本研究主要探討不同聚酯其結構對熱性質與結晶速率之影響，與添加不同比例的不定型聚合物PETG及固定比例的奈米碳管CNT對熱性質與結晶化速率的影響。利用示差掃描熱量儀進行等溫與非等溫結晶，從結果發現，PET與PEN長碳鏈為乙烯基團，具有較高熔融溫度與較大的過冷度。聚酯添加CNT後，其熔融溫度與結晶速率會提高，添加PETG後，隨著比例不同，會使其熔融溫度、結晶溫度降低。由Avrami equation得知，其成核指數n並無明顯的變化，結晶速率k則因添加CNT而變大，代表結晶速率增快，添加PETG後變化幅度不大。

This research is about how the structure of polyester effect on thermal properties and crystallization rate, and different ratio of amorphous polymer PETG and carbon nanotubes effect on thermal properties and crystallization rate.
We crystallize our sample under isothermal and non-isothermal procedure using DSC, and find out that PET and straight-chain of PEN are vinyl group and have high melting temperature and high degree of superercooling. After blending with CNT, the melting temperature and crystallization rate of polyester will increase, and after blending with different ratio of PETG, the melting temperature and crystallization rate of polyester will decrease. We can know from Avrami equation that nucleation index n has no big change; the crystallization rate k will increase because of the adding CNT, and will decrease because of the adding PETG.

[1] S. Yesil and G. Bayram, Poly(ethylene terephthalate)/Carbon Nanotube Composites Prepared With Chemically Treated Carbon Nanotubes. 2011, pp. 1286-1300.
[2] R. R. Chowreddy, K. Nord-Varhaug, and F. Rapp, "Recycled polyethylene terephthalate/carbon nanotube composites with improved processability and performance," Journal of Materials Science, vol. 53, no. 9, pp. 7017-7029, 2018.
[3] C. P. Papadopoulou and N. K. Kalfoglou, "Compatibility behaviour of blends of poly(ethylene terephthalate) with an amorphous copolyester," Polymer, vol. 38, no. 3, pp. 631-637, 1997/02/01/ 1997.
[4] C. P. Papadopoulou and N. K. Kalfoglou, "Blends of an amorphous copolyester with poly (butylene terephthalate)," European Polymer Journal, vol. 33, no. 2, pp. 191-197, 1997/02/01/ 1997.
[5] R. P. Daubeny, C. W. Bunn, and C. J. Brown, "The Crystal Structure of Polyethylene Terephthalate," Proc. Roy. Soc., vol. 226, pp. 531-542, 1954.
[6] C. Y. Liang and S. Krimm, "Infrared spectra of high polymers. Part IX. Polyethylene terephthalate," Journal of Molecular Spectroscopy, Article vol. 3, no. 1-6, pp. 554-574, 1959.
[7] Z. Chen, J. N. Hay, and M. J. Jenkins, "The effect of secondary crystallization on crystallization kinetics – Polyethylene terephthalate revisited," European Polymer Journal, vol. 81, pp. 216-223, 2016/08/01/ 2016.
[8] T. Asano et al., "Crystallization of oriented amorphous poly(ethylene terephthalate) as revealed by X-ray diffraction and microhardness," Polymer, vol. 40, no. 23, pp. 6475-6484, 1999/11/01/ 1999.
[9] M. E. Nichols and R. E. Robertson, "The multiple melting endotherms from poly(butylene terephthalate)," Journal of Polymer Science Part B: Polymer Physics, Article vol. 30, no. 7, pp. 755-768, 1992.
[10] C.-S. Park, K.-J. Lee, J.-D. Nam, and S.-W. Kim, "Crystallization kinetics of glass fiber reinforced PBT composites," Journal of Applied Polymer Science, vol. 78, no. 3, pp. 576-585, 2000/10/17 2000.
[11] Z. Papageorgiou George, P. Karayannidis George, N. Bikiaris Dimitris, A. Stergiou, G. Litsardakis, and S. Makridis Sofoklis, "Wide-angle X-ray diffraction and differential scanning calorimetry study of the crystallization of poly(ethylene naphthalate), poly(butylene naphthalate), and their copolymers," Journal of Polymer Science Part B: Polymer Physics, vol. 42, no. 5, pp. 843-860, 2004/03/01 2004.
[12] G. Wypych, "PBN poly(butylene 2,6-naphthalate)," in Handbook of Polymers (Second Edition), G. Wypych, Ed.: ChemTec Publishing, 2016, pp. 307-309.
[13] L. P. Chen, A. F. Yee, J. M. Goetz, and J. Schaefer, "Molecular structure effects on the secondary relaxation and impact strength of a series of polyester copolymer glasses," Macromolecules, Article vol. 31, no. 16, pp. 5371-5382, 1998.
[14] S.-H. Hwang, K.-S. Jeong, and J.-C. Jung, "Thermal and mechanical properties of amorphous copolyester (PETG)/LCP blends," European Polymer Journal, vol. 35, no. 8, pp. 1439-1443, 1999/08/01/ 1999.
[15] A. Yu and X. A. Huang, "Pyrolysis of an amorphous copolyester," Journal of Applied Polymer Science, vol. 101, no. 5, pp. 2793-2797, 2006/09/05 2006.
[16] H. W. Kroto, J. R. Heath, S. C. O'Brien, R. F. Curl, and R. E. Smalley, "C60: Buckminsterfullerene," Nature, Article vol. 318, no. 6042, pp. 162-163, 1985.
[17] S. Iijima, "Helical microtubules of graphitic carbon," Nature, vol. 354, p. 56, 11/07/online 1991.
