Settings
225
Settings on Discovery 850
STRESS/STRAIN ACCURACY
 Default value of 1 %
(5% on Q800)
 Sets the criteria for point acceptance and stress/strain stability
226
Selecting the right parameters
 Selecting the right parameters when conducting measurements

on the DMA is very important for achieving accurate and
reproducible results. Parameter selection is also typically the
most frequent question for new users. The DMA is equipped with
an on-line signal display that aids the user in selecting valid
instrument parameters before an experiment is actually started.
 The real-time signal display can guide you through just about any
question you may have pertaining to the validity of your
experimental test set-up as long as you know the DMA’s
limitations.
Become VERY familiar with the REAL-TIME Signal Display
227
Real Time Signal Display
228
 After measuring sample dimensions, and mounting the

sample in the appropriate clamp, press the MEASURE key
and view the signal display. When running a dynamic
experiment (multi-frequency and multi-strain mode) pay
special attention to the following signals:
 Amplitude/Strain: Should achieve and maintain the value
programmed. If running a multi-strain experiment, this
amplitude will cycle through the values programmed. It
should be noted that the interpretation of the data might
rely on linear viscoelastic theory in which case the data
should be collected at an amplitude within the linear visco-
elastic region of the material.
 Stiffness: Should be within instruments measurable range
of 100 N/m to 10,000,000 N/m.
229
 Drive Force:
should be between 0.0001 N and 18 N. If the drive force is not within
range (too low), increase the programmed amplitude to increase the
drive force or increase the stiffness of the sample by changing the
physical dimensions of the sample. Increasing the frequency will also
increase the drive force.
 Static Force:
If Force Track is used, the static force should adjust to the set
percentage greater than the drive force required to maintain the
amplitude programmed.
Example:
Amplitude = 20 micron
Force Track = 120%
Suppose 1 N of dynamic force required
Static force should adjust to 1.2 N
If using constant static force mode, the static force should read the
value set in instrument parameters.
230
 If the initial conditions are acceptable i.e., good amplitude/

strain control, operation within the force and stiffness range and
expected modulus values, then start the experiment.
 If the values are not acceptable, then change conditions
appropriately.
Proper inspection of real time signal display prior to start

=> Good results
231
Waveform as a diagnostic tool
Q800: only available after starting the run

(only available on newer models)
Discovery 850 DMA: waveforms during the entire test can be saved
232
Measuring the Linear Viscoelastic Region of a Material
Why is the linear viscoelastic region important ?
 In order to use a DMA to accurately determine

mechanical properties and develop morphology
relationships (crystallinity, molecular weight, crosslinking,
etc), the material must be deformed at an amplitude that
is within the linear viscoelastic region of the material.
Within the linear viscoelastic region, the materials
response is independent of the magnitude of the
deformation and the materials structure is undamaged.
 Characterization of the material within the linear region
yields a “fingerprint” of the structure of the polymer.
Therefore, any differences in the structure of polymers
can easily be measured as differences in the dynamic
mechanical properties.
233
What is the Linear Viscoelastic Region ?
Response of a viscoelastic material to increasing strain (amplitude)
Linear Region:
Non-linear Region: Modulus is a
Modulus is
function of strain
independent of
Strain
E' or G'
Stress

Slope
Strain (amplitude)
234
LVR
 The slope of the stress-strain curve is equal to the modulus.

In the initial stages of deformation, the slope of the stress
versus strain curve is constant. Because the slope of the
stress-strain curve is constant, the modulus is constant. The
response is linear i.e the modulus is independent of the
strain.
 At some point, as the deformation increases, the slope of the
stress-strain curve becomes non-linear and the modulus is
now a function of the magnitude of the strain. In almost all
cases the modulus will decrease with increasing strain.
 The strain at which the slope of the stress-strain curve is no
longer constant, or the point at which the modulus becomes a
function of the applied strain is called the critical strain γc
235
LVR
 To find the end of the linear region, a good rule is to find the
amplitude at which the initial value of the storage modulus
(e.g. the storage modulus at the lowest amplitude in the
sweep) changes by 5%.
 As a general rule of thumb, solids are linear at strains less
than 0.1%. This does not apply to all samples, so the linear
region may require verification.
 Example: normalized storage modulus versus amplitude for a
polystyrene and a filled silicone elastomer sample. The
storage modulus was normalized for comparative purposes.
The polystyrene sample has a much longer linear region as
compared to the filled elastomer. After finding the linear
region, subsequent scans, such as temperature ramps and
frequency sweeps, should be conducted at amplitudes within
the linear viscoelastic region.
236
Determining the LVR using non-tensioning clamps
1.10
–––––– Filled Silicone Elastomer
–––––– General Purpose Polystyrene
Clamp: Single Cantilever
1.05 Frequency: 1 Hz
1.00 


