Thermal expansivity of oriented nylon-6 and nylon-6,6

Measurements on the thermal expansivities along (α ∥) and normal (α⊥) to the draw direction have been carried out from 120 to 380K for nylon-6 and nylon-6,6 with draw ratio λ between 1 and 3.6. The sharp drop in α∥ and the slight increase in α⊥ with increasing λ can be attributed to the gradual alignment of chain segments in both the crystalline and amorphous regions. Using the presently available expansivity data on nylon-6 crystals it is found that the observed orientation dependence below the glass transition can be quantitatively described by a two-phase aggregate model. Water acts as a plasticizer and so its absorption leads to a drop of about 80K in the glass transition temperature. At low temperature, however, water appears to form bridges between molecular chains. This gives rise to a stronger interchain interaction and hence a lowering of the thermal expansivity.