7/22/2020

DMTA- Dynamic Mechanical

Thermal Analysis

Dr. Abdul Shakoor

Polymer Characterization
• Chemical Characterization
• Thermal Characterization
• Mechanical Characterization
• Morphological Characterization
• Electrical Characterization

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Mechanical testing

'simple' static stress-strain experiment

tensile strength
b   f  , T 
  f t , T 
stress 

tensile strength
yield strength

elongation at break b
brittleness B*): tensile strength

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B
b  E '
elongation at break b

strain 

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Mechanical Analysis
• Universal Testing Machine/ Tensometer
• Dynamic Mechanical Analysis (DMA)
• Izod Charpy Testing
• Dart Impact Testing
• Hardness Testing
• Fatigue Testing
• Stress Relaxation
• Creep

Thermomechanical and dynamic

mechanical
• Thermomechanical and dynamic mechanical
tests represent the most useful modern
thermal analysis techniques.
• Three techniques are commonly used to study
polymers:
(1) thermomechanical analysis (TMA)
(2) pressure–volume–temperature (PVT)
measurements,
(3) dynamic mechanical analysis (DMA).

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THERMO-MECHANICAL ANALYSIS (TMA)

• TMA is the technique of measuring the dimensional changes in a
specimen as a function of time or temperature.
• Dimensional properties of a sample are measured as sample is
heated, cooled or held under isothermal conditions. Loading or
force applied can be varied.
• Change of dimensions as a function of temperature is
recorded. These changes in dimensions taken as an indicator
of the changes in free volume of polymer.
• These data allow the calculation of a material’s expansivity or
coefficient of thermal expansion as well as detection of
transitions in the material.
• Free volume related to viscoelasticity, aging, penetration by
solvents, & impact properties.

Dynamic mechanical analysis

• In the case of DMA, a
sinusoidal oscillating stress is
applied to a specimen, a
corresponding oscillating strain
will be produced.
• Unless the material is perfectly
elastic, the measured strain will
lag behind the applied stress by
a phase difference (δ) shown in
here.
• The ratio of peak stress to peak
strain gives the complex
modulus (E*) which comprises
an in-phase component or
storage modulus (E’) and a 90°
out-of-phase (quadrature)
component or loss modulus
(E”).

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Relationships
• The storage modulus, being in-phase with the
applied stress, represents the elastic
component of the material’s behaviour,
whereas the loss modulus, deriving from the
condition at which d /dt is a maximum,
corresponds to the viscous nature of the
material.
• The ratio between the loss and storage moduli
(E ”/E’) gives the useful quantity known as the
mechanical damping factor (tan δ) which is a
measure of the amount of deformational
energy that is dissipated as heat during each
cycle.

• The relationship between these quantities can be illustrated by means of an Argand diagram,
commonly used to visualise complex numbers, which shows that the complex modulus is a
vector quantity characterised by magnitude (E*) and angle (δ) as shown in Figure. E’ and E”
represent the real and imaginary components of this vector thus:
E* = E’ + iE" = (E'2 + E"2)
So that:
E’ = E* cos δ
and
E" = E* sin δ

Tan delta tells us how good a material will be at absorbing

energy.

Basically tan delta can be used to characterize the modulus of

the material. Delta should range between 0° and 90° and as
delta approaches 0° it also approaches a purely elastic
behaviour. As delta approached 90° the material approaches
a purely viscous behaviour.

The tan of delta is defined below:

tan(delta) = E"/E'

E" = Loss modulus

E’ = Storage modulus

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Dynamic Mechanical Analysis (DMA)

• Characterize Visco-Elastic properties
• Dynamic mechanical analysis is the technique of applying
a stress or strain to a sample and analyzing the response
to obtain phase angle and deformation data

• Storage Modulus E’ (elastic response) and Loss

Modulus E’’ (viscous response) of polymers are
measured as a function of T or time as the
polymer is deformed under an oscillatory load
(stress) at a controlled (programmed) T in
specified atmosphere.

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DMA measures stiffness and damping, these are reported

as modulus and tan delta. Because sinusoidal stress is
applied, modulus can be expresesed as;

• in-phase component, the storage modulus (E‘) and

• out of phase component, the loss modulus (E")

Storage modulus (E‘) is a measure of elastic response of a

material. It measures the stored energy.

Loss modulus (E") is a measure of viscous response of a

material. It measures the energy dissipated as heat.