[18] A. G. Rinzler et al., "Large-scale purification of single-wall carbon nanotubes: Process, product, and characterization," Applied Physics A: Materials Science and Processing, Article vol. 67, no. 1, pp. 29-37, 1998.
[19] S. Iijima and T. Ichihashi, "Single-shell carbon nanotubes of 1-nm diameter," Nature, vol. 363, p. 603, 06/17/online 1993.
[20] C. Q. Ru, "Effect of van der Waals forces on axial buckling of a double-walled carbon nanotube," Journal of Applied Physics, Article vol. 87, no. 10, pp. 7227-7231, 2000.
[21] J. P. Lu, "Elastic properties of single and multilayered nanotubes," Journal of Physics and Chemistry of Solids, Article vol. 58, no. 11, pp. 1649-1652, 1997.
[22] M. M. J. Treacy, T. W. Ebbesen, and J. M. Gibson, "Exceptionally high Young's modulus observed for individual carbon nanotubes," Nature, Article vol. 381, no. 6584, pp. 678-680, 1996.
[23] R. S. Ruoff and D. C. Lorents, "Mechanical and thermal properties of carbon nanotubes," Carbon, Article vol. 33, no. 7, pp. 925-930, 1995.
[24] H. Ajiki and T. Ando, "Electronic States of Carbon Nano tubes," Journal of the Physical Society of Japan, Article vol. 62, no. 4, pp. 1255-1266, 1993.
[25] K. Tanaka et al., "Electronic properties of carbon nanotube," Chemical Physics Letters, Article vol. 223, no. 1-2, pp. 65-68, 1994.
[26] R. Androsch, E. Zhuravlev, J. W. P. Schmelzer, and C. Schick, "Relaxation and crystal nucleation in polymer glasses," European Polymer Journal, vol. 102, pp. 195-208, 2018/05/01/ 2018.
[27] R. Androsch, C. Schick, and J. W. P. Schmelzer, "Sequence of enthalpy relaxation, homogeneous crystal nucleation and crystal growth in glassy polyamide 6," European Polymer Journal, Article vol. 53, no. 1, pp. 100-108, 2014.
[28] Z. Pingping and M. Dezhu, "Study on the double cold crystallization peaks of poly(ethylene terephthalate) (PET): 2. Samples isothermally crystallized at high temperature," European Polymer Journal, vol. 35, no. 4, pp. 739-742, 1999/04/01/ 1999.
[29] F. Fontaine, J. Ledent, G. Groeninckx, and H. Reynaers, "Morphology and melting behaviour of semi-crystalline poly(ethylene terephthalate): 3. Quantification of crystal perfection and crystallinity," Polymer, Article vol. 23, no. 2, pp. 185-191, 1982.
[30] Z. Chen, J. N. Hay, and M. J. Jenkins, "The effect of secondary crystallization on melting," European Polymer Journal, vol. 49, no. 9, pp. 2697-2703, 2013/09/01/ 2013.
[31] D. Raabe, N. Chen, and L. Chen, "Crystallographic texture, amorphization, and recrystallization in rolled and heat treated polyethylene terephthalate (PET)," Polymer, vol. 45, no. 24, pp. 8265-8277, 2004/11/01/ 2004.
[32] R.-M. Ho, P.-Y. Hseih, C.-C. Yang, and J.-J. Lin, "Crystallization kinetics for low-ether-content polyether–polyester block copolymers with amide linkages," Journal of Polymer Science Part B: Polymer Physics, vol. 39, no. 20, pp. 2469-2480, 2001/10/15 2001.
[33] A. Keller, "Investigations on banded spherulites," Journal of Polymer Science, vol. 39, no. 135, pp. 151-173, 1959/09/01 1959.
[34] M. Avrami, "Kinetics of Phase Change. II Transformation‐Time Relations for Random Distribution of Nuclei," The Journal of Chemical Physics, vol. 8, no. 2, pp. 212-224, 1940/02/01 1940.
[35] M. Avrami, "Kinetics of Phase Change. I General Theory," The Journal of Chemical Physics, vol. 7, no. 12, pp. 1103-1112, 1939/12/01 1939.
[36] X. F. Lu and J. N. Hay, "Isothermal crystallization kinetics and melting behaviour of poly(ethylene terephthalate)," Polymer, Article vol. 42, no. 23, pp. 9423-9431, 2001.
[37] J.-H. Wu et al., "Poly(ethylene terephthalate)/Poly(ethylene glycol-co-1,3/1,4-cyclohexanedimethanol terephthalate)/Clay nanocomposites: Morphology and isothermal crystallization kinetics," Journal of Applied Polymer Science, vol. 128, no. 1, pp. 487-497, 2013/04/05 2012.
[38] Y. Kong and J. N. Hay, "Multiple melting behaviour of poly(ethylene terephthalate)," Polymer, Article vol. 44, no. 3, pp. 623-633, 2002.
[39] A. Stocco, V. La Carrubba, S. Piccarolo, and V. Brucato, "The solidification behavior of a PBT/PET blend over a wide range of cooling rate," Journal of Polymer Science Part B: Polymer Physics, vol. 47, no. 8, pp. 799-810, 2009/04/15 2009.
[40] T. Nishi and T. T. Wang, "Melting Point Depression and Kinetic Effects of Cooling on Crystallization in Poly(vinylidene fluoride)-Poly(methyl methacrylate) Mixtures," Macromolecules, vol. 8, no. 6, pp. 909-915, 1975/11/01 1975.