Mechanical relaxations in polyamides

Dynamic mechanical measurements were carried out as a function of temperature (?100 to + 180°C) and frequency (3.5 to 110 cps) for a series of aliphatic terpolyamides, nylon 6 and nylon 12. Effect of crosslinking with toluene diisocyanate, of absorbed water, and of frequency are used to estimate the statistical segment length associated with the α′ relaxation. The effects of variations in the aliphatic chain length in the repeating unit on the temperature of the α′ relaxation are examined by means of copolymer rules with a view to explaining the reported insensitivity of the glass transition temperature of these polymers to changes in (CH₂)/(amide) group ratio. From the estimated length of the segmental motion associated with the α′ relaxation it is inferred that in a series of polyamides of the type nylon X or nylon X,Y (where X or Y = 3, 4, 5, 6, etc.) there should be a relatively small change in the temperature of the α′ transition for those polyamides having X or Y less than about 45. Experiments which are intended to establish the position of the crystalline α–γ transition are discussed.