本研究係透過原子力顯微鏡 (AFM)、環境式掃描顯微鏡 (E-SEM)、微分掃描熱卡計 (DSC)、傅立葉紅外光譜分析儀 (FTIR)、廣角X光繞射儀 (WAXD)之測定，針對聚丁二酸丁二醇酯 (PBSu)與聚氧化乙烯 (PEO) 之摻合體球晶形貌進行探討。在結晶溫度70度時，純聚丁二酸丁二醇酯 (PBSu) 系統呈現環帶狀球晶形貌，並在有些區域出現纖維狀形貌，此種同時擁有兩種形貌在同一個球晶中被稱為Janus-faced球晶。而純聚氧化乙烯 (PEO) 系統則只呈現出纖維狀的球晶形貌，但表面較為粗糙。PBSu/PEO混摻系統依其組成的不同會展現出複雜的結晶行為，在與PEO混摻後，PBSu依然會形成Janus-faced球晶，且環帶狀球晶的環帶寬度隨著PEO比例的增加而變大。而本研究利用PBSu/PEO (70/30) 對Janus-faced球晶進行深入的探討。在加入上蓋的實驗中發現，球晶生長空間受到限制會進一步影響混摻系統之球晶形貌。而在改變熔融溫度 (Tmax) 的實驗中，發現PBSu/PEO (70/30) 混摻系統在不同的Tmax熔融會有不同的情況發生，如果Tmax = 150, 160, 170 oC，隨著熔融溫度的上升，PEO微相域會聚集變大，並在樣品降至室溫後結晶 ; 當Tmax = 190, 200 oC時，由於PEO 微相域分布變得均勻，所以無法形成單一的PEO球晶。本研究進一步利用AFM作樣品蝕刻前後的表面觀察，比較之後發現PBSu的球晶表面被片狀的PEO晶板給覆蓋。而藉由DSC做熱行為的分析，發現在各個PBSu/PEO混摻系統中，都有兩個吸熱峰的特徵呈現，沒有新的吸熱峰出現。在WAXD的測定中，發現到此混摻系統並沒有新的繞射峰被觀察到，因此藉由DSC和WAXD結果可以推論，PBSu和PEO的晶格並無發生改變。並利用FTIR確認是否有高分子降解的情況發生，結果顯示Tmax = 190 oC的樣品，PEO分子量並沒有太大的變化。
接下來是針對此PBSu/PEO混摻系統的Janus-faced球晶機制來做介紹。基本上此混摻系統是由環狀和纖維狀的結晶形貌共同組成的，在纖維狀部分的球晶，大部分是由較寬的晶板以flat-on的方向排列，而其纖維狀結構在球晶中所出現的位置並沒有特定的方向。藉由AFM和SEM的表面結果可觀察到，在核心的位置，一部分的晶板是呈現緻密的束狀結構，而這些結構是有其週期性的發展，更為準確地說，週期性的波峰是由edge-on方向的晶板所形成，然而在波谷方面，則是由較為狹窄的flat-on晶板所形成，這些晶板依週期性的發展而生成環帶狀形貌。至於束狀結構以外的區域，主要是由層狀晶板排列並連續性的生長，呈現纖維狀結晶形貌。在球晶成長速率的部分，從結果所得到的環狀與纖維狀球晶之斜率呈現平行，代表兩者間的結晶速率幾乎相同。從纖維狀的結晶上表面部分可以觀察到，其排列方式以較長較寬的晶板沿著徑向方向連續性的生長，在這些晶板的側邊伴隨著小分支以flat-on方向生長，而從纖維狀球晶之斷截面部分觀察，可以發現到其晶板都是以flat-on的方向生成纖維狀球晶形貌。另一方面，針對環狀球晶形貌的晶板部分，不管是從斷截面或是上表面都可以很明顯的看到，在波峰(較亮)的部分，較小的晶板以edge-on的方向排列，而在波谷(較暗)的部分，晶板則是以flat-on的方向排列，其晶板在環帶狀球晶以flat-on方向排列的相較於在纖維狀球晶的晶板狹窄許多。

Morphology of semicrystalline poly(butylene succinate) (PBSu) revealed Janus-faced spherulites with fine banded spherulites. The spherulitic morphology of neat PBSu showed banded spherulites with minor fibrous part at low crystallization temperature of 70 oC. On the other hand, morphology of neat PEO naturally exhibited fibrous pattern or coarse-grained morphology. In brief, the PBSu/PEO blend presented complex crystallization behaviours depending on the blend composition. The band-spacing of neat PBSu became larger with the increasing of PEO content on the blend, the optimum ring-band formation revealed at PBSu/PEO 70/30. Top cover confinement also had influenced on spherulite morphology in the blend. PEO domains were found to nucleate and grow continuously in the blend 70/30 melted at Tmax 150 oC and after melted at 160 and 170 oC those small PEO segregations were increased and growth continuously after crystallized at room temperature for 30 minutes, while in Tmax 190 and 200 oC PEO spherulite disappeared because homogeneous phase segregation (well distributed). From AFM observation, the AFM images of PBSu/PEO blend before and after etching, were found an amount of PEO crystallized on the top of PBSu making the surface of PBSu spherulites mostly covered by plat-like lamellae of PEO. Thermal behaviour observation, two melting endotherm peaks were observed by DSC for all blend system. Blending PBSu with PEO did not