Normalized Storage Modulus
 


0.95 
 



0.90 


0.85


End of Linear
0.80 End of Linear
Region for
Region for
Filled
Polystyrene
0.75 Elastomer
0.70
0 20 40 60 80 100 120 140
Amplitude (µm) Universal V2.4D TA Instruments
237
Measuring the LVR for Tensioning Clamps
 The tension film, tension fiber, three point bend, and compression
clamps are all tensioning clamps, or clamps which require a static
offset force.
 Because these clamps require maintaining a “static force” during the
oscillation, a strain sweep test can not be used to “STRICTLY”
define the linear viscoelastic region of a material. This is because
when a static force is applied to the sample, the material is strained.
The strain applied to the sample as a result of the static force is in
addition to the strain applied to the sample during the oscillation.
However, when we plot the amplitude (or strain) we only see the
strain generated as a result of the dynamic oscillation.
 A method for measuring the LVR of a sample tested in tensioning
clamps is to conduct a force ramp.
238
Force Ramp Test

 deforms the sample at a constant rate of deformation, such as 1 N/min
D e fo rm a tio n
Force (N)
m = fo rc e ra te
(N /m in )
tim e (m in .)
239
LVR
Force Ramp on Polyethylene Sample – Stress vs. Strain

2.0
1.5 

Stress (MPa)

1.0


0.5

 γc = Critical Strain

0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Strain (%) Universal V2.6B TA Instruments
240
 Look at stress versus strain curves.

 Suppose that the critical strain is 0.4 % and you want to
use a force track of 120%. This would enable you to set
the dynamic strain to 0.16%, the static strain placed on
the sample would be 0.19%, giving a total strain of
0.35%, well below the critical strain of the sample.
241
Troubleshooting:
What if E’ Increases in a Strain Sweep
The sample is not flat and not in full contact with the clamp face.
Solutions: (1) Prepare a flat sample
(2) Increase force track or increase static force
10000 10
9000 

8000 
7000
6000 
5000 
[  ] Storage Modulus (MPa)
[  ] Dynamic Force (N)


4000

3000 
 0.1
   
2000 


 

 

 

1000 0.01
0.1 1 10 100 1000
Amplitude (µm) Universal V4.5A TA Instruments
242
Troubleshooting:
What if E’ Increases in a Temp Ramp
E’ of a material should not increase with temperature

unless it is undergoing cold crystalization or crosslinking
expected
Film sample was

not well mounted
and buckled at the
start of the test
243
Troubleshooting: Noisy Modulus Above Tg
What is the problem with this data collected above Tg?
10000 10000
1000 1.0E5 1000
100 10000 100

Loss Modulus (MPa)

10 1000 10
Stiffness (N/m)
78.71°C
39.76N/m
1 100 1
0.1 10 0.1 Sample stiffness is

below the instrument
0.01
What’s wrong here?
1 0.01
spec (100N/m)
Solution: Increase the
0.001 0.1 0.001
sample stiffness
0.0001 0.0001 (wider, thicker,
-100 -50 0 50 100 150
Temperature (°C) Universal V4.5A TA Instruments shorter)
244
Troubleshooting: Sample Sagging
Sample sagging above Tg

Solution: use cantilever clamp instead of 3-point bending
245
DMA-RH Experimental Options
Isohume, Isothermal Isothermal, RH Ramp Isohume, Temp Ramp

Temperature
Temperature
Temperature
RH
RH
RH
Time Time Time
Isothermal, RH Step Isohume, Temp Step RH Step, Temp Step
Temperature
Temperature
Temperature
RH
RH
RH
Time Time Time
246
DMA-RH Instrument Control Software Q800
make sure this signal

is selected to save
most accurate
(calibrated)
only indicative
RH control is incorporated with

the standard DMA control
software after checking
‘humidity chamber’ in tools,
instrument preferences
247
DMA-RH DMA 850
248
DMA-RH Experiment Programming
Isothermal, RH Step
RH Control Segments
Necessary time to reach specified
humidity at 2% RH/min plus desired
equilibration time
249
Isothermal, RH Increment/Repeat
Note:
Motor drive off is floating the shaft instead of locking it (with RH
accessory purge from air bearings is always required); segment must be
preceeded by humidity 0%
250
DMA 850:
use the RH templates to understand
how to setup an RH experiment
Read the full getting started guide prior to using the RH accessory !
251
DYNAMIC MECHANICAL ANALYSIS
APPLICATIONS
252
Applications of Dynamic Mechanical Analysis
 Determine mechanical properties, i.e., modulus

and damping of viscoelastic materials over a
spectrum of time (frequency) or temperature.
 Detect molecular motions.
 Develop relationships between property and
structure or morphology.
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second Edition, Volume I.,
Academic Press, Brooklyn, New York, P. 489.
253
Polymer Structure
 The mechanical properties of a polymer are a due to

