中文摘要
本研究利用微分掃描卡度計(differential scanning calorimetry)、偏光顯微鏡(polarizing-light optical microscopy)、原子力顯微鏡(atomic force microscopy)、廣角X光繞射儀(wide-angle X-ray diffraction)、傅立葉轉換紅外光譜儀(Fourier-transform infrared spectroscopy)以及小角度X光散射儀(small-angle X-ray scattering)探討聚乳酸錯合物(stereocomplexed poly(lactic acid), sc-PLA)及其摻合體之相容性、晶態行為、球晶型貌以及晶板結構。
由微分掃描卡度計的熱分析，可知poly(D-lactic acid)/low-molecular-weight poly(L-lactic acid) (PDLA/LMw-PLLA)之摻合體隨組成變化，存有不同程度的混摻尺度及作用力大小。且由廣角X光繞射儀的晶體分析及傅立葉轉換紅外光譜儀的作用力探討下，可知非當量組成之摻合體存有不同比例的聚乳酸及錯合物，其結果亦顯示在LMw-PLLA組成為30至50 wt%之摻合體，僅存有錯合物晶體。擇以PDLA高含量組成之摻合體(90/10)，觀察PDLA於錯合物模板下之多層次結晶型貌。依據原子力顯微鏡相圖的分析，可知PDLA於錯合物模板下的晶板排列，是由纖維狀晶板(fibril-like)轉變成串珠狀晶板(bead-on-string)，進而增厚成非規則態麻花狀晶板(dough-like)；而後麻花狀晶板如同一基體，供纖維狀至串珠狀的晶板反覆排列，直至接觸另一球晶。在冷結晶過程中，PLLA於當量組成下之摻合體(50/50)，存有非PLLA及錯合物之特殊晶體(meta-crystal)。由廣角X光繞射儀的分析下，可知PLLA於冷結晶溫度為85oC至95oC，同時存有meta-form及alpha'-form晶體，以及溫度為100oC至120oC，則存有alpha-form晶體。並由變溫之小角度X光散射儀分析下，可知meta-form PLLA可能存在於錯合物晶板間，且於升溫過程中，meta-form PLLA部份熔融且以熔融再結晶之機制，直接排列成alpha-form晶體，而非透過形成規則性差的alpha'-form晶體之途徑形成alpha-form晶體。Meta-form晶體之熔融及再結晶的擇優性，則依冷結晶溫度而定。冷結晶溫度為85oC至95oC時，meta-form晶體之再結晶行為較熔融行為，更為顯著。
本研究中首度探討生物可分解性高分子poly(3-hydroxybutyrate)(PHB)與聚乳酸錯合物摻合體之相容性、結晶型態及晶板結構。由微分掃描卡度計的熱分析，可知PHB/sc-PLA摻合體屬一相容系統，且PHB的加入，其錯合物之結晶行為及型貌受到抑制及改變。當熔融結晶溫度為130oC以上，PHB可視為不定形高分子，且隨PHB含量的增加，錯合物的球晶型貌由典型的馬爾他十字轉變為樹枝狀之球晶型貌。依據偏光及原子力顯微鏡的分析，可知在結晶溫度為170oC時，錯合物的球晶型貌不再維持馬爾他十字的型貌，取而代之的是edge-on羽毛狀(feather-like)及flat-on菱形狀(wedge-like)的球晶型貌。並根據動態偏光顯微鏡的結果，可知受PHB導入的影響，錯合物先以羽毛狀(feather-like)的型貌呈現，隨之發展菱形狀(wedge-like)的型貌，且隨結晶時間的增加，羽毛狀(feather-like)與菱形狀(wedge-like)之球晶型貌將一同成長。導致錯合物呈現不同的球晶型貌及晶板排列，可歸因於PHB於錯合物晶體前緣的濃度及分布上的差異。由廣角X光繞射儀的分析，可知此球晶型貌的錯合物，其晶格結構未受改變。
此外，本研究亦針對PHB高分子在機械性質上的缺點，提供一具生物可分解之成核劑，以改善其強度。利用非恆溫結晶曲線，可初步了解添加少量之錯合物晶體有助於提高PHB高分子的結晶能力。並進而利用Avrami學者提出的恆溫結晶動力學理論，針對PHB高分子的結晶動力學進行探討。由Avrami參數n及k值的結果，可知導入少量的錯合物晶體，對於PHB高分子之結晶機制未受改變，並且提升PHB高分子整體的結晶速率。並由偏光顯微鏡的結果，可知添加少量之錯合物晶體有助於提高PHB高分子的成核密度。

The thermal behavior, lamellar assembly and crystallization in fully biodegradable polymer blends of poly(D-lactic acid) with low-molecular-weight poly(L-lactic acid) (PDLA/LMw-PLLA) and poly(3-hydroxybutyrate) with stereocomplexed PLA (PHB/sc-PLA) were probed using differential scanning calorimetry (DSC), polarizing-light optical microscopy (POM), atomic force microscopy (AFM), wide-angle X-ray diffraction (WAXD), Fourier-transform infrared spectroscopy (FTIR), and small-angle X-ray scattering (SAXS).