generate any new endotherm peak of the blend. By WAXD, PBSu/PEO blend did not show any new crystal peak, from DSC and WAXD indicated that both of PBSu and PEO were crystallized in their own crystal lattices. From the FTIR result, the usage of 190 oC melting temperature did not give any significant effect on PEO degradation. The mechanism of Janus-faced spherulites of PBSu/PEO blend composed a ring-band and fibrous pattern. The fibrous lamellae packed by wider lamellae in flat-on orientation. The growth rate of fibrous lamellae had possibility to grow in all directions. From top view by AFM and SEM images, proved that the lamellae in the nuclei part composed by “tied” or sheaf-like lamellae bundled compactly. The sheaf-like or tied lamellae were discerned to grow radially as a periodic ridge consist of edge-on orientation while the valley composed by narrow flat-on lamellae, such phenomenon occured periodically. It led to the formation of the ring-banded pattern. The areas without sheaf-like lamellae was covered by plated lamellae that tent to grow as fibrous continuously. The ring-banded and fibrous pattern were parallel with each other, suggesting identical growth rates for these two regions. The growth rates of both regions were quite similar. From top view the lamellar arrangement in the fibrous pattern as flat-on orientation growth with small branches on the side part and growth continuously along radial direction and packed of long and wide lamellae. From lateral view of fibrous region, the lamellae orientation composed by flat-on lamellae, resulting in the formation of a fibrous pattern. On the other hand, with the same view , the center part was stood as the main ridge consisting of edge-on lamellae and bending to form flat-on lamellae on the valley composed by narrow lamellae in flat-on orientation. From top view, it was shown that the valley (darker region) packed by flat-on lamellae and ridge region packed with small edge-on lamellae resulting the formation of ring-banded pattern.

[1] J. G. Zeikus, M. K. Jain, and P. Elankovan, "Biotechnology of succinic acid production and markets for derived industrial products," Applied Microbiology and Biotechnology, vol. 51, pp. 545-552, 1999.
[2] B. D. Ahn, S. H. Kim, Y. H. Kim, and J. S. Yang, "Synthesis and characterization of the biodegradable copolymers from succinic acid and adipic acid with 1,4-butanediol," Journal of Applied Polymer Science, vol. 82, pp. 2808-2826, 2001.
[3] Z. He, Y. Liang, and C. C. Han, "Confined Nucleation and Growth of Poly(ethylene oxide) on the Different Crystalline Morphology of Poly(butylene succinate) From a Miscible Blend," Macromolecules, vol. 46, pp. 8264-8274, 2013.
[4] Y. Ichikawa, J. Suzuki, J. Washiyama, Y. Moteki, K. Noguchi, and K. Okuyama, "Strain-induced crystal modification in poly(tetramethylene succinate)," Polymer, vol. 35, pp. 3338-3339, 1994.