 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
254
Polymer Structure-Property Characterization
 Glass transition: DMA provides higher sensitivity than DSC

 Secondary transitions
 Crystallinity
 Molecular weight/cross-linking
 Phase separation (polymer blends)
 Composites
 Aging
 Curing of networks
 Orientation
 Effect of additives
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second Edition, Volume I., Academic
Press, Brooklyn, New York, P. 489.
255
Most Common DMA Test – Temp Ramp
 The most common DMA measurement is a dynamic temperature ramp
 The test results report modulus (E’, E”), damping factor (Tan δ) and
transition temperatures (relaxations, e.g. Tg)
 Provide information on polymer’s structure-property relationship
256
What is the Glass Transition (Tg)?
 A transition over a temperature range from a glassy state

to a rubber state of the amorphous phase of the material
 Mechanical:
 Below the Glass Transition, the material is in a brittle, glassy
state, with a modulus of 109 Pa
 Above the Glass Transition, the material becomes soft and
flexible, and the modulus decreases two to three decades
 Molecular:
 Below the Glass Transition, polymer chains are locked in place,
without sufficient energy to overcome the barrier for rotational or
translational motion.
 At temperatures above the Glass Transition, there is molecular
mobility, and chains can slide past each other
257
How to Define Tg in DMA?
Glass transition is a temperature range, not a single temperature !
Onset of E’ < Peak of E” < Peak of Tan δ
258
E' Onset, E" Peak, and tan δ Peak
 E' Onset:
Occurs at lowest temperature, relates to mechanical failure.
 E" Peak:
Occurs at middle temperature, more closely related to the
physical property changes attributed to the glass transition in
plastics. It reflects molecular processes, agrees with the idea
of Tg as the temperature at the onset of segmental motion.
 tan δ Peak:
Occurs at highest temperature, used historically in literature, a
good measure of the "leatherlike" midpoint between the
glassy and rubbery states, height and shape change
systematically with amorphous content.
259
The Glass Transition & Secondary Transitions
 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 group motion 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 (e.g. plasticizer)
260
Polycarbonate Tg
2.5 0.5
156.14°C
160.64°C
2.0 0.4
1.5
[ – – – – ] Loss Modulus (GPa)

151.76°C
[ ––––– · ] Tan Delta

1.5 0.3
Use Peak In Loss Modulus for
Calibration
True value should be 153°C 1.0

when Measured at 1 Hz Fixed Frequency
1.0 0.2
156.32°C(I)
0.5
0.5 0.1
158.94°C
0.0 0.0
100 110 120 130 140 150 160 170 180
Temperature (°C)
261
Polycarbonate: Gamma & Beta Transition
10000 1000
0.05
1000
0.04 100
Loss Modulus (MPa)

Tan Delta
100 0.03
0.02 10
10
0.01
1 1
-200 -150 -100 -50 0 50 100 150
Temperature (°C) Universal V3.5B TA Instruments
262
Kapton Film – Tg and Secondary Transitions
8 0.25
DMA Multi-Frequency - Strain
326.26°C
Complete Analysis 339.99°C

of E3121 Bad Kapton
0.20
6

117.82°C 0.2
[ ––––– · ] Tan Delta

0.15
-74.36°C
0.10
0.1
308.84°C
2
0.05
326.59°C(I)
139.31°C
-72.09°C
344.98°C
0 0.00
-100 -50 0 50 100 150 200 250 300 350 400
Temperature (°C)
263
β-relaxation as the Major Predictive Parameter
for Recrystallization of Amorphous Drugs
E. Ofosu Kissi, H. Grohganz, K. Löbmann, M. T. Ruggiero,
J. Axel Zeitler, and T. Rades, J. Phys. Chem. B 2018, 122, 2803−2808
RT
Tgβ < RT = Tgβ > RT =

