Abstract
Direct evidence of nucleation during the induction period of nucleation from the melt is obtained for the first time by means of small angle X-ray scattering (SAXS). This confirmed that the induction period of crystallization from the melt corresponds to the process of nucleation, not to that of spinodal decomposition. This success is due to a significant increase in the scattering intensity (Ix) from the nuclei (104 times as large as is normal), which was achieved by adding a nucleating agent (NA) to a “model polymer” of polyethylene (PE). Ix increased soon after quenching to the crystallization temperature (Tc) and saturated after the induction time (τi). Lamellae start stacking later than the Mn.
Power laws of the molecular weight (Mn) dependence of the primary nucleation rate (I) and the growth rate (V) of PE, i.e., I or V ∝ Mn−H where H is a constant, were found for both morphologies of folded chain crystals (FCCs) and extended chain crystals (ECCs). As the power law was also confirmed on isotactic polypropylene (iPP), universality of the power law is suggested. It is to be noted that the power H increases significantly with increase of the degree of order of the crystal structure. The power law confirms that the topological nature of polymer chains, such as chain sliding diffusion and the chain entanglement within the interface between the nucleus and the melt or those within a nucleus, adopts a most important role in the nucleation and growth of polymers. This is theoretically explained by improving the “chain sliding diffusion theory” proposed by Hikosaka.
Entanglement dependence of the nucleation rate I is qualitatively obtained for the first time by changing the number density of entanglement (νe) within the melt. An experimental formula of I as a function of νe was obtained on PE, I(νe) ∝ exp(−γνe) where γis a constant.
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References
Becker R, Döring W (1935) Ann Phys 24:719
Zeldovich YaB (1943) Acta Physicochim USSR 18:1
Frenkel J (1946) Kinetic Theory of Liquids. Oxford University, London
Turnbull D, Fisher JC (1949) J Chem Phys 17:71
Flory PJ (1953) Principles of Polymer Chemistry. Cornell University, Ithaca, New York
de Gennes PG (1979) Scaling Concepts in Polymer Physics. Cornell University, Ithaca, New York
Doi M, Edwards SF (1986) The Theory of Polymer Dynamics. Clarendon Press, Oxford
Hikosaka M, Amano K, Rastogi S, Keller A (2000) J Materials Sci 35:5157
Hikosaka M, Amano K, Rastogi S, Keller A (1997) Macromolecules 30:2067
Hikosaka M, Tsukijima K, Rastogi S, Keller A (1992) Polymer 33:2502
Bassett DC, Block S, Piermarini GJ (1974) J Appl Phys 45:4146
Yasuniwa M, Enoshita R, Takemura T (1976) Jpn J Appl Phys 15:1421
Hikosaka M, Minomura S, Seto T (1980) Jpn J Appl Phys 19:1763
Hikosaka M (1987) Polymer 28:1257
Hikosaka M (1990) Polymer 31:458
Frisch HL (1957) J Chem Phys 27:90
Andres RP, Boudart M (1965) J Chem Phys 42:2057
Akpalu YA, Amis EJ (1999) J Chem Phys 111:8686
Imai M, Mori K, Kizukami T, Kaji K, Kanaya T (1992) Polymer 33:4457
Nishi M, Hikosaka M, Ghosh SK, Toda A, Yamada K (1999) Polym J 31:749
Nishi M, Hikosaka M, Toda A, Takahashi M (1998) Polymer 39:1591
Rastogi S, Hikosaka M, Kawabata H, Keller A (1991) Macromolecules 24:6384
Hikosaka M, Okada H, Toda A, Rastogi S, Keller A (1995) J Chem Soc Faraday Trans 91:2573
Frank FC, Tosi M (1961) Proc Roy Soc A263:323
Price F (1969) Nucleation in polymer crystallization. In: Zettlemoyer AC (ed) Nucleation. Marcel Dekker, Inc, New York
