Journal of Polymer Science Part B: Polymer Physics, Vol.38, No.24, 3302-3308, 2000
Discovery in nylon-8 chain-folded lamellar crystals of new structure - lambda-structure - with progressive intersheet shear along the chain axis
Structural studies on solution-grown, chain-folded nylon-8 lamellar crystals, using transmission electron microscopy (imaging and diffraction) together with X-ray diffraction from oriented mats, have led to the discovery of a new crystal structure. This has been termed the lambda -structure because of its similarity to tale recently reported lambda -structure found for the nonfolded, monodisperse 5-amide nylon-6 oligomer. In the stable nylon-8 monoclinic alpha -structure, the flat hydrogen-bonded sheets (cre plane; chain axis c), composed of antiparallel chains, stack via van der Waals interactions with alternating c-axis shear. Thus, in chain-folded lamellae, the cl lain direction is orthogonal to the lamellar surface. However, in the nylon-8 lambda -structure the same hydrogen-bonded sheets stack with severe progressive c-axis intersheet shear (44 degrees), generating an antiparallel two-chain triclinic unit cell with the parameters: a (hydrogen-bonding direction) = 0.980 nm; b = 0.544 nm; c = 2.24 nm; alpha = 49 degrees; beta = 90 degrees; gamma = 71.4 degrees, The structure bears a resemblance to the classic, heavily intersheet-sheared (41 degrees) nylon-6 6 alpha -structure reported by Bunn et al. in 1947. As far as we are aware, this is the first time the lambda -structure has been identified in polymeric even nylons and in chain-folded lamellar crystals. Changes to the principal diffraction signal spacings and the unit cell parameters with increasing temperature have been recorded. On heating, the chain-folded hydrogen-bonded sheets remain intact and move apart. Two regimes of intersheet movement have been identified: (1) the low-temperature regime (T < 120 C), in which the sheets move apart along the b direction only; and (2) the high-temperature regime (T > 120 degreesC), where the sheets move along both the b and c directions.