unstable practically stable
Clamp = powder clamp
264
What Will Affect Tg and/or Modulus?
 Heating rate
 Thermal lag
 Test frequency
 Polymer structure
 Rigid polymer chain shows higher Tg (e.g. PS)
 Flexible polymer chain shows lower Tg (e.g. PE)
 Crystallinity
 MW
 Degree of crosslinking
 Plasticization
 Fillers
 Anisotropy
 Blending
265
The Effect of Test Frequency on the Glass
Transition
 The glass transition is a kinetic transition. It is therefore influenced

strongly by the frequency or RATE of the test. The Tg is a molecular
relaxation that involves cooperative segmental motion. Because the
RATE of segmental motion depends on temperature, as the
frequency increases, the relaxations associated with the Tg can only
happen at higher temperatures.
 In general increasing the frequency will

 Increase the Tg value
 Decrease the intensity of tan δ or loss modulus
 Broaden the peak
 Decrease the slope of the storage modulus curve in the region of
the transition.
Reference: Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second Edition, Volume I., Academic Press,
Brooklyn, New York, P. 529.
266
Frequency dependence of Tg – PET Film
5
DMA Multi-Frequency - Tension: Film
0.1, 0.2, 0.5, 1, 2, 5, 10,
20 Hz
0.5
2
0.375
Loss Modulus (GPa)

0.2
Tan Delta
-1
0.225
Tg Increasing with
Frequency
-0.1
-4
0.075
-7 -0.4
40 60 80 100 120 140 160
Temperature (°C)
TA423
267
Effect of Crystallinity on Tg
 Semi-crystalline polymers can be thought of as being

made up of an amorphous phase containing dispersed
crystalline units.
 Simple picture of two phase system - crystalline phase acts

to restrain mobility of neighboring amorphous regions
 Increasing crystallinity for semi-crystalline polymers will:

 increase the glass transition temperature
 decrease the intensity of the glass transition peak
 broaden the transition temperature range
Turi, Edith, A, Thermal Characterization of Polymeric Materials, Second Edition, Volume I., Academic Press, Brooklyn,
New York, P. 518.
268
Effect of Crystallinity on Tg and Modulus
Increase Tg  Crystallinity mostly affects the

sample at Tg <T < Tm
65%  Below Tg the effect on the
modulus is small
40%  The modulus at T > Tg of a
semi-crystalline polymer is
25% directly proportional to the
degree of crystallinity
 Remains independent of
0% Crystallinity M.P. temperature if the amount of
(100% Amorphous)
crystalline order remains
Temperature unchanged
Cowie, J.M.G., Polymers: Chemistry & Physics of Modern Materials, 2nd Edition, Blackie academic & Professional,
and imprint of Chapman & HallBishopbriggs, Glasgow, 1991p. 330-332. ISBN 0 7514 0134 X
269
Polymer Cold Crystallization (PET)
Modulus (E’) increase due to cold crystallization
270
Effect of Molecular Weight on Modulus and Tg
 Molecular Weight has practically no effect on the modulus

below Tg.
 With the exception of low molecular weight (below Mc where
there are no entanglements), the rubbery plateau region
above Tg 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.
271
Molecular Structure - Effect of Molecular Weight
Glassy Region Rubbery

Transition Plateau
Region Region
MW has practically
no effect on the
modulus below Tg
log E' (G')
Low Med. High

MW MW MW
Temperature
272
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, John Wiley & Sons Ltd., New York, 1993, p.2.
273
Effect of Crosslinking on Tg and Modulus
 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 a rise in the glass transition temperature.
 For low values of crosslink density, Tg can be found to
increase linearly with the number of crosslinks.
 For high crosslink density the Tg 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
274
Effect of Crosslinking
Increase Tg Mc = MW between
crosslinks
120
160
300
1500
9000
30,000
Temperature
275
Summary of Effects of Crystallinity,
Molecular Weight, and Crosslinking
Increasing
Crystallinity
log Modulus
Amorphous Crystalline
3 decade drop Cross-linked

in modulus at Tg
Increasing MW Tm
Temperature
276
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:
 To lower the Tg to make a rigid polymer become soft
and rubbery.
 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:
 Lowering the glass transition temperature and
 Broadening the tan peak
277
Effect of Plasticizer on Vinyl Flooring
Higher % Plasticizer
278
Analysis of Nylon 6 with RH Accessory
TA364
279
DMA-RH Analysis of a Gelatin Capsule
DMA-RH Analysis of a Gelatin Capsule
even at RT keep RH below

