本研究利用偏光顯微鏡(POM)、電子顯微鏡(SEM)、原子力顯微鏡(AFM)、及小角度X光散射儀(SAXS)探討生物可分解高分子聚羥基丁酸酯(PHB)摻合了聚丙二醇己二酸酯(PTA)及聚乙二醇(PEO)後的結晶行為，且特別控制結晶溫度使PTA與PEO在系統中扮演不定型稀釋劑的角色。第一部分是PHB/PTA摻合系統，首先改變組成比例、結晶溫度(Tc)以POM進行球晶形貌的初步觀察，選擇75/25的組成比例做進一步的分析，發現隨著結晶溫度(Tc)的上升，環帶寬度(band spacing)會有先增加後減小的趨勢，接著利用AFM以及SEM對於高結晶溫度以及低結晶溫度進一步分析及比較，並探討環帶狀球晶的上表面與內部晶板排列對應關係，建立三維生長機制。第二部分為，PHB/PEO (75/25)摻合系統，同樣以POM初步觀察球晶形貌，可觀察到與第一部分有非常相似的環帶寬度變化，但較特別的是會在部分結晶溫度出現相分離現象(phase separation)，因此以SEM分別針對相分離的結晶溫度以及均勻相的結晶溫度進一步觀察內部與上表面結構，最後透過SAXS輔助證明生長機制的正確性。透過本研究的結果，可了解PHB球晶是由兩種不同排列方向、不連續的晶板週期性重複而形成，而非傳統觀念的連續性晶板扭轉所組成，並且在稀釋劑的作用下能夠更清楚的觀察到晶板的分枝與排列。

A semi-crystalline polymer, poly(3-hydroxybutyrate) (PHB), was crystallized in the presence of poly(1,3-trimethylene adipate) (PTA) and poly(ethylene oxide) (PEO), respectively. PTA and PEO played the role of amorphous diluent in the blend system and manipulate the crystallization kinetics and loose the structure of PHB spherulites. In PHB/PTA (75/25) and PHB/PEO (75/25) systems, ring-banded spherulites could be observed, and the band spacing of the ring-band present a similar trend, both increased first and then decreased. PHB/PTA (75/25) showed the clockwise spiral and counterclockwise spiral at different crystallization temperatures (Tcs). At higher and lower Tcs, the lamellae grew in a clockwise and counterclockwise direction, respectively. In order to construct a spherulite model, we also use scanning electron microscopy (SEM) to observe the fractured surface in order to explore the inner lamellar arrangement. PHB/PEO (75/25) exhibited phase separation at a specific Tc. SEM was used to further observe the interior structure and top surface structures for the phase separation Tc and the homogeneous phase Tc. Finally, through SAXS to prove the growth mechanism.

[1] Y.-L. Tseng, K.-N. Chuan, and E. M. Woo, "Unusual Ringed/Dendritic Sector Faces in Poly(butylene succinate) Crystallized with Isomeric Polymer," Industrial & Engineering Chemistry Research, vol. 59, no. 16, pp. 7485-7494, 2020.
[2] Y.-T. Yeh and E. M. Woo, "Anatomy into Interior Lamellar Assembly in Nuclei-Dependent Diversified Morphologies of Poly(l-lactic acid)," Macromolecules, vol. 51, no. 19, pp. 7722-7733, 2018.
[3] E. M. Woo, Y.-H. Chou, W.-J. Chiang, I.-T. Chen, I.-H. Huang, and N.-T. Kuo, "Amorphous phase behavior and crystalline morphology in blends of poly (vinyl methyl ether) with isomeric polyesters: poly (hexamethylene adipate) and poly (ɛ-caprolactone)," Polymer journal, vol. 42, no. 5, pp. 391-400, 2010.
[4] J. Schultz and D. Kinloch, "Transverse screw dislocations: A source of twist in crystalline polymer ribbons," Polymer, vol. 10, pp. 271-278, 1969.
[5] A. Toda, M. Okamura, M. Hikosaka, and Y. Nakagawa, "Three-dimensional shape of polyethylene single crystals grown from dilute solutions and from the melt," Polymer, vol. 46, no. 20, pp. 8708-8716, 2005.