[5] Z. Qiu, T. Ikehara, and T. Nishi, "Miscibility and crystallization in crystalline/crystalline blends of poly(butylene succinate)/poly(ethylene oxide)," Polymer, vol. 44, pp. 2799-2806, 2003.
[6] M. Hedenqvist and U. W. Gedde, "Diffusion of small-molecule penetrants in semicrystalline polymers," Progress in Polymer Science, vol. 21, pp. 299-333, 1996.
[7] S. Doroudiani, C. B. Park, and M. T. Kortschot, "Effect of the crystallinity and morphology on the microcellular foam structure of semicrystalline polymers," Polymer Engineering & Science, vol. 36, pp. 2645-2662, 1996.
[8] J. Xu and B.-H. Guo, "Microbial Succinic Acid, Its Polymer Poly(butylene succinate), and Applications," in Plastics from Bacteria. vol. 14, G. G.-Q. Chen, Ed., ed: Springer Berlin Heidelberg, 2010, pp. 347-388, 2010.
[9] M. Avella, E. Bonadies, E. Martuscelli, and R. Rimedio, "European current standardization for plastic packaging recoverable through composting and biodegradation," Polymer Testing, vol. 20, pp. 517-521, 2001.
[10] G. Karlstroem, "A new model for upper and lower critical solution temperatures in poly(ethylene oxide) solutions," The Journal of Physical Chemistry, vol. 89, pp. 4962-4964,1985.
[11] Y. He, B. Zhu, and Y. Inoue, "Hydrogen bonds in polymer blends," Progress in Polymer Science, vol. 29, pp. 1021-1051, 2004.
[12] S. Nuño-Donlucas, J. Puig, and I. Katime, "Hydrogen Bonding and Miscibility Behavior in Poly[ethylene-co-(acrylic acid)] and Poly(N-vinylpyrrolidone) Mixtures," Macromolecular Chemistry and Physics, vol. 202, pp. 3106-3111, 2001.
[13] E. Meaurio, L. Cesteros, L. G. Parada, and I. Katime, "Blends of poly (mono n-alkyl itaconates) with tertiary polyamides: Specific interactions and thermal degradation," Polymer journal, vol. 36, pp. 84-90, 2004.
[14] X. Lu and R. A. Weiss, "Relationship between the glass transition temperature and the interaction parameter of miscible binary polymer blends," Macromolecules, vol. 25, pp. 3242-3246, 1992.
[15] T. G. Fox, "Influence of diluent and of copolymer composition on the glass temperature of a polymer system," Bull Am Phys Soc, vol. 1, pp. 22060-6218, 1956.
[16] M. Gordon and J. Taylor, "ournal of Applied," Chemistry, vol. 2, p. 493, 1952.
[17] T. K. Kwei, "The effect of hydrogen bonding on the glass transition temperatures of polymer mixtures," Journal of Polymer Science: Polymer Letters Edition, vol. 22, pp. 307-313, 1984.
[18] Z. He, Y. Liang, P. Wang, and C. C. Han, "Effect of lower critical solution temperature phase separation on crystallization kinetics and morphology of poly(butylenes succinate)/poly(ethylene oxide) blend," Polymer, vol. 54, pp. 2355-2363, 4/19/ 2013.
[19] J. S. Lee, A. A. Prabu, and K. J. Kim, "UCST-Type Phase Separation and Crystallization Behavior in Poly(vinylidene fluoride)/Poly(methyl methacrylate) Blends under an External Electric Field," Macromolecules, vol. 42, pp. 5660-5669, 2009.
[20] L. Robeson, "Historical Perspective of Advances in the Science and Technology of Polymer Blends," Polymers, vol. 6, pp. 1251-1265, 2014.
[21] V. Ratta, "Crystallization, morphology, thermal stability and adhesive properties of novel high performance semicrystalline polyimides," Virginia Polytechnic Institute and State University, 1999.
[22] M. L. Di Lorenzo, "Spherulite growth rates in binary polymer blends," Progress in Polymer Science, vol. 28, pp. 663-689, 2003.