75% to ensure mechanical
integrity of the material
film was cut out of it
TA367
280
Submersion Clamps: Dry Coating (Empty Bath)
5 0.5
57.88°C
0.6
50.05°C
Sample submerged in
Water
4 0.4
43.25°C

[ ––––– · ] Tan Delta

0.4
3 Plot 001 - Analysis of Dry 0.3
Grey coating
2 0.2
49.17°C(I)
0.2
1 0.1
53.86°C
0 0.0
20 30 40 50 60 70 80
Temperature (°C)
281
Submersion Clamps: Soaked Coating (in Water Bath)
5 45.07°C
0.5
54.20°C
0.6
4 Sample submerged in 0.4

Water
37.88°C

[ ––––– · ] Tan Delta

0.4
3 0.3
2 43.74°C(I) 0.2
0.2
Plot 002 - Analysis of Soaked
Grey coating
1 0.1
49.96°C
0 0.0
20 30 40 50 60 70 80
Temperature (°C)
282
Submersion Clamps: Dry versus Soaked
Coating in Solution
5 1.0
––––––– Grey Sample - Dry
–––– Grey Sample - 65 Hr soak
2 0.7
Tg shifts down due to
Plasticisation by water 1.8
Loss Modulus (GPa)

-1 0.4
Tan Delta
1.2
-4 0.1
0.6
-7 -0.2
-10 -0.5
30 40 50 60 70 80
Temperature (°C)
283
Effect of Fillers on Modulus
60% mica
40% mica
60% asbestos
Storage Modulus (E’)
40% asbestos
20% mica
20% asbestos
20% calcium carbonate
polystyrene control
20 40 60 80 100 120 140 160

TEMP. (°C)
Nielson, L. E., Wall, R. A., and Richmond, P. G., Soc. Plastics Eng. J., 11, 22 (1966)
284
Anisotropic Materials
 Anisotropic materials have different properties in

different directions.
 fibers, wood, fiber-filled composites
 oriented amorphous polymers, injection molded
specimens
 crystalline polymers in which the crystalline phase is
not randomly oriented
 Show different moduli at different measurement direction
Nielsen, Lawrence E., Mechanical Properties of Polymers and Composites, Marcel Dekker, Inc., New
York, 1974, pp. 39-40.
285
Anisotropic Material
Thermoset Polyester/Glass Fiber Composite
1.0E5 1.0E5
––––––– Fibers Parallel to Length
–––– Fibers Perpindicular to length
Storage Modulus
10000 10000
Loss Modulus (MPa)

1000 Loss Modulus 1000
100 Notes: 100

Frequency = 1 Hz
Amplitude = 40 microns
Force Track = 150%
Ramp Rate = 3°C/min.
length
10 10
20 40 60 80 100 120 140 160 180 200
Temperature (°C) Universal V2.6D TA Instruments
286
Anisotropic Material
Thermoset Polyester/Glass Fiber Composite
0.12
––––––– Fibers Parallel to Length
96.82°C –––– Fibers Perpindicular to Length
Notes:
0.10 Frequency = 1 Hz
Force Track = 150%
104.55°C Ramp Rate = 3°C/min.
0.08
Tan Delta
0.06
0.04
length
0.02
25 50 75 100 125 150 175 200
287
Blending of Amorphous Polymers
• Blending polymers with different glass transition

temperatures and modulus will create new materials that
may show better physical properties.
• 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.
• If the polymers are incompatible, then the blend will show

separate glass transitions.
288
Miscible Polymer Blend - Aerospace Coating
10000
–––––– Polymer A
 – – – Polymer Blend: A + B
–––– ∙ Polymer B

  
  
 
   Polymer Blend

1000  A+B
100 % Polymer A 

       
 


100

 

100%
Polymer B    
    
10



1
-25 0 25 50 75 100 125
289
Miscible Polymer Blend - Aerospace Coating
1.5
–––––– Polymer A
46.46°C  – – – Polymer Blend: A + B
 –––– ∙ Polymer B
 100%
Polymer B Polymer Blend
1.0  A+B
76.19°C
  89.77°C


Tan Delta
 
0.5  
 
100 % Polymer A  
 

 
    
    

   



     
0.0   
-0.5
-25 0 25 50 75 100 125
290
Immiscible Blend – PS/SB Rubber
9
10
8
10 10
Modulus (Nm-2)
Tan delta
7
10 1.0
6
10 0.10
5
10 0.01
-50 0 50 100 150
Temperature (°C)
291
Using Glass Transition to Evaluate Blending
Investigating manufacturing blend uniformity
292
Evaluating Coatings on a Substrate
 Use bending mode (3PB or cantilever) to get transition temperature info

