本研究探討poly(styrene-block-ethylene oxide (PS-b-PEO)和poly(styrene-block-acrylic acid) (PS-b-PAA)之雙成份混摻物的相行為與結晶行為。利用random phase approximation理論計算出團聯共聚物不同鏈段間的χ值。我們將PS-b-PEO與PS-b-PAA混摻系統視為PS-b-PEO、PS-b-PAA和PEO/PAA三個部分之間作用力的整合，並分析其相行為。在低溫環境時，PS-b-PEO/PS-b-PAA混摻物中之PS相容，而PEO和PAA相容，因此可形成微相分離結構；而在升溫過程中，由於氫鍵消失，系統趨於不相容，當溫度超過135 oC後，系統巨觀相分離，形成PS-b-PEO rich phase和PS-b-PAA rich phase 兩相，其中分離強度不足的PS-b-PEO rich phase，在升溫過程處於disorder狀態；相反的，有較大分離強度的PS-b-PAA rich phase，在升溫過程中則出現有序無序相轉換現象。另一方面，我們將對稱型PS-b-PEO與對稱型PS-b-PAA以不同比例混摻，在PS相的hard confinement下，PEO結晶之方向性會受到PEO鏈段之結晶摺疊長度與PEO微域尺寸影響，若PEO結晶摺疊長度大於PEO微域的尺寸，結晶c ̂軸之方向垂直於PS/PEO的界面之法向量，以符合PS相的空間限制；相反的，若PEO結晶摺疊長度小於PEO微域的尺寸，結晶c ̂軸之方向可平行於PS/PEO的界面之法向量。此外，PEO結晶受到 PAA鏈段氫鍵作用力影響，使得混摻系統之結晶度降低，方向性變差。

This study aims at understanding the phase and crystallization behaviors of binary block copolymer blends composed of poly(styrene-block-ethylene oxide) (PS-b-PEO) and poly(styrene-block-acrylic acid) (PS-b-PAA). The random phase approximation theory was used to calculate the χ values between the different segments of the block copolymers. The phase behavior of the PS-b-PEO/PS-b-PAA blends was considered to be affected by various contributions, including the interaction between PS and PEO in PS-b-PEO, the interaction between PS and PAA in PS-b-PAA, and the interaction between PEO and PAA. At low temperatures, the PS-b-PEO/PS-b-PAA blend underwent microphase separation because of the two identical PS blocks and the favorable compatibility between PEO and PAA blocks. At elevated temperatures, the system tended to be more incompatible because of the disappearance of hydrogen bonds between PEO and PAA. When the temperature exceeded 135 °C, the system macrophase separated into two phases: PS-b-PEO rich phase and PS-b-PAA rich phase. During the heating process, the PS-b-PEO rich phase with weak segregation strength was at a disorder state. By contrast, the PS-b-PAA rich phase with strong segregation strength underwent an order-to-disorder phase transition. Furthermore, we prepared symmetric PS-b-PEO/symmetric PS-b-PAA blends with different compositions, and investigated the orientation of PEO crystals within the hard confinement between the PS microdomains. The crystal orientation was strongly depended on the lamellar thickness of PEO crystals and the PEO microdomain size. When the lamellar thickness of PEO was larger than the PEO microdomain size, the direction of the c ̂ axis of crystals was perpendicular to the PS/PEO interface normal to satisfy the spatial restriction of the PS phase. By contrast, when the lamellar thickness of PEO was smaller than the PEO microdomain size, the direction of the crystal c ̂ axis was parallel to the PS/PEO interface normal. In addition, the crystallization behavior of PEO was affected by the hydrogen bonding between PAA and PEO. The hydrogen bonds reduced the crystallinity and disturbed the crystal orientation of the blends.

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