[23] M. H. Abdolrasouli, G. M. M. Sadeghi, H. Nazockdast, and A. Babaei, "Polylactide/Polyethylene/Organoclay Blend Nanocomposites: Structure, Mechanical and Thermal Properties," Polymer-Plastics Technology and Engineering, vol. 53, pp. 1417-1424, 2014.
[24] H. M. Shabana, R. H. Olley, D. C. Bassett, and B. J. Jungnickel, "Phase separation induced by crystallization in blends of polycaprolactone and polystyrene: an investigation by etching and electron microscopy," Polymer, vol. 41, pp. 5513-5523, 2000.
[25] T. Russell et al., "X-RAY and optical studies of the morphology of polymer blends. Polymer Research Institute, Department of Chemistry, and," in Journal of polymer science: Polymer symposia, 1978, p. 313.
[26] H.-L. Chen, L.-J. Li, and T.-L. Lin, "Formation of Segregation Morphology in Crystalline/Amorphous Polymer Blends:  Molecular Weight Effect," Macromolecules, vol. 31, pp. 2255-2264, 1998.
[27] P. Svoboda, J. Kressler, T. Chiba, T. Inoue, and H. W. Kammer, "Light-Scattering and TEM Analyses of Virtual Upper Critical Solution Temperature Behavior in PCL/SAN Blends," Macromolecules, vol. 27, pp. 1154-1159, 1994.
[28] H. D. Keith and F. J. Padden, "Spherulitic Crystallization from the Melt. I. Fractionation and Impurity Segregation and Their Influence on Crystalline Morphology," Journal of Applied Physics, vol. 35, pp. 1270-1285, 1964.
[29] J. D. Hoffman, "Regime III crystallization in melt-crystallized polymers: The variable cluster model of chain folding," Polymer, vol. 24, pp. 3-26, 1983.
[30] B. Kalb and A. J. Pennings, "General crystallization behaviour of poly(l-lactic acid)," Polymer, vol. 21, pp. 607-612, 1980.
[31] W. Hoogsteen, A. R. Postema, A. J. Pennings, G. Ten Brinke, and P. Zugenmaier, "Crystal structure, conformation and morphology of solution-spun poly(L-lactide) fibers," Macromolecules, vol. 23, pp. 634-642, 1990.
[32] R. J. Pazur, P. J. Hocking, S. Raymond, and R. H. Marchessault, "Crystal Structure of Syndiotactic Poly(β-hydroxybutyrate) from X-ray Fiber and Powder Diffraction Analyses and Molecular Modeling," Macromolecules, vol. 31, pp. 6585-6592, 1998.
[33] E. M. Woo and M. C. Wu, "Thermal and X-ray analysis of polymorphic crystals, melting, and crystalline transformation in poly(butylene adipate)," Journal of Polymer Science Part B: Polymer Physics, vol. 43, pp. 1662-1672, 2005.
[34] Z. Gan, K. Kuwabara, H. Abe, T. Iwata, and Y. Doi, "Metastability and Transformation of Polymorphic Crystals in Biodegradable Poly(butylene adipate)," Biomacromolecules, vol. 5, pp. 371-378, 2004.
[35] Y. Ichikawa, H. Kondo, Y. Igarashi, K. Noguchi, K. Okuyama, and J. Washiyama, "Crystal structures of α and β forms of poly(tetramethylene succinate)," Polymer, vol. 41, pp. 4719-4727, 2000.
[36] K. J. Ihn, E. S. Yoo, and S. S. Im, "Structure and Morphology of Poly(tetramethylene succinate) Crystals," Macromolecules, vol. 28, pp. 2460-2464, 1995.
[37] S. Y. Hwang, E. S. Yoo, and S. S. Im, "The synthesis of copolymers, blends and composites based on poly(butylene succinate)," Polym J, vol. 44, pp. 1179-1190, 2012.
[38] H. D. Keith, "On the relation between different morphological forms in high polymers," Journal of Polymer Science Part A: General Papers, vol. 2, pp. 4339-4360, 1964.
