Abstract
Effect of epitaxy of nucleating agent (NA) on nucleation of polymers was investigated based on kinetic study. Nucleation rate (I) of polymers is given by I = Io exp(−ΔG*/KTC) (I), where Io is prefactor, ΔG* is free energy for forming critical nucleus, k is Boltzmann constant and Tc is crystallization temperature. We reported in the previous paper that decreasing the size of NA is important for increasing Io, i.e., I. In this study we focus on ΔG* dependence of I. In the case of heterogeneous nucleation, ΔG* is a function of interfacial free energy between NA and nucleus (Δσ). Δσ/σ varies between 0 and 1 where a is lateral surface free energy of nucleus. Δσ/σ of isotactic polypropylene (iPP) mixed with three NAs were between 0.13 and 0.23, which were evaluated by the fit of eq 1 to the experimental data of I. I increased by 38 orders of magnitude for ΔT = 30 K with decreasing Δσ/σ from 1 to 0. In the case of NA, I increased by 60 times for ΔT = 30 K with decreasing Δσ/σ from 0.23 to 0.13. I significantly depends on Δσ. Therefore we concluded that ΔG*(Δσ) is essentially important for acceleration of nucleation.
Similar content being viewed by others
Article PDF
References
K. Okada, K. Watanabe, T. Urushihara, A. Toda, and M. Hikosaka, Polymer, 48, 401 (2007).
T. Urushihara, K. Okada, K. Watanabe, A. Toda, E. Tobita, N. Kawamoto, and M. Hikosaka, Polym. J., 39, 55 (2007).
R. Becker and W. Doring, Ann. Phys., 24, 719 (1935).
D. Turnbull and J. C. Fisher, J. Chem. Phys., 17, 71 (1949).
F. P. Price, in ‘Nucleation,” A. C. Zettlemoyer, Ed., Marcel Dekker, New York, 1969, chap. 8, p 405.
Y. Takeda, in “Epitakisharu Seityono Mekanizumu (Mechanism of epitaxial growth),” K. Nakajima, ed., Kyoritsu Shuppan, Tokyo, 2002, chap. 5, pi 80.
S. Yoshimoto, T. Ueda, K. Yamanaka, A. Kawaguchi, E. Tobita, and T. Haruna, Polymer, 42, 9627 (2001).
M. Hikosaka and T. Seto, Polym. J., 5, 111 (1973).
E. J. Clark and J. D. Hoffmann, Macromolecules, 17, 878 (1984).
K. Yamada, M. Hikosaka, A. Toda, S. Yamazaki, and K. Tagashira, J. Macromol. Sci. Part B, Phys., 42, 733 (2003).
J. Brandrup, E. H. Immergut, D. R. Bloch, and E. A. Grulke, in “Polymer Handbook,” 4th ed., John Wiley & Sons, New York, 2003, V/23.
J. J. Janimak, S. Z. D. Cheng, and P. A. Giusti, Macromolecules, 24, 2253 (1991).
K. Yamada, M. Hikosaka, A. Toda, S. Yamazaki, and K. Tagashira, Macromolecles, 36, 4790 (2003).
K. Yamada, M. Hikosaka, A. Toda, S. Yamazaki, and K. Tagashira, Macromolecles, 36, 4802 (2003).
A. Ohkawa, in “Kessho-Seicho (Crystal Growth),” Shokabo Publishing, Tokyo, 1977, chap. 1, p 23.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Urushihara, T., Okada, K., Watanabe, K. et al. Acceleration Mechanism in Critical Nucleation of Polymers by Epitaxy of Nucleating Agent. Polym J 41, 228–236 (2009). https://doi.org/10.1295/polymj.PJ2008116
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.PJ2008116
Keywords
This article is cited by
-
Characterization of dual nano-size effects of ACC-cellulose nanofibrils on crystallization behavior of hydrophilic poly(vinyl alcohol)
Journal of Wood Science (2021)
-
The nucleation effect of self-dispersed β-nucleating agent in ethylene-propylene block copolymerized polypropylene
Colloid and Polymer Science (2018)
-
Nucleation ability of nonmetallic organophosphate derivatives in isotactic polypropylene
Journal of Thermal Analysis and Calorimetry (2017)
-
Thermodynamic effect on interaction between crystalline phases in size-controlled ACC-bacterial nanocellulose and poly(vinyl alcohol)
Cellulose (2017)
-
Joint effects of molecular structure and crystal morphology of organophosphate monovalent salts on nucleated isotactic poly(propylene)
Journal of Polymer Research (2016)