Glass Transition Temperature , Tg

Glass Transition Temperature , Tg

Viscous liquid Both segmental & molecular motion
Visco fluid state Flow temperature
Only mixture ( no sharp mpt)

Tf

Rubbery state
(soft, flexible) Segmental motion
(visco elastic state) not Molecular motion

Tg

Glassy state : Segmental motion No

amorphous polymer Molecular motion
(hard , brittle plastic) Rigid solid
(frozen state)
Importance of Tg Value

Tg is not only measure of flexibility of a polymer but also gives thermal expansion,
heat capacity, electrical and mechanical properties of the polymer.

Thus, workability and usefulness of a polymer over a range of temperature can be

obtained from its Tg.
Factors that affect the value of Tg

1. Crystallinity

Crystaline polymer arranged regular parallel fashion

Each chain bound strong force ( H- bonding)

Therefore, crystalline Tg > amorphous Tg

2 Molecular mass MM Tg

3 Side chain present Side chain Tg Hinder free rotation

4. plasticizers Plasticizers Tg Impurities on mpt

5. Stereo regularity Stereo regularity Tg

Tg isotactic > syndiotactic > atactic

7.6 Structure and property relationship of polymer

The properties like crystallinity , tacticity, tensile strength, elasticity, resistance to

chemicals, wear and tear etc. depends on the structure of polymers.

It is very important topic polymer science.

1. Crystallinity of polymer
2. Impact and tensile strength of polymer and molar mass
3. Plastic Deformation ( Rheology) of polymer
4. Chemical Resistivity
5. Tacticity of Polymers
6. Viscoelasticity of polymer
Crystallinity of polymer
polymer ----- crystalline ; molecules are arranged in an orderly , systematically
higher force of attraction
Any polymer---- definite % of crystalline parts and amorphous parts

Degree of crystallinity depends on how polymers closely packed.

Crystalline regions of a polymer ------ individual chains are linear (without branching, bulky
substituents), losely arranged // to each other

The strains of polymer may be held ---- Vander Waal’s force , hydrogen bonding or polar interacti

Polymer with high degree crystallinity HDPE,isotactic & syndrotactic polypropenes, PVC
•High tensile strength
•Impact and wear resistance
atactic polypropenes, PVC, polystyrene
•High density and high fusion temperature
•High Tg and melt viscosity
•Stero regular arrangement of their pendent group

Characteristics of crystalline polymers are

•High density
•Hard but brittle and strong
•Solubility and permeability decrease with increase in crystallinity
2. Impact and tensile strength of polymer and molar mass

Mechanical properties of polymer : density, melt viscosity , impact and

tensile strength influenced by molar masses of polymers.

Melt, viscosity ( low molar mass) low

Molar mass viscosity
Tensile strength and impact strength molar mass 2000 DP
Beyond molar mass 2000 DP --- increase is negligible
Each polymer has a limiting molar mass at which its tensile strength and workability
are good.
3. Plastic Deformation ( Rheology) of polymer

Thermoplastics : on heating to their Tg or pressure -----

flexible and rubbery ---- deformation.
On further heating( beyond their flow temp:) :
viscous liquid to flow
on cooling ; they turn to their original state.
( this property used in moulding of thermoplastic)

Thermosetting : no deformation . First soften and then hard mass.

On further heating – no change and charring.
( primary bonds cannot be easily broken by heat.)
4. Chemical Resistivity
Attacked by a reagent, it becomes softening , swelling and losses strengt

Chemical resistivity depend on

•Presence or absence of residual unsaturation
•Presence or absence of polar groups
•Molar mass, degree of crystallinity and extent of cross linking
Polymer swelling non-polar solvent
(non-polar groups) dissolution (benzene, toluene, CCl4)
H/C polymer

Polymer soluble polar solvent

(polar groups) (water, alcohols)
( -OH gps or -COOH)
Polymer hydrolysis strong alkali (at high temp)
(ester gps)
polyester

Polymer hydrolysis strong acid or alkali (at high temp)

(nylon)
polyamide

Polymer degradative oxidation

(Unsaturated residue)
(natural rubber & some synthetic rubber) in the air in light or ozone

(Natural some synthetic rubbers undergo degradative oxidation in air)

Poly alkenes, PVC, fluorocarbon ------ high degree of chemical resistance.

Molar mass crystallinity chemical resistivity

5. Tacticity of Polymers
Polymer molecules have different arrangement of adjacent chiral centers within molecules

Actactic useless gummy solid

Isotactic crystalline , tough
6. Viscoelasticity of polymer

Few polymeric materials exhibits both viscous and elastic characteristics under conditions.
Viscoelastic materials have elements have on both properties and exhibit time dependent strain

Elasticity: bond stretching along crystallographic planes in an ordered solid.

Viscoelasticity : the diffusion of the atoms or molecules inside of and amorphous
material.
Physical state of polymer are dependent on their chain length and molecular weight.
Elastic solid or viscous liquids depending on their physical state.
The change of physical properties of polymer is due to the effect of temperature.

They transform to hard and brittle when cooled slowly or vice versa.
The rate of cooling affects the properties of polymer.