Effect of temperature on viscoelastic behavior

Conducted by: - Md.Yeasin Arafat Tarek

Id:- 1018032711 (M.Sc-October-2018)

Viscoelastic Materials
Viscoelasticity is the property of materials that exhibit both viscous and elastic characteristics
when undergoing deformation. Viscous materials, like water, resist shear flow and strain linearly
with time when a stress is applied. Elastic materials strain when stretched and immediately return to
their original state once the stress is removed. This is termed as Anelasticity too.

Viscoelastic materials have elements of both of these properties.

Example: - Glasses or Amorphous Materials.

• Viscosity is the result of the diffusion of atoms or molecules inside an amorphous material.
• Whereas elasticity is usually the result of bond stretching along crystallographic planes in an
ordered solid.

Effect of temperature on viscoelastic behavior

Before we know the Effect of temperature on viscoelastic behavior we have to know some
temperature related term’s: -

1.Glass Transition Temperature, (Tg for amorphous materials and Semi-Crystalline Materials.)

• The temperature region where the polymer transitions from a hard, glassy material to a soft,
rubbery material.

2.Melting Temperature, (Tm Only for Semi-crystalline Materials.)

• The temperature at which Polymer materials especially Semi- Crystalline Materials started
to melt.
3.Heatdeflection temperature, (HDT)
The heat deflection temperature or heat distortion temperature is the temperature at which
a polymer or plastic sample deforms under a specified load.

General Concept
The modulus (E) which means, the stiffness or rigidity, very much dependent on
Temperature. ( = E ) where, = stress , =strain.

Modulus decreases with increasing temperature for thermoplastics.

• Modulus decreases suddenly as T exceeds Tg or Tm . (Semi-Crystalline)

• Above Tg , E increases or becomes flat for Crosslinked Polymers.

Fig:- Schematic of the dynamic modulus, E as a function of temperature for a

amorphous, crosslinked thermoset, and a semi-crystalline polymer.
Amorphous Material: -
For a linear amorphous polymer, there is a large drop in the modulus as the temperature
increases from region 1 (glassy modulus) to region 3 (rubbery modulus). The softening and hence
the deflection in the HDT is largely controlled by the glass transition of the polymer matrix.
Below Tg, it is glassy and have higher elastic modulus and elastic behavior. After Tg it becomes
soft and because of high viscosity the polymer chain still cannot move easily and becomes
leathery, rubbery and so on….to viscous flow liquid.
For both linear amorphous polymers and crosslinked thermosets (i.e. epoxies), the HDT will
be below the glass transition temperature.

Fig: - E as a function of temperature for an amorphous, crosslinked thermoset,

and a semi-crystalline polymer
Semi-Crystalline and Crosslinked Polymers: -
In the case of a Semi-crystalline polymer, the melting point (Tm) is caused by the melting of the
crystalline domains and the (Tg) is attributed to the change in modulus in the amorphous
region.
Depending on the degree of crystallinity, the modulus decreases between region 1 and region 2
will change. Higher crystallinity will result in a higher plateau modulus.

In the case of the Crosslinked thermoset, there is also a very large modulus drop at Tg, but there
is a plateau due to the crosslinked network in the rubbery region.

Illustration with some polymers

Effect of Crystallinity and Cross-linking Polymers

Why amorphous Polymers achieve flow like property with temperature?
-with the increasing of temperature, the viscosity decreases and the polymer chain or material
in amorphous liquid will move easily.
Why this phenomenon doesn’t exhibit in case of Crystalline solid?
-Because higher Crystallinity means higher degree of uniformity and higher amount of cross
linking. And we know, with heat cross-linkers become stronger. As, a result the phenomena
can’t be seen in Crystalline Solid.
Similarly, For Semi-Crystalline Solid A rubbery flow is highest possible region but
viscous flow is not possible due have some cross-linking.
A couple take-aways:

• Tg and HDT are not to be used interchangeably, especially in semi-crystalline polymers

• Tg measured by DSC, TMA, and DMA are typically higher than the HDT of amorphous
polymers and thermosets
• HDT is influenced by the filler loading, filler type, and reinforcement geometry (woven
fabric, random fibers, and particulates)

Two mentioned topic after my presentation

mentioned by (Dr. Chanchal Kumar Roy-Sir) are
given below: -
Effect of temperature and behavior of Polymer in different region:

For amorphous ,semi-crystalline and Crosslinked material’s:-

Difference between Tg and Tm

Contents Tg Tm

Definition The temperature region The temperature at which

where the polymer transitions Polymer materials especially
from a hard, glassy material to Semi- Crystalline Materials
a soft, rubbery material. started
to melt.

Conversion Glassy state into rubbery state Solid Crystalline state into
Solid amorphous state.

Phase of matter Changes from solid to Changes from a solid phase to

another solid phase, thus no
Semi solid or Rubbery Phase. change of phase matter.

Type of polymer For amorphous and semi- For Semi-crystalline and

crystalline polymers Crystalline Polymers.

Applicable Categories Mainly for thermosetting Mainly for thermo- Plastics

Plastics Polymers. Polymers.

Above the temperature Polymer has rubbery state and Polymer has crystalline region.
thus less rigid and not brittle.

Below the temperature Polymer has glassy state, thus Polymer has amorphous
rigid and brittle. region.
References: -
1. https://polymerinnovationblog.com/characterization-thermosets-part-19-heat-
deflection-temperature-hdt-2/
2. https://www.youtube.com/watch?v=r8eup6hSx3E (42.30 min-47.10 min)
3. https://en.wikipedia.org/wiki/Viscoelasticity
4. Meyers and Chawla (1999): "Mechanical Behavior of Materials“ (Page:-98-103)
5. McCrum, Buckley, and Bucknell (2003): "Principles of Polymer Engineering," 117-176