[6] J. Eshelby, "Screw dislocations in thin rods," Journal of Applied Physics, vol. 24, no. 2, pp. 176-179, 1953.
[7] A. Toda, M. Okamura, K. Taguchi, M. Hikosaka, and H. Kajioka, "Branching and higher order structure in banded polyethylene spherulites," Macromolecules, vol. 41, no. 7, pp. 2484-2493, 2008.
[8] A. Toda, I. Kojima, and M. Hikosaka, "Melting kinetics of polymer crystals with an entropic barrier," Macromolecules, vol. 41, no. 1, pp. 120-127, 2008.
[9] B. Lotz and S. Z. Cheng, "A critical assessment of unbalanced surface stresses as the mechanical origin of twisting and scrolling of polymer crystals," Polymer, vol. 46, no. 3, pp. 577-610, 2005.
[10] E. M. Woo, G. Lugito, and C.-E. Yang, "Analysis of crystal assembly in banded spherulites of phthalic acid upon solvent evaporation," CrystEngComm, vol. 18, no. 6, pp. 977-985, 2016.
[11] X. Cui, A. G. Shtukenberg, J. Freudenthal, S. Nichols, and B. Kahr, "Circular birefringence of banded spherulites," Journal of the American Chemical Society, vol. 136, no. 14, pp. 5481-5490, 2014.
[12] M. Kunz, M. Drechsler, and M. Möller, "On the structure of ultra-high molecular weight polyethylene gels," Polymer, vol. 36, no. 7, pp. 1331-1339, 1995.
[13] T. Ikehara and T. Kataoka, "Relation between the helical twist and S-shaped cross section of the lamellar crystals of polyethylene," Scientific reports, vol. 3, p. 1444, 2013.
[14] E. M. Woo, L.-Y. Wang, and S. Nurkhamidah, "Crystal lamellae of mutually perpendicular orientations by dissecting onto interiors of poly(ethylene adipate) spherulites crystallized in bulk form," Macromolecules, vol. 45, no. 3, pp. 1375-1383, 2012.
[15] G. Lugito and E. M. Woo, "Interior lamellar assembly in correlation to top-surface banding in crystallized poly(ethylene adipate)," Crystal growth & design, vol. 14, no. 10, pp. 4929-4936, 2014.
[16] C.-H. Tu, E. M. Woo, and G. Lugito, "Structured growth from sheaf-like nuclei to highly asymmetric morphology in poly(nonamethylene terephthalate)," RSC advances, vol. 7, no. 75, pp. 47614-47618, 2017.
[17] T.-Y. Chen, E. M. Woo, and S. Nagarajan, "Periodic fractal-Growth Branching to Nano-Structured Grating Aggregation in Phthalic Acid," Scientific reports, vol. 10, no. 1, pp. 1-14, 2020.
[18] G. Lugito, S. Nagarajan, and E. M. Woo, "Explosive Fibonacci-Sequence Growth into Unusual Sector-Face Morphology in Poly(L-lactic acid) Crystallized with Polymeric Diluents," 2020.
[19] S. Nurkhamidah and E. M. Woo, "Effects of crystallinity and molecular weight on crack behavior in crystalline poly(L‐lactic acid)," Journal of Applied Polymer Science, vol. 122, no. 3, pp. 1976-1985, 2011.
[20] S. Nurkhamidah and E. M. Woo, "Unconventional Non‐birefringent or Birefringent Concentric Ring‐Banded Spherulites in Poly(L‐lactic acid) Thin Films," Macromolecular Chemistry and Physics, vol. 214, no. 6, pp. 673-680, 2013.
[21] C.-C. Su, E. M. Woo, and Y.-T. Hsieh, "Perpendicularly oriented lamellae in poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) blended with an amorphous polymer: ultra-thin to thick films," Physical Chemistry Chemical Physics, vol. 15, no. 7, pp. 2495-2506, 2013.
[22] L. Chang, Y.-H. Chou, and E. M. Woo, "Effects of amorphous poly(vinyl acetate) on crystalline morphology of poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid)," Colloid and Polymer Science, vol. 289, no. 2, pp. 199-211, 2011.
