Effect of the blend ratio of cyclic and linear polyethylene blends on isothermal crystallization in the quiescent state

• Published in: Polymer journal Vol. 55; no. 12; pp. 1393 - 1398
• Main Authors: Kobayashi, Keiko, Atarashi, Hironori, Yamazaki, Shinichi, Kimura, Kunio
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.12.2023; Nature Publishing Group
• Subjects: 639/638/298; 639/638/455; Biomaterials; Bioorganic Chemistry; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Crystallization; Differential scanning calorimetry; Entanglement; Heat transmission; Optical microscopy; Polyethylene; Polyethylenes; Polymer blends; Polymer Sciences; Supercooling; Surfaces and Interfaces; Thin Films
• ISSN: 0032-3896; 1349-0540
• DOI: 10.1038/s41428-023-00833-1

The role of entanglements that form between cyclic and linear polymers in crystallization is of particular interest, but it is not fully understood. We investigated the crystallization behaviors of blends of cyclic polyethylene (C-PE) and linear polyethylene (L-PE) in a quiescent state to elucidate the role of this novel entanglement in crystallization. The samples were prepared by mixing the prepared C-PE and L-PE specimens at L-PE weight fraction ( Φ L-PE ) values of 0–100 wt%, with the weight average molecular weights of C-PE and L-PE being 175 × 10 3 and 154 × 10 3 , respectively. The isothermal crystallization behaviors were analyzed through polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The morphology observed through POM was similar to that of Φ L-PE . From the time evolution of the heat flow measured via DSC, we obtained the half-crystallization time ( t 1/2 ) values as functions of Φ L-PE at different degrees of supercooling (Δ T ). The 1/ t 1/2 values of the C-PE and L-PE homopolymers were approximately the same at Δ T  = 25.5 and 26.5 K. At a larger Δ T value, the 1/ t 1/2 value of C-PE was significantly larger than that of L-PE. In contrast, 1/ t 1/2 reached a minimum value at Φ L-PE  = 30–40 wt%, irrespective of Δ T . As the entanglement density increased with increasing Φ L-PE , the crystallization rate was expected to decrease monotonically. By considering the experimental relationship between 1/ t 1/2 and Φ L-PE , we speculated that the suppression of crystallization in the blended system was caused by a novel entanglement formed by the penetration of the L-PE chain into the C-PE chain. The isothermal crystallization behaviors of blends of cyclic polyethylene (C-PE) and linear polyethylene (L-PE) in a quiescent state were investigated. This figure shows the inverse of the half-crystallization time (1/ t 1/2 ) as a function of the weight fraction of L-PE ( Φ L-PE ) at different degrees of supercooling (Δ T ). The 1/ t 1/2 showed a minimum at Φ L-PE  = 30–40 wt%, irrespective of Δ T . By considering the experimental relationship between 1/ t 1/2 and Φ L-PE , we speculated that the suppression of crystallization in the blended system was caused by a novel entanglement formed by the penetration of the L-PE chain into the C-PE chain.