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The long-term stability of

a polymer will depend on
its aging characteristics
As the space between both physical and
the chains increases, chemical. Physical aging is
the term used to describe
the chain can move. the observed changes in
properties of glassy
materials as a function of
Physical aging storage time, at a
temperature below the
glass transition, T g

Tg

Increase in free volume caused by increased energy absorbed in

chains and this increased free volume permits various types of chain
movement to occur. Below Tg various paths with different free
volume exist depending on heat history & processing of polymer,
where the path with the least free volume is most relaxed. 13

Test configurations

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Dynamic Mechanical Analysis

Viscoelastic Properties of Polymers

 A polymer may exhibit mechanical behaviour characteristic
of either an elastic solid or a viscous liquid, depending upon
temperature, in relation to the glass-transition temperature
(Tg) of the polymer and the time scale of the deformation.
 Two extremes types of stress-strain curves are those for
elastic solid ( , Hooke’s law) and fluid (  d/dt,
Newton’s law)
relationship between moduli: E = 3B(1-2) = 2(1+)G

E: Young’s modulus; B: bulk modulus; G: shear modulus; : Poisson’s ratio

*For polymer, if d/dt = constant, a curve like the following will be observed

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 For this forced-vibration situation, complex variables (i.e. ) is used for

analysis The modulus can also be written as G* = G + iG where G is
called the storage modulus and G is called the loss modulus.

 The outputs of the test are usually temperature variation plots of either
tan , G and/or G or some other combinations of these parameters.

DMA response of DMA spectrum of polysulfone.

polystyrene cross-linked
with 2% divinyl benzene o : storage_modulus;  : loss-modulus. (Tg 480K)

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 The sample is set in cyclic tensile load, a linear variable differential transformer
(LVDT) is used to monitor the frequency and the amplitude of vibration.
 The preset oscillation amplitude is maintained by a feedback control loop and
the driving force required to do so is a measure of the energy dissipation of the
sample

• Tg in polymer corresponds to the expansion of free volume

allowing greater chain mobility above this transition.

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Typical behaviour

For purely crystalline

materials, Tg occurs

Tg is related to molecular mass

up to a limiting value
b transitions are often related In semicrystalline polymers,
to the toughness a crystal-crystal slip, Ta * occurs

Rubbery plateau (2)

For thermosets,
Rubbery plateau is related no Tm occurs
to Me between cross-links or Tll in some
entanglements amorphous Tm = melting (1)
polymers

“Memory” of Previous State

Poly(styrene)
Tg ~ 100 °C

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Dynamic mechanical analysis

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An oscillatory strain is applied to sample in bending or

tensile deformation modes as a function of T or time.
Frequency & strain pre-selected & maintain constant.
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Dynamic
mechanical
analysis

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Dynamic Mechanical Analysis (DMA)

• Sample is fixed between 2 parallel arms that are set
into oscillation by an electromagnetic driver at an
amplitude selected by operator.
• DMA module measure changes in viscoelastic
properties of materials resulting from changes in T,
atm and time.
• It then detects changes in the system’s resonant
frequency and supplies the electrical energy needed to
maintain the preset amplitude.
• Frequency of oscillation is a measure of modulus of
the material. The amount of electrical energy needed
to maintain constant amp  damping properties.
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DMA-Applications
• 3 parameters are calculated : dynamic storage
modulus, E’, dynamic loss modulus, E’’, &
dissipation or damping factor, tan  = E’’/E’.
• Application :
– examine viscoelastic behavior as a function of
stress, strain, frequency, time & T.
– measure modulus vs T.
– examine additive (filler, plasticizer) & cure time
effects on viscoelastic properties & Tg.
– examine mechanical behavior.
– quantify impact properties / toughness.
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A – linear amorphous
polymers.
B – crosslinked
polymers.
C semicrystalline
polymers.
D & E – poly(ester
urethane)s.
# elastic modulus
plotted as a
function of T.

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Dynamic Temperature Ramp or Step and Hold:

Material Response

Glassy Region
Transition
Region Rubbery Plateau
Region Terminal Region

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Storage Modulus (E' or G')
Loss Modulus (E" or G") 2

Courtesy: TA Instruments
Temperature

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DMTA Results

Master Curve

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Impact resistance in nylon

High- and low-impact nylon

samples showing how the b
transition is related to sample
toughness as measured by
impact testing.
The (a) lines show a material
with good impact strength by
the falling dart test and the (b)
line shows one with poor values
by the same test.

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DMA vs DSC

• DMTA vs DSC – advantage of measuring side-chain

and main-chain motion in specific regions of polymer,
as well as relaxation.
• Also, DTMA is more sensitive in detecting Tg
especially Tg of minor component.
• The elastic modulus plotted as a function of T give
characteristic profile for polymer system.
• Limitation – cannot measure mechanical properties
over full T range, because sample excessively dampens
the applied oscillation as it approaches its softening
point.
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Material specification

Definition of operating range based on position of Tg in epoxy circuit board.

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Thermoset cure

The Tg of a chip encapsulation material was measured by DSC and DMA as a

function of post cure time.

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Determination of Tg

Methods of determining Tg. (a) Multiple methods of determining Tg are shown for
DMA. Tg varies by up to 10°C in this example, depending on the value chosen.
Differences as great as 25°C have been reported. (b) Four of the different methods
used to determine Tg in DSC are shown. The half-height and half-width methods are
not included.

