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Isothermal crystallization kinetics of syndiotactic polystyrene exposed to gamma radiation in vacuum

  • Yu-Fan Chuang (a1), Yi-Wen Ting (a1), Chen-Ti Hu (a1), Julie P. Harmon (a2) and Sanboh Lee (a3)...


The effect of gamma radiation in vacuum on the isothermal crystallization kinetics of syndiotactic polystyrene (sPS) was investigated via differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and x-ray diffraction (XRD). Amorphous sPS samples were irradiated in vacuum, heated to 310 °C, cooled down to crystallization temperatures (Tcs) from 220 to 260 °C, and annealed for different times. Upon reheating, overlapping endothermic melting peaks depicted the various crystallization forms, α, β, and β′. The endotherms were resolved using Gaussian functions relating enthalpy changes to the endothermic envelope. Isothermal crystallization kinetic data were analyzed using Avrami's model with Gaussian functions. The extent of crystallization of β and β′ forms increased with increasing crystallization time and temperature, while that of α form decreased. Crystallization half-time followed a modified Arrhenius equation. Crystallization activation energies for the β and β′ forms of sPS increased with increasing radiation doses. The results are compared to those of air irradiated sPS reported in the literature.


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1.Torikai, A. and Shibata, H.: Photodegradation of polystyrene: Effect of structure on the formation of degradation products. Arabian J. Sci. Eng. 27, 11 (2002).
2.Moser, S.W., Harder, W.F., Hurlbut, C.R., and Kusner, M.R.: Principles and practice of plastic scintillator design. Radiat. Phys. Chem. 41, 31 (1993).
3.Harmon, J.P., Gaynor, J.F., and Taylor, S.G.: Approaches to optimize scintillator polymers for optical radiation hardness. Radiat. Phys. Chem. 41, 153 (1993).
4.Feygelman, V., Harmon, J., and Walker, J.: Polysiloxane-based scintillators: 1,1′,2,2′-tetraphenylbutadiene as a secondary fluor. Nucl. Instrum. Methods Phys. Res., Sect. A 295, 94 (1990).
5.Wallace, J.S., Sinclair, M.B., Gillen, K.T., and Clough, R.L.: Color center annealing in γ-irradiated polystyrene under vacuum and air atmospheres. Radiat. Phys. Chem. 41, 85 (1993).
6.Chiang, I.J., Hu, C.T., and Lee, S.: Isothermal annealing of color centers in irradiated polystyrene in vacuum and air atmospheres. Mater. Chem. Phys. 70, 61 (2001).
7.Onyiriuka, E.C., Hersh, L.S., and Hertl, W.: Surface modification of polystyrene by gamma-radiation. Appl. Spectrosc. 44, 808 (1990).
8.Clough, R.L., Gillen, K.T., Mallone, G.M., and Wallace, J.S.: Color formation in irradiated polymers. Radiat. Phys. Chem. 48, 583 (1996).
9.Harmon, J.P. and Gaynor, J.: The effect of gamma irradiation on color center formation in optical polymers. J. Polym. Sci., Part B: Polym. Phys. 31, 235 (1993).
10.Diola, T., Okada, A., Mihara, M., and Nichols, K.: Applications of syndiotactic polystyrene. In Syndiotactic Polystyrene, Schellenberg, J. ed.; John Wiley & Sons, Inc, New York, 2010; p. 321.
11.Hermanson, N.J. and Wessel, T.E.: Syndiotactic polystyrene: A new polymer for high-performance medical applications. Medical Plastics and Biomaterials 1998,
12.Guerra, G., Vitaglian, V.M., Rosa, C.D., Petraccone, V., and Corradini, P.: Polymorphism in melt crystallized syndiotactic polystyrene samples. Macromolecules 23, 1539 (1990).
13.Lu, M., Zhao, X., Chen, L., Xiong, X., Zhang, J., Mai, K., and Wu, C.: Nucleation effect on polymorphism of melt-crystallized syndiotactic polystyrene. Polymer 52, 1102 (2011).
14.Tashiro, K., Ueno, Y., Yoshioka, A., and Kobayashi, M.: Molecular mechanism of solvent-induced crystallization of syndiotactic polystyrene glass. 1. Time-resolved measurements of infrared/Raman spectra and X-ray diffraction. Macromolecules 32, 310 (2001). Candia, F., Carotenuto, M., Guadagno, L., and Vittoria, V.: Polymorphism of syndiotactic polystyrene: Morphology of the solvent-induced crystalline forms. J. Macromol. Sci., Part B: Phys. 35, 265 (1996).
