Spinodal Crystallization of Polymers: Crystallization from the Unstable Melt

  • Keisuke KajiEmail author
  • Koji Nishida
  • Toshiji Kanaya
  • Go Matsuba
  • Takashi Konishi
  • Masayuki Imai
Part of the Advances in Polymer Science book series (POLYMER, volume 191)


This paper reviews the authors' investigation into polymer crystallization, especially involving a spinodal decomposition (SD) type phase separation due to the orientation fluctuation of stiff segments prior to crystal nucleation. Evidences for SD obtained from small-angle X-ray and neutron scattering (SAXS and SANS), depolarized light scattering (DPLS), Fourier-transform infrared spectroscopy (FT-IR) are discussed in detail in the case of the glass crystallization of poly(ethylene terephthalate) (PET) just above Tg. SD-like optical micrographs are also shown as a function of crystallization temperature for the melt crystallization of PET; their characteristic wavelengths Λ, which are of the order of μm above 120 °C, follow a van Aartsen equation derived from the Cahn–Hilliard theory for SD. By fitting the equation to the observed characteristic wavelengths the spinodal temperature Ts was determined to be Ts = 213 ± 5 °Cfor the PET melt, above which the SD pattern suddenly changed to the usual spherulite pattern. On the basis of a theory by Olmsted et al. [4], the general mechanisms of polymer crystallization are also discussed; the crystallization from the metastable melt causes the nucleation and growth (N&G) of dense (nematic) domains while that from the unstable melt causes SD into the dense (nematic) and less dense (isotropic) domains. Furthermore, the secondary phase separation of the SD-type phase separation into smectic and amorphous domains subsequently occurs inside the nematic domain for both these cases.

Induction period Melt and glass crystallization Nucleation and growth Optical microscopy Scattering techniques Spinodal decomposition 


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This study was supported by the Grant-in-Aid for Scientific Research on Priority Area “Cooperative Phenomena in Complex Liquids” (1995–1997), Grant-in-Aid for Scientific Research on Fundamental Research (A-2) (1998–2001), and Grant-in-Aid for Scientific Research on Priority Area “Mechanism of Polymer Crystallization” (2000–2002) from the Ministry of Education, Science, Sports and Culture of Japan, and by the International Joint Research Grant for the Project “Fundamental Studies on Crystallization of Polymers” (1995–1998) and Industrial Technology Research Grant (ITRG) Program “Control of Higher Order Structure of Polymer Materials” (2001–2004) of the New Energy and Industrial Technology Development Organization (NEDO), Japan.


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Authors and Affiliations

  • Keisuke Kaji
    • 1
    • 2
    Email author
  • Koji Nishida
    • 1
  • Toshiji Kanaya
    • 1
  • Go Matsuba
    • 1
  • Takashi Konishi
    • 1
  • Masayuki Imai
    • 3
  1. 1.Institute for Chemical ResearchKyoto UniversityKyoto-fuJapan
  2. 2.OsakaJapan
  3. 3.Department of PhysicsFaculty of Science, Ochanomizu UniversityTokyoJapan

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