Summary: Poly(ethylene 2,6‐naphthalate) (PEN) can crystallize either from the glassy state or from the melt state. When crystallized from the glassy state, the sample was quenched from the melt in liquid nitrogen and then annealed at certain crystallization temperatures. When crystallized from the melt state, the sample was cooled to a preset temperature from the melt and then annealed for a certain time. The crystal modifications, morphologies and melting behaviors of PEN were investigated by means of wide‐angle X‐ray diffraction (WAXD), polarized optical microscopy (POM), small‐angle light scattering (SALS) and differential scanning calorimetry (DSC). The results show that an α crystal modification of PEN was obtained when PEN crystallized from the glassy state, whilst a β crystal modification was obtained when PEN crystallized from the melt state at a higher temperature. An hedritic morphology of PEN crystal was obtained with only one melting peak observed in DSC curves when PEN was crystallized at a higher temperature from either the glassy state or the melt state. The α crystal modification could also be obtained when PEN was crystallized at a lower temperature from the melt. Spherulitic or banded spherulitic morphologies of PEN crystals, exhibiting multiple melting peaks in DSC curves, were observed when PEN was crystallized at a lower temperature. The multiple melting behaviors of PEN crystals may be associated with spherulitic structures composed of lamellae of varying thickness.
WAXD patterns of PEN isothermally crystallized from different states.
