Crystallite morphology in thermotropic random copolymers: Application of transmission electron microscopy

The morphology of nonperiodic layer (NPL) crystallites appearing in three thermotropic random copolyesters composed of 30/70, 58/42, and 75/25 monomer ratios of p-oxybenzoate (B) and 2,6-oxynaphthoate (N) is investigated with transmission electron microscopy. Copolymer films, produced by shearing the materials above their melting points and subsequently annealing them above their glass transition temperature, exhibit ordered entities averaging no more than 20 nm thick and 40–60 nm long, as observed with dark-field imaging. Selected-area electron diffractograms exhibit sharp equatorial reflections, indicating ordered packing of random intramolecular sequences of the molecules. Microdensitometry of these diffraction patterns reveal that both the equatorial and first meridional reflections are radiation sensitive, decaying exponentially with dose. Saturation doses (v) for the crystallites depend on the copolymer composition and degree of polymerization (DP) and are estimated to be approximately 130–150C/m² for the high-molecular-weight copolymers (DP ≈ 150), with the N-rich copolymer possessing greater radiation resistance, and about 430 C/m² for a low-molecular-weight copolymer (DP ≈ 25).