[23] P. Atkins, J. De Paula, and R. Friedman, Physical Chemistry: Quanta, Matter, and Change. Oxford University Press, USA, 2013.
[24] K. Tashiro et al., "Relationship between twisting phenomenon and structural discontinuity of stacked lamellae in the spherulite of poly(ethylene adipate) as studied by the synchrotron X-ray microbeam technique," Polymer Journal, vol. 51, no. 2, p. 131, 2019.
[25] S. Nagarajan and E. M. Woo, "Morphological analyses evidencing corrugate-grating lamellae assembly in banded spherulites of Poly(ethylene adipate)," Polymer, vol. 188, p. 122141, 2020.
[26] P. Barham and A. Keller, "The relationship between microstructure and mode of fracture in polyhydroxybutyrate," Journal of Polymer Science Part B: Polymer Physics, vol. 24, no. 1, pp. 69-77, 1986.
[27] N. Grassie, E. Murray, and P. Holmes, "The thermal degradation of poly(-(D)-β-hydroxybutyric acid): part 2—changes in molecular weight," Polymer degradation and stability, vol. 6, no. 2, pp. 95-103, 1984.
[28] P. Barham, A. Keller, E. Otun, and P. Holmes, "Crystallization and morphology of a bacterial thermoplastic: poly-3-hydroxybutyrate," Journal of Materials Science, vol. 19, no. 9, pp. 2781-2794, 1984.
[29] G. De Koning and P. Lemstra, "Crystallization phenomena in bacterial poly[(R)-3-hydroxybutyrate]: 2. Embrittlement and rejuvenation," POLYMER-LONDON-, vol. 34, pp. 4089-4089, 1993.
[30] H. Mitomo, P. J. Barham, and A. Keller, "Crystallization and morphology of poly(β-hydroxybutyrate) and its copolymer," Polymer journal, vol. 19, no. 11, pp. 1241-1253, 1987.
[31] P. Holmes, "Biologically produced (R)-3-hydroxy-alkanoate polymers and copolymers," in Developments in crystalline polymers: Springer, 1988, pp. 1-65.
[32] Y. Doi, Microbial polyesters. Vch, 1990.
[33] Y. Doi, S. Kitamura, and H. Abe, "Microbial synthesis and characterization of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)," Macromolecules, vol. 28, no. 14, pp. 4822-4828, 1995.
[34] T. Watanabe, Y. He, T. Fukuchi, and Y. Inoue, "Comonomer compositional distribution and thermal characteristics of bacterially synthesized poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)s," Macromolecular Bioscience, vol. 1, no. 2, pp. 75-83, 2001.
[35] J. Asrar, H. E. Valentin, P. A. Berger, M. Tran, S. R. Padgette, and J. R. Garbow, "Biosynthesis and properties of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) polymers," Biomacromolecules, vol. 3, no. 5, pp. 1006-1012, 2002.
[36] F. Shi, R. D. Ashby, and R. A. Gross, "Fractionation and characterization of microbial polyesters containing 3-hydroxybutyrate and 4-hydroxybutyrate repeat units," Macromolecules, vol. 30, no. 8, pp. 2521-2523, 1997.
[37] H. Yang, Z.-S. Li, H.-J. Qian, Y.-B. Yang, X.-B. Zhang, and C.-C. Sun, "Molecular dynamics simulation studies of binary blend miscibility of poly(3-hydroxybutyrate) and poly(ethylene oxide)," Polymer, vol. 45, no. 2, pp. 453-457, 2004.
[38] Y.-H. Na, Y. He, N. Asakawa, N. Yoshie, and Y. Inoue, "Miscibility and phase structure of blends of poly(ethylene oxide) with poly(3-hydroxybutyrate), poly(3-hydroxypropionate), and their copolymers," Macromolecules, vol. 35, no. 3, pp. 727-735, 2002.
[39] Y. An, L. Dong, G. Li, Z. Mo, and Z. Feng, "Miscibility, crystallization kinetics, and morphology of poly(β‐hydroxybutyrate) and poly(methyl acrylate) blends," Journal of Polymer Science Part B: Polymer Physics, vol. 38, no. 14, pp. 1860-1867, 2000.