Sigmoidal Tg-composition relationship in blend of PDLA/LMw-PLLA indicates that interactions and scales of mixing vary with the blend composition. Blending LMw-PLLA with PDLA at 1:1 weight ratio led to formation of sc-PLA crystal. Crystallization of nonequimolar compositions of the blends leads to formation of various fractions of sc-PLA crystallites and homocrystallites (PDLA or PLLA). For the PDLA/LMw-PLLA blends within the composition window of LMw-PLLA content between 30 and 50 wt%, only sc-PLA crystal exists and no homocrystal is present. On the other hand, for PDLA/LMw-PLLA blends with excess PDLA, e.g. PDLA/LMw-PLLA=90/10, AFM characterization on various stages of crystallization of sc-PLA crystal with PDLA homocrystal shows a repetitive stacking of excess PDLA on pre-formed sc-PLA crystal serving as crystallizing templates. The crystallization initially begins with string-like (fibril-like) PDLA lamellae, followed with PDLA aggregating on sc-PLA crystal into a bead-on-string crystal, then growing to thicker irregularly-shaped dough-like lamellae. Repetitive growth cycle from strings to bead-on-string lamellae continues on top of the dough-like lamellae as new substrates, until ending impingement of the PDLA spherulites. A unique crystalline structure of homopolymeric PLLA, appearing as a meta-crystal, was discovered in PDLA/LMw-PLLA blend. In PDLA/LMw-PLLA blend, both meta-crystal and alpha'-crystal form in PLLA were found to form when crystallized at cold-crystallization temperature (Tcc) of 85-95oC and the alpha-crystal PLLA formed at 100 ≤ Tcc < 120oC, respectively. The SAXS result indicates that the meta-crystal PLLA may be incorporated in the sc-PLA lamellar region. During a heating process, the meta-crystal PLLA first partially melts and subsequently it repacks directly into the alpha-crystal PLLA without going through the less stable alpha'-form, by melt-recrystallization mechanism. For the PDLA/LMw-PLLA mixtures crystallized at Tcc from 85oC to 95oC, the re-crystallization of the meta-crystal becomes more predominant than the melting of the meta-form PLLA crystal.
The PHB/sc-PLA blend system shows a single composition-dependent Tg in all composition, indicating miscibility and interactions between PHB and sc-PLA, which leads to that crystallization growth of sc-PLA in blends is hindered by presence of PHB and final morphology of the sc-PLA complexes is altered. When crystallized at high Tc (130oC or above), morphology transition of sc-PLA occurs from original well-rounded Maltese-cross spherulites to dendritic form in blends of high PHB contents (50 wt% or higher), where PHB acts as an amorphous species. Microscopy characterizations show that morphology sc-PLA in PHB/sc-PLA blends crystallized at Tc=170oC no longer retain original complexed Maltese-cross well-rounded spherulites; instead, the spherulites are disintegrated and restructured into two types of dendrites: (1) edge-on feather-like dendrites (early growth) and (2) flat-on wedge-like crystal plates (later growth) by growing along different directions and exhibiting different optical brightness. The concentration and/or distribution of amorphous PHB at the crystal growth front, corresponding to variation of the slopes of spherulitic growth rates, is a factor resulting in alteration and restructuring of the sc-PLA spherulites in the blends. Despite of spherulite disintegration, WAXD result shows that these two PHB-induced dendrites still retain the original unit cells of complexes, and thus these two new dendrites are sc-PLA.
Small amount crystalline nuclei of sc-PLA (2-10 wt%) were incorporated into PHB for investigating melt-crystallization kinetics. The Avrami equation was employed to analyze the isothermal crystallization of PHB. The sc-PLA crystallites acted as nucleation sites in blends, and accelerated the crystallization rates of PHB by increasing the crystallization rate constant k and decreasing the half-time (t1/2). The PHB crystallization was nucleated most effectively with 10 wt% stereocomplexed crystallites, as evidenced by POM results. The sc-PLA complex nucleated PHB crystals exhibit much small spherulite sizes but possess the same crystal cell morphology as that of neat PHB based on the WAXD result.

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