The crystal structure and drawing-induced polymorphism in poly(aryl ether ketone)s .1. Poly(oxybiphenyl-4-4'-diyloxy-1,4-phenylenecarbonyl-1,3-phenylenecarbonyl-1,4-phenylene)

Crystal structure and polymorphism induced by uniaxial drawing of a poly(aryl ether ketone) [PEDEKmK] prepared from 1,3-bis(4-fluorobenzoyl)benzene and biphenyl-4,4'-diol have been investigated by means of transmission electron microscopy (TEM), electron diffraction (ED), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC) techniques. The melting and recrystallization process in the temperature range of 250-260 degrees C, far below the next melting temperature (306 degrees C), was identified and found to be responsible for the remarkable changes in lamellar morphology. Based on WAXD and ED patterns, it was found that crystal structure of isotropic-crystalline PEDEKmK obtained under different crystallization conditions (melt-crystallization, cold-crystallization, solvent-induced crystallization, melting-recrystallization, and crystallization from solution) keeps the same mode of packing, i.e., a two-chain orthorhombic unit cell with the dimensions a = 0.784 nm, b = 0.600 nm, and c = 4.745 nm (form I). A second crystal modification (form II) can be induced by uniaxial drawing above the glass transition temperature, and always coexists with form I. This form also possesses an orthorhombic unit cell but with different dimensions, i.e., a = 0.470 nm, b = 1.054 nm, c = 5.064 nm. The 0.32 nm longer c-axis of form II as compared with form I is attributed to an overextended chain conformation due to the expansion of ether and ketone bridge bond angles during uniaxial drawing. The temperature dependence of WAXD patterns for the drawn PEDEKmK suggests that form II can be transformed into the more stable form I by relaxation of overextended chains and relief of internal stress at elevated temperature in absence of external tension.