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MOLECULAR WEIGHT PROPERTIES

BY NEERAJ SHARMA -12210108 SWATI SHARMA -12210113 THARAKESWARI -12210114

Molecular weight
Molecular weight and molecular weight distribution in polymers plays an important role in determining their bulk properties. The most important feature distinguishing polymers from low molecular weight species is the molecular weight of polymers. Molecular weight of commercial polymers ranges between 10,000 g/mol to 10,00,000 g/mole.

TENSILE ST

MOLECUL AR WEIGHT PROPERTI ES

Tg

Crystallanity

High

Non Polymeric

Hard, brittle

Hard, strong, stiff

Crystallinity

Soft, waxy

Tough, flexible

None < 1000 1000 10,000 Molecular weight >10,000

Crystallanity
Mechanism of crystal formation requires two steps: Nucleation and Growth. Low MW polymer have less stable nuclei but growth rate is high where as in high MW polymers the nuclei is stable but growth is slow. If the material is highly crystalline it will be more brittle due to restricted segmental motion where as low crystalline material are relatively tough because they will allow the chain movement and absorbs the energy applied by impact.

Tensile Strength and Toughness


Portion where the polymers attains full strength

Molecular weight

Tensile strength increases with molecular weight up to a certain point and then levels off as shown in the graph. Higher molecular weight permits greater degree of chain entanglements resulting in higher tensile strength. Due to chain entanglements, orientation becomes difficult thus resulting in slow crystal formation. Due to this slow crystal formation there is no further increase in mechanical properties

Mechanical properties

Viscosity
The relationship between viscosity and MW is explained by logarithmic plot. The value of Mc varies form one polymer to another polymer. Below Mc, the molecules move independently same as in liquid but above this point entanglement of chain molecules is so prominent that movement of one involve dragging of another. Very high rate of viscosity with increase in MW

Log viscosity, poise

Slope 3.4

Slope 1.75
Critical Molecular Weight (Mc)

Log Molecular weight

Melting point
Callister, rubber Fig. 16.9 tough plastic Tm Tg

mobile liquid

viscous liquid

crystalline solid Molecular weight

partially crystalline solid

Tm is the melting point of most of the perfect crystalline region. For higher MW polymers crystallize in the form of folded chains where as low MW polymers crystallize in the form of extended chains. This leads to formation of large crystals thus resulting in increased Tm.

Glass Transition Temperature


=
K

Molecular weight Around 20,000

Higher MW restricts the segmental rotation and hence causes rise in Tg

Tg

Molecular weight