Plastic deformation of crystalline polymers

Under uniaxial tensile load, the plastic deformation of unoriented crystalline polymers first transforms the lamellae into a fibrous structure. Usually the drawing is inhomogeneous with a neck propagating through the sample. The higher the draw ratio, the higher the axial elastic modulus as a consequence of the larger fraction of taut tie molecules in amorphous layers connecting the crystalline blocks of each microfibril. As a consequence of the almost 1/(1 − α) times higher strain of amorphous layers under tensile load, the taut tie molecules are much more strained than the chains in crystal blocks. Hence, their contribution to elastic modulus is substantially higher than one would guess from their fraction β. This is more so in polyethylene with higher crystallinity (α = 0.8) than in nylon 6 with low crystallinity (α = 0.5). Even for the highest modulus polyethylene E = 70 GPa ∼ 0.3 × E c , one needs less than 7.5 percent of taut tie molecules. The plastic deformation of the fibrous structure markedly enhances the number of interfibrillar tie molecules in nylon 6 and to a lesser extent in polyethylene and polypropylene. Homogeneous drawing without a neck transforms the whole sample into a fibrous structure rather uniformly so that for a long while one has the lamellar and fibrillar morphology side by side. The end effect on the structure obtained does not differ appreciably from inhomogeneous drawing with neck propagation. The drawing of polymers with a liquid crystal structure yields a highly aligned fibrous structure with very few chain folds and an exceptionally high elastic modulus and strength. But the axial connection of individual highly oriented and ordered domains is affected by a relatively small fiaction of tie molecules, and this is responsible for reduction of the elastic modulus below the value of the ideal crystal lattice.