 No quantitative E’ info for the coating
 e.g. metal bar with PET coating
2.0
99.68°C
95
90.33°C
0.030
133.55°C
95.02°C(I)
1.5
130 140 150

90 0.025
[ ––––– · ] Tan Delta

104.16°C
Tg of PET
Coating 99.68°C 195.80°C
130.99°C 0.020
85 1.0
Re-crystallisation Re-ordering
above Tg near melt
0.015
83.07°C 201.05°C
80 130.88°C
240.23°C 0.5
0.010
75
84.01°C 0.005
PET Melting
0.0
50 100 150 200 250
Temperature (°C)
293
Evaluating Curing of a Thermoset
 Use dual cantilever to get transition info (smaller span length might be required)
 Impregnate liquid resin on a support and wrap protecting foil around it
 No quantitative E’ info
8 0.20
12.16min
140
Vitrification
120
6 0.15
9.18min 100
[ ––––– · ] Temperature (°C)

[ – – – – ] Tan Delta
80
Temperature Programme
4 60 0.10
Curing
40
Araldite Supported on
Glass Braid (Wrapped in foil) 20
2 0.05
0
9.36min
97.31°C
-20
DMA Multi-Frequency - Strain

0 0.00
0 10 20 30 40 50
Time (min)
294
Curing of Rubber (Shear Clamps)
295
Polypropylene - Onset of Crystallization – Shear Clamps
1.0E7
 sample5.003 Exxon Sample #5

 sample9.001 Exxon Sample #9
 Testing Conditions
Heat to 210°C for 5 min.
Cool to 180°C for and Ramp down at 0.5°C/min.
 Frequency = 1 Hz
1.0E6 Clamp Type: Shear Sandwich
 Sample Size: 10 mm x 10 mm x 0.5 mm
Storage Modulus (Pa)
Without nucleating agent

1.0E5 
Cooling
 
 
 
10000 
129.01°C    
 138.58°C 

 
       
With nucleating agent 
1000
120 130 140 150 160 170 180
296
Tg of powder for coating instant-release tablets
* Mainly response of powder holder

0.05

* 4.45°C 0.2
GPa
[ ––––– · ] Tan Delta

34.96°C
1.28°C 65.23°C
5
GPa Tg ?
sample after drying
sample as received
Melting and
decomposition
-50 0 50 100 150 200

Temperature (°C)
297
Tg of a Liquid with DMA Powder Holder
5% w/v trehalose in phosphate buffered saline:
* Mainly response Sample impregnated on glass microfiber filter paper (slight

of holder wetting only !) and mounted in DMA powder holder
12
0.4
10 1.5
-42.92°C
0.3
* 8
1.0
Loss Modulus (GPa)

6
Tan Delta
0.2
0.5
4
0.1
2
0.0
0 0.0
-0.5
-2
-80 -60 -40 -20 0 20
Temperature (°C) Universal V4.5A TA Instruments
298
Oriented Polymer: Shrink Wrap
 “Shrink Wrap” is widely used in packaging

to conveniently label irregularly shaped
containers
 When this kind of biaxially oriented film is
heated, it turns to shrink and returns to lower
energy random-coil state.
 Characterize shrinkage (force) in both x and
z directions
 Iso-force or iso-strain testing
Z
X
299
Iso-force Temp Ramp: measure shrinkage
z
Length (mm)
Z
Hold force at 0.05N
Temperature : ambient to 120˚ C
X
Ramp rate: 3˚ C/min
300
Iso-strain Temp Ramp: measure shrinking force
Strain = 0.05%
x
Temperature :
ambient to 120˚C
Ramp rate: 3˚C/min
(kPa)
Stress
z Z
301
O-rings: Stress Relaxation
Squeeze the O-ring to a certain strain. Hold it

constant, then measure how long it takes for the
force to relax
302
Creep Tests on Packaging Bags
Apply a load force, then measure

how much the bag is stretched
120000
 Poor Performance
 Good Performance
 Excellent Performance
100000
 
Creep Compliance (µm^2/N)
     
80000

60000
    
 


40000
 
 




20000

0 


0 1 2 3 4 5 6 7 8 9 10
Time (min) Universal V2.1A TA Instruments
303
Coefficient of Hygroscopic Expansion for Film,
RH Chamber
Nylon 6, 25°C
304
Time-Temperature Superposition
305
Some References for TTS
 Ward, I.M. and Hadley, D.W., "Mechanical Properties of Solid

Polymers", Wiley, 1993, Chapter 6.
 Ferry, J.D., "Viscoelastic Properties of Polymers", Wiley, 1970,

Chapter 11.
 Plazek, D.J., "Oh, Thermorheological Simplicity, wherefore art thou?"