[40] P. Greco and E. Martuscelli, "Crystallization and thermal behaviour of poly(d (—)-3-hydroxybutyrate)-based blends," Polymer, vol. 30, no. 8, pp. 1475-1483, 1989.
[41] Y. An, L. Li, L. Dong, Z. Mo, and Z. Feng, "Nonisothermal crystallization and melting behavior of poly(β‐hydroxybutyrate)–Poly(vinyl‐acetate) blends," Journal of Polymer Science Part B: Polymer Physics, vol. 37, no. 5, pp. 443-450, 1999.
[42] P. Iriondo, J. Iruin, and M. Fernandez-Berridi, "Association equilibria and miscibility prediction in blends of poly(vinylphenol) with poly(hydroxybutyrate) and related homo-and copolymers: an FTIR study," Macromolecules, vol. 29, no. 17, pp. 5605-5610, 1996.
[43] P. Xing, L. Dong, Y. An, Z. Feng, M. Avella, and E. Martuscelli, "Miscibility and crystallization ofpoly (β-hydroxybutyrate) and poly(p-vinylphenol) blends," Macromolecules, vol. 30, no. 9, pp. 2726-2733, 1997.
[44] A. El-Hadi, R. Schnabel, E. Straube, G. Müller, and S. Henning, "Correlation between degree of crystallinity, morphology, glass temperature, mechanical properties and biodegradation of poly(3-hydroxyalkanoate) PHAs and their blends," Polymer testing, vol. 21, no. 6, pp. 665-674, 2002.
[45] L. Chang and E. M. Woo, "Effects of molten poly (3-hydroxybutyrate) on crystalline morphology in stereocomplex of poly (L-lactic acid) with poly (D-lactic acid)," Polymer, vol. 52, no. 1, pp. 68-76, 2011.
[46] L. Chang and E. M. Woo, "Crystallization of poly(3‐hydroxybutyrate) with stereocomplexed polylactide as biodegradable nucleation agent," Polymer Engineering & Science, vol. 52, no. 7, pp. 1413-1419, 2012.
[47] M. L. Focarete, G. Ceccorulli, M. Scandola, and M. Kowalczuk, "Further Evidence of Crystallinity-Induced Biodegradation of Synthetic Atactic Poly(3-hydroxybutyrate) by PHB-Depolymerase A from Pseudomonas l emoignei. Blends of Atactic Poly(3-hydroxybutyrate) with Crystalline Polyesters," Macromolecules, vol. 31, no. 24, pp. 8485-8492, 1998.
[48] Y.-T. Hsieh and E. M. Woo, "Phase diagrams in blends of poly(3-hydroxybutyric acid) with various aliphatic polyesters," Express Polymer Letters, vol. 5, no. 7, 2011.
[49] N. Lotti, M. Pizzoli, G. Ceccorulli, and M. Scandola, "Binary blends of microbial poly(3-hydroxybutyrate) with polymethacrylates," Polymer, vol. 34, no. 23, pp. 4935-4940, 1993.
[50] M.-S. Lee and E. M. Woo, "Systematic probing into periodic lamellar assembly via induced cracks in crystallized polyesters," Polymer, vol. 166, pp. 88-97, 2019.
[51] G. Lugito, C.-Y. Yang, and E. M. Woo, "Phase-separation induced lamellar re-assembly and spherulite optical birefringence reversion," Macromolecules, vol. 47, no. 16, pp. 5624-5632, 2014.
[52] E. M. Woo, W.-T. Tsai, and G. Lugito, "Interior dissection on domain-dependent birefringence types of poly(3-hydroxybutyrate) spherulites in blends," Macromolecules, vol. 50, no. 1, pp. 283-295, 2017.
[53] 吳純寧, "聚羥基丁酸酯共聚羥基戊酸酯與不定型態聚己二酸二丙酯混摻系統球晶形貌之晶板與組裝," 碩士, 化學工程學系, 國立成功大學, 台南市, 2016.
[54] J. M. Schultz, "Unusual “twisting” morphology in poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) spherulites," Macromolecules, vol. 46, no. 10, pp. 4227-4229, 2013.