DYNAMIC MECHANICAL ANALYSIS

Selvakumar Murugesan
Assistant Professor,
Department of Metallurgical and Materials Engineering,
National Institute of Technology Karnataka Surathkal,
DYNAMIC MECHANICAL ANALYSIS
Liner Viscoelastic Region (LVR): Stress is proportional to strain
 VISCOELASTICITY

➢ All real polymeric materials have viscoelasticity, viscosity and elasticity

in varying amounts

➢ When the load applied to a polymeric material is time dependant, we

need to consider not only its strength, but the extent to which inputted
energy is dissipated (viscous) and retrieved (elastic)

➢ Viscoelasticity of polymeric materials can be explained mathematically

as Maxwell element where the system consists of dashpot element and
spring element in series.
 DYNAMIC TESTING - 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).
 In Industries, engineers do not evaluate the dynamic properties of
polymers by bouncing rubber balls.
– Examine the dynamic elasticity as a function of temperature and/or
frequency.
– Impose a small, sinusoidal shear or tensile strain (linear σ−ε region)
and measure the resulting stress (or vice versa)

What is DMA ?
DMA can be described as applying an oscillatory force to a sample and
analyzing the material’s response to that force.
 DYNAMIC MECHANICALTESTING

Deformation
• An oscillatory (sinusoidal)
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.
 DMA: Response for Classical Extremes

Purely Viscous
Purely Elastic Response Response
(Hookean Solid) (Newtonian Liquid)
δ = 90°
δ = 0°

Stress Stress

Strain Strain

In purely elastic response there is In purely viscous response there is

no phase lag 900 phase lag
 Storage and Loss of
Viscoelastic Materials
Typical DMA Result
 HOW DMA WORKS ?
➢ Consider the constant input and output
functions

➢ A sine wave current is added to the force

coil

➢ The resultant sine wave voltage of the

LVDT is compared to the sine wave force

➢ LVDT is an electromechanical sensor

used to transform mechanical motion into
a variable electrical signal (current or
voltage) and is used for measurement of
displacement.

➢ The amplitude of LVDT is related to the

storage modulus,E’ via the spring constant
K

➢ The phase lag δ, is related to the E” via

the damping constant D
 COMMON GEOMETRIES OF DMA

The sample can be mounted in the DMA in a number of ways

depending on the characteristics of the sample
Modes of Deformation
 DMA: Oscillatory Testing and Viscoelastic Response

Phase angle 0° < δ < 90°

Strain

Stress

In viscoelastic response, the phase angle δ is in between 00 and 900

The Modulus: Measure of materials
overall resistance to deformation. E = Stress/Strain
The Elastic (Storage) Modulus:
Measure of elasticity of material. The
ability of the material to store energy.
E' = (stress/strain)cosδ

The Viscous (loss) Modulus:

The ability of the material to dissipate E" = (stress/strain)sinδ
energy. Energy lost as heat.

Tan Delta:
Measure of material damping - such
as vibration or sound damping. Tan δ = E"/E'
 Typical DMA DATA

Glassy Region
Transition
Region
Rubbery
Plateau
Region Terminal Region

Viscoelastic
Log E’ and E”

liquid
Very hard and
rigid solid

Stiff to Soft rubber

Storage Modulus (E' or G')

Loss Modulus (E" or G")

Temperature/Time/Frequency-1
➢ Why do E’ and E” vary with frequency and temperature?
– The extent to which a polymer chains can store/dissipate energy depends on the rate
at which the chain can alter its conformation and its entanglements relative to the
frequency of the load.
➢ Terminal Zone:
– Period of oscillation is so long that chains can snake through their entanglement
constraints and completely rearrange their conformations

➢ Plateau Zone:
– Strain is accommodated by entropic changes to polymer segments between
entanglements, providing good elastic response

➢ Transition Zone:
– The period of oscillation is becoming too short to allow for complete rearrangement of
chain conformation. Enough mobility is present for substantial friction between chain
segments.
➢ Glassy Zone:
– No configurational rearrangements occur within the period of oscillation. Stress
response to a given strain is high (glass-like solid) and tanδ is on the order of 0.1
 How DMA is useful ?

When looking at glass transitions

• More sensitive than standard DSC (10-1000x)

• Can detect secondary transitions

• Measure mechanical response

• Many clamp types for various shapes and sizes

 Measuring Tg by DMA
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.
PSA Tg Measurement by DMA

Sample: PSA (Polysialic acid polymer)

Size: 7.62 x 6.0 x 0.9
Method:3°C/min, Freq = 1 Hz, amp = 10 mm

CMT
 Effect of Cross linking on Tg

• 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 an 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.
 Effect of Cross linking on Modulus

High crosslink density

log E' (G')

Tg increasing

Low crosslink density

Temperature
The viscoelatic behavior of polymers means that there is often a time
dependence of their properties in addition to any temperature effects. An
example of this is shown for poly(ethylene terephalate) measured at

different mechanical oscillation frequencies:

• Dynamic Mechanical Analysis (DMA) can be used to study the effects of
blending two polymers together or adding plasticisers to polymeric
systems.