Journal of Rheology, vol 40, 1996, p987.
 Lesueur, D., Gerard, J-F., Claudy, P., Letoffe, J-M. and Planche, D.,
"A structure related model to describe asphalt linear viscoelasticity",
Journal of Rheology, vol 40, 1996, p813.
TA144 TA287 AAN005e
306
Time and Temperature: Two Sides of the Same Coin
(E' or G') (E' or G')

(E" or G") (E" or G")
log Frequency Temperature
log Time
307
Time & Temperature Effects
 Rheological behavior of viscoelastic materials vary with both

time (or frequency) and temperature
 To fully understand a materials properties we need short time
(or high frequency) and long time (or low frequency) data
 Low frequencies can take long time to collect data
 Ultra high frequencies cannot be measured by existing
instruments
 Time scales of weeks (or even years) are impractical to be
measured
 Observations that time and temperature of time-dependent
processes have equivalent effects on rheological properties
 Principal effect of changing temperature is to rescale time:
temperature changes shift the viscoelastic functions along the
time (or frequency) scales without changing the shape
308
Time-Temperature Superposition (TTS)
 Can create a “master curve” from a series of curves

collected at different temperatures
 This procedure is referred to as Time-Temperature
Superposition (TTS)
 Data over a range of temperatures with a modest
frequency range can predict behavior over a wider
frequency range than practical/possible to determine
experimentally
 Can be used to gauge long-time properties in a more
reasonable experimental time by performing short
stress-relaxation or creep tests at different temperatures
 An empirical method for polymers
based on observation/experience
i.e. it either works or it doesn’t
309
TTS, Briefly
Oscillation Example
Higher frequencies
experimentally
G’
inaccessible
200ºC
frequency
310
TTS, Briefly
Oscillation Example
140ºC
160ºC
G’
180ºC
200ºC
frequency
311
TTS, Briefly
140
160
180
G’
200
frequency
312
TTS, Briefly
Oscillation Example
Master-curve at 200°C
G’
frequency
313
TTS, Briefly
140
160
G’
180
aT=180
200
frequency
314
TTS, Briefly
Oscillation Example
Arrhenius or WLF
(temperature dependence
of ViscoElastic properties)
aT
0.0
140 160 180 200

Temperature
315
WLF Equation
 Shift factors can be fitted to models

 Williams, Landel, Ferry (WLF) equation
Log aT= -c1(T-T0)/c2+(T-T0)
 aT = temperature shift factor

 T0 = reference temperature
 c1 & c2 = constants from curve fitting
 generally, c1=17.44 & c2=51.6 when T0=Tg
Typically used to describe amorphous polymers

in the Tg region
316
When not to use the WLF Equation but Arrhenius
 Arrhenius form
Ln aT = (Ea/R)(1/T-1/T0)
 aT = temperature shift factor

 Ea = apparent activation energy associated with the
relaxation
 T0 = reference temperature
 If T > Tg + 100°C
 β and γ relaxations
 Tg of semi-crystalline polymers
 If temperature range is small, as then c1 and c2 from
WLF cannot be calculated precisely
317
What Materials can TTS be Applied to?
 Material must be thermo-rheological simple

 Thermo-rheological simple material:
all relaxations times shift with the same shift factor aT
i.e. all relaxation times have the same temperature
dependence
 Can be applied to amorphous, non modified polymers
318
When not to Use TTS
 Sample is partially crystallized, crosslinked or highly

filled
 The structure changes with temperature
 Cross linking, decomposition, crystallization, melting occurring
 Material is a block copolymer (TTS may work within a
limited temperature range)
 Material contains multiple phases e.g. composites or
blends
 Viscoelastic mechanisms other than configurational
changes of the polymer backbone occur
 e.g., side-group motions, especially near the Tg
319
Cole-Cole Plot to Validate TTS
The Cole-Cole plot is

(Pa)
commonly used to
validate the application
Loss modulus
of Time-Temperature
Superposition.
320
van Gurp-Palmen Plot to Validate TTS
The van Gurp-Palmen

(°)
plot is commonly used to

Phase angle
validate the application

of Time-Temperature
Superposition.
321
Guidelines for TTS
 Decide first on the Reference Temperature - Tr