Wunderlich B (1980) Macromolecular Physics. Academic Press, London
Okada M, Nishi M, Takahashi M, Matsuda H, Toda A, Hikosaka M (1998) Polymer 39:4535
Hoffman JD, Frolen LJ, Ross GS, Lauritzen JI (1975) J Res NBS 79A:671
Hikosaka M, Yamazaki S, Wataoka I, Das NC, Okada K, Toda A, Inoue K (2003) J Macromol Sci B42:847
Guinier A (1967) Theory of technique of the radiocrystallograpy, (Japanese ed). Rigaku Denki, Tokyo
Roe RJ (2000) Methods of X-rayand neutron scattering in polymer science. Oxford Univ Press, New York
Olmsted PD, Poon WCK, McLeish TCB, Terrill NJ, Ryan AJ (1998) Phys Rev Lett 81:373
Ghosh SK, Hikosaka M, Toda A (2001) Colloid Polym Sci 279:382
Ghosh SK, Hikosaka M, Toda A, Yamazaki S, Yamada K (2002) Macromolecules 18:6985
Garti N, Sato K (eds) (2001) Crystallization Process in Fats and Lipid Systems. Marcel Dekker, Inc, New York
Nozaki K, Hikosaka M (2000) J Material Sci 35:1239
Wunderlich B (1973) Macromolecular Physics, vol 1&2. Academic Press, New York
Magill JH, Kojima M, Li HM (1973) the IUPAC Symp Macromol, Aberdeen, UK
Labaig JJ (1978) PhD Thesis, Faculty of Science, University of Strasbourg
Hoffman JD (1982) Polymer 23:656
Hoffman JD, Miller RL (1988) Macromolecules 21:3038
Kossel W (1927) Nach Ges Wiss Gottingen 135
Volmer M (1939) Kinetik der Phasenbildung
Burton WK, Cabrera N, Frank FC (1950-1951) Phil Trans Roy Soc A243:299
Watanabe H (1986) Kobunnshi High Polym Jpn 35:111046
Hoffman JD (1994) International Polymer Physics Symposium (Honoring Prof Kawai) p 19
Toda A (1992) Colloid Polym Sci 270:667
Hikosaka M, Rastogi S, Keller A, Kawabata H (1992) J Macromol Sci Phys B31:87
Yamazaki S, Hikosaka M, Gu F, Ghosh SK, Arakaki M, Toda A (2001) Polym J 33:906
Yamazaki S, Hikosaka M, Toda A, Wataoka I, Gu F (2002) Polymer 43:6585
Psarski M, Piorkowska E, Galeski A (2000) Macromolecules 33:916
Yamazaki S, Hikosaka M, Toda A, Okada K, Gu F, Watanabe K, submitted to Polymer
Alfonso GC, Scardigli P (1997) Macromol Symp 118:323
Acknowledgments
The authors are grateful to Prof. Akihiko Toda, Dr. Isao Wataoka, Dr. Swapan K. Ghosh of Hiroshima University, Dr. K. Yamada of SunAllomer Co. Ltd., Dr. Katsuaki Inoue of the Japan Synchrotron Radiation Institute (JASRI) and Dr. Zdenek Kozisek of the Institute of Physics, Academy of Sciences of the Czech Republic for their help with the experiments and discussions. SAXS experiments were carried out at the BL40B2 of SPring8 (SP8) at JASRI (Proposal No. 2001B0187-NDL-np—2004A0224-NL-2b-np) in Harima and at the BL-10C small angle installation of the Photon Factory (PF) at KEK in Tsukuba. The authors also thank Asahi Denka Kogyo K.K. for supplying the nucleating agent. This work was partly supported by the Grant-in-Aid for Scientific Research on Priority Areas B2 (No.12127205) and Scientific Research A2 (No. 12305062). The authors are grateful to the financial support from the International Joint Research grant, NEDO, 1996–1998.
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Hikosaka, M., Watanabe, K., Okada, K., Yamazaki, S. Topological Mechanism of Polymer Nucleation and Growth – The Role of Chain Sliding Diffusion and Entanglement. In: Allegra, G. (eds) Interphases and Mesophases in Polymer Crystallization III. Advances in Polymer Science, vol 191. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_010
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DOI: https://doi.org/10.1007/12_010
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