A novel composite film of hydroquinone/resorcinol-based poly(arylene ether nitrile) (HQ/RS-PEN) improved by bisphenol A based poly(arylene ether nitrile) (BPA-PEN) was prepared, in which BPA-PEN acts as a plasticizer, leading to improved fluidity of the material, thereby favoring the crystallinity of HQ/RS-PEN. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and mechanical and rheological tests have shown that the composites exhibited outstanding thermal and mechanical properties as well as improved fluidity and processing applicability compared with HQ/RS-PEN. At the same time, the crystallization of the poly(arylene ether nitrile) blends with 5 wt % BPA-PEN could be promoted under both static and shear flow fields. Polarizing microscope (POM) and scanning electron microscopy (SEM) showed that the crystalline morphology of HQ/RS-PEN was converted from spherulites to fibrous crystals under shearing. DSC, X-ray diffraction (XRD), and dynamic storage modulus results proved that the crystallization rate and crystallinity of HQ/RS-PEN increased significantly under the shear field. The crystallinity enhanced to a maximum of 20.1% and the melting enthalpy increased to 33.4 J/g at 310 °C under the frequency of 0.01-100 Hz for 20 min.
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