16.Suna, Z., Morgana, R.J., and Lewis, D.N.: Crystallization of syndiotactic polystyrene under pressure. Polymer 33, 660 (1992).
17.Olson, B.G., Prodpran, T., Jamieson, A.M., and Nazarenko, S.: Positron annihilation in syndiotactic polystyrene containing α and β crystalline forms. Polymer 43, 6775 (2002).
18.Larobina, D., Sanguigno, L., Venditto, V., Guerra, G., and Mensilieri, G.: Gas sorption and transport in syndiotactic polystyrene with nanoporous crystalline phase. Polymer 45, 429 (2004).
19.Prodpran, T., Shenogin, S., and Nazarenko, S.: Gas transport behavior of semicrystalline syndiotactic polystyrene containing α and β crystalline forms. Polymer 43, 2295 (2002).
20.Ho, R.M., Lin, C.P., Tsai, H.Y., and Woo, E.M.: Metastability studies of syndiotactic polystyrene polymorphism. Macromolecules 33, 6517 (2000).
21.Rapacciuolo, M., Derosa, C., Guerra, G., Mensitieri, G., Apicella, A., and Delnobile, M.A.: Different solvent stability of the crystalline polymorphic forms of syndiotactic polystyrene. J. Mater. Sci. Lett. 10, 1084 (1991).
22.Lin, R.H. and Woo, E.M.: Melting behavior and identification of polymorphic crystals in syndiotactic polystyrene. Polymer 41, 121 (2000).
23.Hong, B.K., Jo, W.H., Lee, S.C., and Kim, J.: Correlation between melting behavior and polymorphism of syndiotactic polystyrene and its blend with poly(2,6-dimethyl-1-1,4-phenylene oxide). Polymer 39, 1793 (1998).
24.Wang, C., Hsu, Y.C., and Lo, C.F.: Melting behavior and equilibrium melting temperatures of syndiotactic polystyrene in α and β crystalline forms. Polymer 42, 8447 (2001).
25.Zhou, W., Lu, M., and Mai, K.: Isothermal crystallization, melting behavior and crystalline morphology of syndiotactic polystyrene blends with highly-impact polystyrene. Polymer 48, 3858 (2007).
26.Rosa, C.D., de Ballesteros, O.D., Gennaro, M.D., and Auriemma, F.: Crystallization from the melt of α and β forms of syndiotactic polystyrene. Polymer 44, 1861 (2003).
27.Ting, Y.W., Nyugen, T., Hu, C.T., Chen, C.C., and Lee, S.: Effect of gamma ray on isothermal crystallization kinetics of syndiotactic polystyrene. J. Mater. Res. 28, 3053 (2013).
28.Ho, R.M., Lin, C.P., Hsieh, P.Y., and Chang, T.M.: Isothermal crystallization-induced phase transition of syndiotactic polystyrene polymorphism. Macromolecules 34, 6727 (2001).
29.Liu, C.K., Nguyen, T., Yang, T.J., and Lee, S.: Melting and chemical behaviors of isothermally crystallized gamma-irradiated syndiotactic polystyrene. Polymer 50, 499 (2009).
30.Avrami, M.: Granulation, phase change, and microstructure kinetics of phase change I. J. Chem. Phys. 7, 1103 (1939).
31.Avrami, M.: Transformation-time relations for random distribution of nuclei kinetics of phase change II. J. Chem. Phys. 8, 212 (1940).
32.Avrami, M.: Granulation, phase change and microstructure kinetic of phase change III. J. Chem. Phys. 9, 177 (1941).
33.Woo, E.M. and Wu, F.S.: On the melting behavior of polymorphic syndiotactic polystyrene and its behavior in a miscible state. Macromol. Chem. Phys. 199, 2041 (1998).
34.Wessen, R.D.: Melt crystallization kinetics of syndiotactic polystyrene. Polym. Eng. Sci. 34, 1157 (1994).
35.Chen, Q., Yu, Y., Na, T., Zhang, H., and Mao, Z.: Isothermal and non-isothermal melt-crystallization kinetics of syndiotactic polystyrene. J. Appl. Polym. Sci. 83, 2528 (2002).
36.Wu, T.M., Hsu, S.F., Chen, C.F., and Wu, J.Y.: Isothermal and non-isothermal crystallization kinetics of syndiotactic polystyrene/clay nano-composite. Polym. Eng. Sci. 44, 2288 (2004).
37.Wang, C., Huang, C.L., Cheng, Y.W., Cheng, Y.C., and Shong, J.: Radiation effects and re-crystallization mechanism of syndiotactic polystyrene with β′ crystalline form. Polymer 48, 7393 (2007).
38.Rabek, J.F.: Polymer Photodegradation: Mechanism and Experimental Methods (Chapman & Hall, New York, 1995); p 185.


Isothermal crystallization kinetics of syndiotactic polystyrene exposed to gamma radiation in vacuum

  • Yu-Fan Chuang (a1), Yi-Wen Ting (a1), Chen-Ti Hu (a1), Julie P. Harmon (a2) and Sanboh Lee (a3)...


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