New developments in the melt rheology of nylons. I: Effect of moisture and molecular weight

Abstract Peculiar observations on the melt rheology of ultra‐dry nylon resins, nylon 6 in particular, are reported. One aspect of this study deals with a sharp increase in zero shear melt viscosity (e.g. 2 to 5 times) as the nylon 6 resin moisture is taken from 0.10 down to 0.00%; the effect being reversible. Changes of such magnitude are unexpected considering that there are no detectable variations of the chemical/compositional/molecular weight type in the starting resin, when subjected to the imposed drying conditions. Another aspect of this study deals with a deviation of nylons (6, 6,6, and 12) from the Bueche (1952) relationship, well accepted for polymers to date. Under moderate drying conditions (e.g. 50°C/17 h/110 millitorr), the molecular weight exponent is found to be 3.8, which is within the range of 3.4 to 3.8 reported for nylon 6. However, under more severe drying conditions (e.g. 110°C/17 h/110 millitorr), the molecular weight exponents for nylon 6, nylon 66, and nylon 12 are 4.8, 5.4, and 4.6, respectively. We are proposing that a sharp increase in melt viscosity of ultra‐dry nylon 6 is partly due to an increase in the molecular weight of the melt (extrudate) which then, has a more pronounced impact on melt viscosity in view of the 4.8 exponent. Such unique results, in contrast to polyethylene (free radical polymer) and poly(ethylene terephthalate) (condensation polymer) are tentatively attributed to H‐bonding in nylon melts. Yet another aspect of this study deals with the rheology of supercooled molten polymers that can offer advantages for analytical characterization.