Polymer Science

MT 1063 - Semester 4 - 15 Batch

Average Molecular Weight

D
During polymerization, not all polymer molecular weight for a polymer to begin to exhibit
chains grow to the same length. Therefore sufficient strength to be useful. Most practical
individual chain molecules in polymer applications of polymers require higher molecular
chain are not at all of the same weight. weights to obtain higher strengths. But too high
Average molecular weights are therefore mechanical properties make polymers too tough to
considered. process.
Monodisperse polymer : (Some natural Polymers)
All polymer molecules have same molecular
weights.
polydisperse polymers (Synthetic Polymers) :
The molecular weights of polymers are distributed
has an anisotropic properties.
Mchanical properties that are uniquely associated
with polymeric materials are a consequence of their
high molecular weight. Most important mechanical
properties depend on and vary considerably with
molecular weight. Properties other than strength also show a
There is a minimum polymer molecular weight significant dependence on molecular weight.
(A), usually a thousand or so, to produce any However, most properties show different
significant mechanical strength at all. Above A, quantitative dependencies on molecular weight.
strength increases rapidly with molecular weight Different polymer properties usually reach their
until a critical point (B) is reached. Mechanical optimum values at different molecular weights.
strength increases more slowly above B and Further, a few properties may increase with
eventually reaches a limiting value (C). The critical molecular weight to a maximum value and then
point B generally corresponds to the minimum decrease with further increase in molecular weight.

Commonly Used Average Molecular Weights

V
arious methods based on solution
properties are used to determine the
average molecular weight of a polymer
sample. These include methods based on
colligative properties, light scattering, and
viscosity. The various methods do not yield the
same average molecular weight. Different Where the summation is over all the different
average molecular weights are obtained because size of polymer molecules from i=1 to i= and
the properties being measured are biased Ni is the number of molecules whose molecular
differently toward the different-sized polymer weight is Mi .
molecules in a polymer sample. Some methods Weight Average Molecular weight.
are biased toward the larger-sized polymer
molecules, while other methods are biased
toward the smaller-sized molecules. The result is
that the average molecular weights obtained are
correspondingly biased toward the larger- or
smaller-sized molecules. The following average Where Wi is the weight fraction of molecules
molecular weights are determined. whose weight Mi (Wi=NiMi)

Number Average Molecular weight. The

number average molecular weight is not too
difficult to understand. It is just the total weight
of all the polymer molecules in a sample, divided
by the total number of polymer molecules in a
sample.

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 Polymer Science
Viscosity Average Molecular Weight : Z average molecular weight
Viscosity is an internal property of a fluid that Mz isnt common technique for molecular weight
offers resistance to flow. Molecular weight can of polymers
also be calculated from the viscosity of a polymer
solution. The principle is a simple one: Bigger
polymers molecules make a solution more
viscous than small ones do. The molecular weight
obtained by measuring the viscosity is a different General equation of average molecular weight
from either the number average or the weight
average molecular weight. But it's closer to the
weight average than the number average.

0, 1, 2,

Where a is a constant

Schematic illustration of molecular weight

distributions

Mn
can be correlative
with polymer
colligative
properties, e.g.
freezing point depression, Mw may
be correlated with properties such
as melt viscosity. Mz may be
correlated with properties such as
toughness.

Polydispersity index
Mw/Mn is called as polydispersity index. Polydispersivity = 1 for a monodisperse polymer. It is greater
than 1 for all other polymers and increases with increasing polydispersity.

Effect of Polydispersity on a Polymer