• The position of the Tg can be predicted from the Fox equation:

1/Tgblend = WA/TgA + WB/TgB

Where WA & WB are the weight fraction of each polymer who's glass
transition temperatures are TgA &TgB respectively.
Immiscible Polymer Blends
 Immiscible Polymer Blends
polycaprolactone/nitrocellulose
Case Study 1: Effect of Carbon Silica dual
phase filler on Chlorobutyl vulcanizates
 Variation of storage modulus with temperature in
CSDPF-CIIR vulcanizates at different filler loadings

Characteristic sigmoidal variation

of storage modulus with temperature
was observed from figure

❖ In the glassy region (-600c to -300c) the augmentation in E’ with fillers can
be attributed to the hydrodynamic effect of the filler particle embedded into
the polymer continuum.

❖ In rubbery region at higher filler loadings, agglomeration of the CSDPF

aggregates form filler cluster and at filling fractions
(larger than a certain threshold) the clusters from an irregular network
leading to additional reinforcement.
 STRAIN DEPENDENT DYNAMIC PROPERTIES
Variation in storage modulus with dynamic
strain amplitude at different filler loading.
30
40 phr
Storage Modulus (MPa)

25 30 phr
20 phr
Unfilled
20 All vulcanizates show highest
modulus at low strain which
15 decreases with strain.

10

5 With Increasing strain amplitude

the decrease in storage modulus
0 is due to the gradual breakdown
0 1 2 3 4 5 of secondary structure.
Dynamic strain amplitude (%)

❖ At lower strains the three-dimensional filler-filler and filler-polymer

structure act as a rigid unit against the imposed strain, and hence
gives higher modulus.
 Variation in tanδ with dynamic strain amplitude at different
filler loading.
1.4
40 phr
1.2 30 phr
20 phr Below 1% DSA tanδ variation
is marginal.
Loss tangent,tanδ

Unfilled
1.0

0.8
Above 2% DSA, increase in
0.6 tanδ is more pronounced
in vulcanizates of higher
0.4 filler concentrations
0.2

0 1 2 3 4 5
Dynamic strain amplitude (%)

Attributed to :
1. Polymer filler interaction
2. Desorption and reabsorption of hard rubber shell
3. Breaking-Deformation of crosslink
Case Study 2: Effect of Carbon black on
Chlorobutyl vulcanizates
 Variation of tanδ with temperature

➢Below Tg ,tanδ increases with decreasing surface area of fillers.

 Dynamic mechanical Characteristics
Sample Temperature, Loss Tangent
Ttan ∂ max Tan∂ max

ISAF -32.44 0.69

HAF(N375) -30.43 0.74
HAF(N330) -31.45 0.71
GPF -29.09 1.04
SRF -29.79 1.23
MT -28.34 1.33

➢All the samples show the glass transition in the range of –280 to –320C

➢The peak magnitude is found to decrease in the order

C ISAF < C N375 < C N330 < C SRF < C GPF

➢Among the two HAF blacks, not much difference in loss tangent is observed with
the lower structured HAF (N330), which shows slightly lower value.
 Effect of temperature on Storage modulus (E’)
1000
ISAF
HAF-N375
HAF-N330
GPF
SRF
MT
Storage Modulus, MPa 100

10

1
-60 -40 -20 0 20 40 60 80 100
Temperature, 0C

➢The characteristic sigmoidal variation of the storage modulus E’ with temperature

is apparent from the plot for all compositions

➢In the glassy region, irrespective of the type of filler, particle size and structure,
increased filler loading enhances the storage modulus.

➢Among the two HAF blacks, the higher structured, N375 gives comparatively
higher values of E’ compared to lower structured N330
 Effect of Temperature on Loss Modulus (E”)
1000
ISAF
HAF-N375
HAF-N330
GPF
100 SRF
MT
Loss Modulus, MPa

10

-60 -40 -20 0 20 40 60 80 100

Temperature, 0C

➢α peak is not affected by filler loading whereas intensity of α peak increases

with increase in particle size of the filler.

➢E” decreases with lower structure and lower particle size of blacks due to
influence of filler-polymer interaction on the loss modulus.

