Rubbers exhibit predominantly entropy-driven elasticity. This was concluded
already by William Thomson (Lord Kelvin) (1857) and James Prescott Joule (1859)
through measurements of force and specimen length at different temperatures. They
discovered the thermo-elastic effects: (a) a stretched rubber sample subjected to a
constant uniaxial load contracts reversibly on heating; (b) A rubber sample gives out
heat reversibly when stretched. These observations were consistent with the view that
the entropy of the rubber decreased on stretching. The molecular picture of the
entropic force originates from theoretical work during the 1930’s. It was suggested
that the covalently bonded polymer chains were oriented during extension. Further
theoretical development occurred during the 1940's and the stress-strain behaviour
was traced back to the conformational entropy. The view that the long chain
molecules are stretched to statistically less favourable states still prevails (Fig. 3.1).
You can make a very simple demonstration with a piece of rope, which will act as a
model of the polymer chain. Take the ends of the rope with your two hands. If you
keep your hands close, the rope can take many different shapes. If you separate the
ends of the rope, fewer shapes are possible. Hence, the number of shapes the rope can
take decreases with the displacement of the ends. The force acting on the polymer
molecule is equal to the slope of the free energy vs. displacement curve (Fig. 3.1). The
instantaneous deformation occurring in rubbers is due to the high segmental mobility
and thus to the rapid changes in chain conformation of the molecules. The energy
barriers between different conformational states must therefore be small compared to
the thermal energy (RT).
The reversible character of the deformation is a consequence of the fact that
rubbers are lightly crosslinked (Fig. 3.2). The crosslinks prevent the chains from
slipping past each other. The chains between adjacent crosslinks contain typically