[39] F. Khoury, E. Passaglia, and N. Hannay, "Treatise on solid state chemistry," Crystalline and noncrystalline solids, 1976.
[40] Y.-X. Liu and E.-Q. Chen, "Polymer crystallization of ultrathin films on solid substrates," Coordination Chemistry Reviews, vol. 254, pp. 1011-1037, 2010.
[41] Y. Wang, M. Rafailovich, J. Sokolov, D. Gersappe, T. Araki, Y. Zou, et al., "Substrate Effect on the Melting Temperature of Thin Polyethylene Films," Physical Review Letters, vol. 96, p. 028303, 2006.
[42] E. M. Woo and Y.-F. Chen, "Single- and double-ring spherulites in poly(nonamethylene terephthalate)," Polymer, vol. 50, pp. 4706-4717, 2009.
[43] Y.-F. Chen and E. M. Woo, "Annular Multi-Shelled Spherulites in Interiors of Bulk-Form Poly(nonamethylene terephthalate)," Macromolecular Rapid Communications, vol. 30, pp. 1911-1916, 2009.
[44] E. M. Woo, S. Nurkhamidah, and Y.-F. Chen, "Surface and interior views on origins of two types of banded spherulites in poly(nonamethylene terephthalate)," Physical Chemistry Chemical Physics, vol. 13, pp. 17841-17851, 2011.
[45] D. Braun, M. Jacobs, and G. P. Hellmann, "On the morphology of poly(vinylidene fluoride) crystals in blends," Polymer, vol. 35, pp. 706-717, 1994.
[46] K. Cramer, M. F. Lima, S. N. Magonov, E. H. Hellmann, M. Jacobs, and G. P. Hellmann, "Atomic force microscopy on tree-like crystals in polyvinylidene fluoride blends," Journal of Materials Science, vol. 33, pp. 2305-2312, 1998.
[47] Y.-F. Chen, E. M. Woo, and S.-H. Li, "Dual Types of Spherulites in Poly(octamethylene terephthalate) Confined in Thin-Film Growth," Langmuir, vol. 24, pp. 11880-11888, 2008.
[48] H. Ni'mah and E. M. Woo, "Coexisting Straight, Radial, and Banded Lamellae on the Six Corners of Hexagon-Shaped Spherulites in Poly(l-Lactide)," Macromolecular Chemistry and Physics, vol. 215, pp. 1838-1847, 2014.
[49] E. M. Woo, H. Ni’mah, and Y.-H. Wang, "Anisotropic Nucleation and Janus-Faced Crystals of Poly(l-lactic acid) Interacting with an Amorphous Diluent," Industrial & Engineering Chemistry Research, vol. 53, pp. 9772-9780, 2014.
[50] H. Ni’mah, E. Woo, and S. Nurkhamidah, "Diversification of spherulite patterns in poly(ethylene succinate) crystallized with strongly interacting poly(4-vinyl phenol)," Journal of Polymer Research, vol. 21, pp. 1-17, 2013.
[51] H. Ni’mah and E. M. Woo, "Dendritic Morphology Composed of Stacked Single Crystals in Poly(ethylene succinate) Melt-Crystallized with Poly(p-vinyl phenol)," Crystal Growth & Design, vol. 14, pp. 576-584, 2014.
[52] K. C. Yen, E. M. Woo, and K. Tashiro, "Six types of spherulite morphologies with polymorphic crystals in poly(heptamethylene terephthalate)," Polymer, vol. 51, pp. 5592-5603, 2010.
[53] J. M. Marentette and G. R. Brown, "Polymer spherulites: I. Birefringence and morphology," Journal of Chemical Education, vol. 70, p. 435, 1993.
[54] F. J. Bailey, Poly (ethylene oxide): Elsevier, 2012.
[55] H. Wang, J. M. Schultz, and S. Yan, "Study of the morphology of poly(butylene succinate)/poly(ethylene oxide) blends using hot-stage atomic force microscopy," Polymer, vol. 48, pp. 3530-3539, 2007.