Effect of plasticiser

Shear modulus and loss factor

(tan d) for PVC plasticised
with diethylphthalate (DEP),
dibutyl phthalate (DBP) and n-
dioctyl phthalate (DOP).

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Epoxy

Nylon-6 as a function of humidity

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Tg 87 °C

stress relief

Stress relief at the Tg in DMA. The overshoot is similar to that seen in DSC and is caused
by molecular rearrangements that occur owing to the increased free volume at the
transition.

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Static Modulus of Amorphous PS

Glassy

Leathery

Rubbery

Viscous
Polystyrene

Stress applied at x
and removed at y

Static Testing of Rubber Vulcanizates

• Static tensile tests measure
retractive stress at a constant
elongation (strain) rate.
– Both strain rate and
temperature influence the
result

Note that at common static

test conditions, vulcanized
elastomers store energy
efficiently, with little loss of
inputted energy.

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Tan d of paint as it dries

Epoxy and epoxy with clay filler

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Dynamic Testing of Rubber Vulcanizates: Resilience

Resilience tests reflect the ability of an

elastomeric compound to store and
return energy at a given frequency
and temperature.

Change of rebound
resilience (h/ho) with
temperature T for:
•1. cis-poly(isoprene);
•2. poly(isobutylene);
•3. poly(chloroprene);
•4. poly(methyl methacrylate).

PET

Cold crystalisation in poly(ethylene terephthalate) caused a large increase in the storage

modulus, E', above the Tg. A DSC scan of the same material is included.

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effect of frequency

DMA results for poly(ethylene terephthalate) film measured in tension at different

frequencies shown. The measurements were performed isothermally in 5°C increments
and the apparatus allowed to come to thermal equilibrium for 5 minutes before the
sequence of measurements was performed.

Effect of molecular weight

Molecular weight and flow: the terminal zone or melting region follows the rubbery plateau
and is sensitive to the Mw of the polymer.

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Gellation of polymer solution

The crossover point between either E' and E'' or between E' and h* for a material
corresponds to the relative molecular weight and molecular weight distribution.

thermoset curing

The DMA cure profile of a two-part epoxy showing the typical analysis for minimum
viscosity, gel time, vitrification time, and estimation of the action energy.

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• For example, the DMA curve of polycaprolactone measured at a meachnical

vibration frequency of 1 Hz is shown below:
• The drop in storage modulus (E') and peak in damping factor (tan delta) between -
60 and -30°C is due to the glass transition (Tg) of the amorphous polymer in this
semi-crystalline material.
• Above 50°C the sample begins to melt and flow, thus loosing all mechanical
integrity.
• Below the Tg small peaks are evident in the tan delta curve at -80 and -130°C.
• These are the beta and gamma transtions in this polymer (the glass transition is
known also as the alpha transition) and are caused by local motion of the polymer
chains as opposed to large scale co-operative motion that accompanies the Tg.
• These small transitions are very difficult to observe by DSC but are often very
important in determining the impact resistance of the polymer.

Transition phenomena / mechanical relaxation in HDPE. Low-

T relaxation, γ in polymers is normally associated with
improved toughness & impact behavior. α-relaxation is
assigned as Tg of polyethylene. α-relaxation requires
mobility within crystalline phase & coincides with
accelerated softening. 58

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DMA of 2 diff samples of

PE. (a) 2 peaks : lower T
peak attributed to long
chain (-CH2-)n relaxation in
amorphous region, & higher
T peak to similar motion in
crystalline phase. T &
elative size can be related
to degree of crystallinity.
(b) Branched PE show 3
peaks, 1st and 3rd as above,
and 2nd peak is attributed
to –CH3 relaxation in
amorphous phase.
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Behavior of styrene-butadiene-
rubber (SBR). Various
formulations of SBR –
different styrene-butadiene
ratios, diff butadiene isomers,
diff additives, i.e carbon black
affected Tg, modulus of
elasticity.
# Changes in Young’s modulus
indicate changes in rigidity and
hence strength. Damping
measurements give practical
info on Tg, change in
crystallinity, occurrence of
cross-linking, & show up
features of polymer chains. 60

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Study of thermoset
curing process (cure T &
time fixed) – amount of
cross-linker
(hexamethylene
tetramine) is shown to
effect not only the Tg,
but also modulus-T
behavior..

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recommended reading

M. Reading and P.J. Haines; “Thermomechanical, dynamic mechanical and associated

methods” in; P. J. Haines; “Thermal methods of analysis: Principles, Applications and
Problems” Blackie, London (1995) pp.123-160.

K.P. Menard; “Dynamic Mechanical Analysis: A Practical Introduction to Techniques and

Applications”, CRC Press, Boca Raton (1999)

D. M. Price, “Thermomechanical and Thermoelectrical Methods”, in P.J. Haines (ed.)

Principles of Thermal Analysis & Calorimetry, ch. 4, Royal Society of Chemistry,
Cambridge (2002) pp. 94-128.

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