➢N330 being low particle size has the maximum loss modulus at all
temperatures and MT black due to its high particle size results on low
filler-polymer interaction, hence shows the lowest loss modulus.
Effect of Molecular weight
Effect of plasticizer on DMA
 STANDARADS
• ISO 6721-1 (General principles)
• ISO 6721-2 (Torsion-pendulum method)
• ISO 6721-4 (Tensile vibration, non-resonance method)
• ISO 6721-5 (Flexural vibration, non-resonance method)
• ISO 6721-6 (Shear vibration, non-resonance method)
• ISO 6721-7 (Torsional vibration, non-resonance method)
• ISO 6721-8 (Longitudinal and shear vibration)
• ISO 6721-9 (Tensile vibration
 REFERENCES
1. J. J. Aklonis and W. J. MacKnight, Introduction to Polymer Viscoelasticity, John
Wiley and Sons Ltd (1983).
2. J. D. Ferry, Viscoelastic Properties of Polymers, John Wiley and Sons Ltd (1980).
3. J. M. G. Cowie, Polymers: Chemistry & Physics of Modern Materials, Chapman
and Hall (1991).
4. A. N. Gent, Engineering with Rubber: How to design Rubber Components,
Hanser Publishers (1992).
5. J. E. Mark, B. Erman and F. R. Eirich, Science and Technology of Rubber,
Academic Press (1994).
6. L. R. G. Treloar, The physics of Rubber Elasticity, Clarendon Press (1975).
7. I. M. Ward, The Mechanical Properties of Solid Polymers, John Wiley and Sons
Ltd (2004).
8. K. P. Menard, Dynamic Mechanical Analysis A practical Introduction, CRC Press
LLC(1999).
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Atomic Force Microscopy (AFM)
The atomic force microscope (AFM) was invented
in 1986 by Binnig, Quate and Gerber.
The AFM raster scans a sharp probe over the
surface of a sample and measures the changes in
force between the probe tip and the sample.
Scanning at atomic level
The ability of an AFM to achieve near atomic scale resolution depends
on the three essential components:

(1) a cantilever with a sharp tip,

(2) a scanner that controls the x-y-z position, and
(3) the feedback control and loop.
 Parts of AFM
1. Laser – deflected off cantilever
2. Mirror –reflects laser beam to
photodetector
3. Photodetector –dual element
photodiode that measures differences in
light intensity and converts to voltage
4. Amplifier
5. Register
6. Sample
7. Probe –tip that scans sample made of Si
8. Cantilever –moves as scanned over
sample and deflects laser beam
 Principle
• The AFM consists of a cantilever with a sharp tip (probe) at its end that
is used to scan the specimen surface.
• The cantilever is typically tungsten,silicon/nitride with a tip radius of
curvature on the order of nanometers.
• When the tip is brought into proximity of a sample
surface, forces between the tip and the sample lead to a deflection of
the cantilever.
• Depending on the situation, forces that are measured in AFM include
mechanical contact force, van der Waals forces, capillary
forces, chemical bonding, electrostatic forces.
 Working Concept
The physical parameter probed is a force resulting from
different interactions.
Thus, an AFM image is generated by recording the force
changes as the probe (or sample) is scanned in the x and
y directions.
The sample is mounted on a piezoelectric scanner, which
ensures three-dimensional positioning with high
resolution.
The force is monitored by attaching the probe to a pliable
cantilever, which acts as a spring, and measuring the
bending or "deflection" of the cantilever.
 Modes of AFM

1. Contact Mode
2. Non-Contact Mode
3. Tapping (Intermittent contact) Mode
 Contact Mode
• Measures repulsion between tip and sample
• Force of tip against sample remains constant
• Feedback regulation keeps cantilever deflection
constant
• Voltage required indicates height of sample
• Problems: excessive tracking forces applied by
probe to sample
 Non-Contact Mode
• Measures attractive forces between tip and
sample
• Tip doesn’t touch sample
• Van der Waals forces between tip and sample
detected
• Problems: Can’t use with samples in fluid
• Used to analyze semiconductors
• Doesn’t degrade or interfere with sample- better
for soft samples
 Tapping Mode
(Intermittent-Contact)
• Tip vertically oscillates between contacting sample
surface and lifting of at frequency of 50,000 to
500,000 cycles/sec.
• Oscillation amplitude reduced as probe contacts
surface due to loss of energy caused by tip
contacting surface
• Advantages: overcomes problems associated with
friction, adhesion, electrostatic forces
• More effective for larger scan sizes
 Advantages and
Limitations of AFM
• Easy sample • Limited vertical
preparation range
• Accurate height • Tip or sample can
information be damaged
• Works in vacuum,
air, and liquids
• Living systems can
be studied
Interpretation
Interpretation of force-distance
curves
β-sheet of Spider Silk by AFM
Scratch Resistance
Polymer Blends
Polymer Blends
Lamellae