What is the use temperature ?
 If you want to obtain information at higher frequencies, you will

need to conduct frequency scans at temperatures lower than Tr
 If you want to obtain information for shorter times, you will need
to conduct stress relaxation or creep tests at temperatures lower
than Tr
 If you want to obtain information at lower frequencies, you will
need to conduct frequency scans at temperatures higher than Tr
 If you want to obtain information for longer times, you will need to
conduct stress relaxation or creep tests at temperatures higher
than Tr
 Good idea to first scan the material at a single frequency to get

an idea of modulus-temperature and transition behavior.
322
Setting up TTS procedure on Q800 DMA
Amplitude within the linear region
323
Setting up TTS procedure on DMA850
324
Analyzing TTS data – Trios
325
Analyzing TTS data - Trios
326
Analyzing TTS data – Trios
 use the TTS wizard
327
TTS – Trios
 For analyzing creep tests with TTS:

as a first step plot log compliance versus step time
328
Help !?
329
Help !?
 On your PC :
Case sensitive help, help topics, manual
 E-training (basic)
www.tainstruments.com
 TATechTips & Webinars

 Application library
330
Help and data analysis from your laptop ? Simply download the S/W !
331
Help on Desktop
332
Thermal Advantage Help
Help Topics
For help topics on your laptop browse to:

C:\Program Files(x86)\TA Instruments\Thermal
Advantage\Qseries\Help\QDMA\qdma.htm
333
Trios Help
Similar on controlling PC and laptop,

but offline on laptop.
334
Data Analysis: Universal Analysis versus Trios
 Trios files can be saved in UA format and opened in UA
 Advantage/UA files can be opened in Trios directly
335
336
or on You Tube !
 Penetration clamp
 Shear sandwich clamp
 Compression clamp
 .... and much more
337
338
339
Thank You !
340

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Dynamic Mechanical Analysis

 Introduction to the technique, terminology,

 DMA is the general name given to an instrument that

 Thermal Analysis is the measurement of some

 Rheology is the science of flow and deformation of

Liquids Gels Solids

 For many applications, mechanical properties and how

 For materials selection it’s important to have desirable

 Need to have an understanding of how the mechanical

Modulus (E, G) / Compliance (J)

A single polymer can exhibit an extremely wide range of

Glassy Region Rubbery Terminal

 All materials change in shape, volume, or both under the

 The Modulus measures the resistance to deformation of a

 We can define three kinds of Moduli for a material

Young’s Shear Bulk

 Poisson's ratio, ν, is the ratio of transverse to axial strain

 If the volume of the specimen remains

 In general, there is an increase in volume

Material E(GPa) ν G (GPa)

 Elastic Isotropic materials are materials in which the

 If any of the two elastic constants of a homogenous

 Anisotropic materials have different properties in

 Anisotropic materials are really much more common

 Have more than two independent moduli - generally a

 The number of independent moduli depends on the

 Stress = Force / Area [Pa]

In classical mechanics, stress is applied to a material

 For an Elastic Solid, Stress and Strain

1687: Isaac Newton addresses liquids and steady shearing flow in

Newton’s Law: stress = (coefficient of viscosity) • strain rate

 For a Viscous Liquid,

Range of Material Behavior

Solid Like ---------- Liquid Like

Viscoelastic Materials: Force depends on both Deformation and

Kelvin-Voigt Model (Basic Creep) Maxwell Model (Stress Relaxation)

T is short (< 1s) T is long (> 24 hours)

High De Solid-like behavior

Material can appear solid-like because:

 Short deformation time: pitch behaves like a

(E' or G') (E' or G')

log Frequency Temperature

Time-Temperature Superposition (TTS)

If the deformation is small, or applied sufficiently slowly, the molecular

Measuring linear viscoelastic properties helps us bridge the

Linear Region: Non-linear Region:

Constant γc = Critical Strain

 The phase angle δ, or phase

Purely Elastic Response Purely Viscous

Viscoelastic material response: 0° < δ < 90°

 The stress in a dynamic experiment is referred to as the complex stress σ*

The Complex Modulus: Measure

SUPER BALL LOSS

Stiff to Soft rubber

Storage Modulus (E' or G')

Stress Relaxation and Creep

 Strain is applied to sample instantaneously (in principle)

 Stress is monitored as a function of time σ(t).

stress for t>0 is 0

Response of Viscoelastic Material

Stress decreases with time

For small deformations (strains within the linear region)

This function is a material property known as the