Segmented polyurethanes are a broad class of polymers whose properties
range from those characteristic of tough plastics to very soft rubbers, depending
on the soft segment length and concentration. Polyurethane elastomers are high
quality engineering materials combining high elasticity with high hardness and
low wear. When discussing the mechanical properties of segmented polyurethanes
we should bear in mind that we are dealing with two classes of
materials: tough plastics and elastomers, the latter being of predominant
interest. Elastomers are defined as materials displaying high, reversible deformations.
In order to obtain reversibility of extension, elastomers must be
crosslinked. In polyurethane elastomers crosslinks may be of a chemical or of
a physical nature. In segmented polyurethanes hard domains play the role of
physical crosslinks. Since hard domains may undergo physical and phase transitions
(glass transition and melting) this type of crosslink is thermally reversible,
making the mechanical behavior of these elastomers highly temperaturedependent.
The elasticity of segmented polyurethanes can be analyzed using the theory
of rubber elasticity of polymer networks. The differences in the specific properties
of polyurethanes from those of natural rubber, for example, arise from the
fact that hard domains are not point crosslinks but that they may occupy a very
large volume. Thus, they play the role of an active filler. Moreover, the hard
phase is also deformable. The size and shape of the hard domains affects
strongly the relaxation spectrum of polyurethane elastomers.