Role of entanglement in nucleation and 'melt relaxation' of polyethylene

Shinichi Yamazaki, Masamichi Hikosaka, Akihiko Toda, Isao Wataoka, Fangming Gu

Research output: Contribution to journalArticlepeer-review

60 Citations (Scopus)


An experimental formula of the nucleation rate I of polyethylene as a function of number density of entanglement ve within the melt was obtained as I(ve) ∝ exp(- γve), where y is a constant. In order to obtain a functional form of I(ve), I is determined by changing ve within the melt. The ve within the melt can be changed when crystals with different lamellar thickness I are melted. It is shown that the ve within the melt just after melting is related to I before melting. The ve of folded chain crystals (FCCs) is large, while that of extended chain single crystals (ECSCs) is very small. Therefore, strictly speaking, the experimental formula is a kind of 'semi -experimental' one. Because it is obtained by combining an experimental formula of I as a function of I before melting I(1) and a formula between l and ve based on the most probable model. It was found that the ve dependence of I is mainly controlled by the topological diffusion process within the interface between the melt and a nucleus and/or within the nucleus not by the forming process of a critical nucleus. The slope of the plots of log I against ΔT-2 was constant, irrespective of morphologies, FCCs and ECSCs, where ΔT is the degree of supercooling. From this fact, it was concluded that the fold type nucleus are formed from the melt of ECSCs as well as from the melt of FCCs. In our previous study, we found that I decreases exponentially with increase of annealing time Δt at a temperature above the melting temperature. From these results, we proposed a 'two-stage melt relaxation', i.e. fast conformational and slow topological relaxations. When the ECSCs are melted, extended chains within ECSCs are rapidly changed to random coiled chain conformation and then chains gradually entangle each other. We also proposed a formula, ve(Δt) ∝ -ln{const. + A exp(-Δt/τm)}, where A is a constant and τm is the 'melt relaxation' time.

Original languageEnglish
Pages (from-to)6585-6593
Number of pages9
Issue number24
Publication statusPublished - Oct 7 2002
Externally publishedYes


  • Entanglement
  • Melt relaxation
  • Nucleation

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry


Dive into the research topics of 'Role of entanglement in nucleation and 'melt relaxation' of polyethylene'. Together they form a unique fingerprint.

Cite this