將對位聚苯乙烯(sPS)摻入同排聚苯乙烯(iPS)可形成雙結晶性之摻合體，利用enthalpy relaxation、OM與SEM來探討相溶性。sPS/iPS=50/50的系統於熔融態(300oC)淬冷，在sub-Tg下長時間回火後，由DSC升溫曲線可得兩個recovery peak，且在150oC附近有一個冷結晶峰以及一個shoulder，利用FTIR判斷皆為sPS結晶所造成，判斷此系統為相分離。sPS/iPS=30/70的系統雖然只有一個recovery peak，但在DSC升溫曲線可發現有三個冷結晶峰，同樣由FTIR判斷為sPS結晶造成。由OM的影像顯示，sPS/iPS=30/70、50/50、70/30三個系統，於280～300oC等溫時為spinodal decomposition的相分離。而由SEM的結果，sPS/iPS=30/70、50/50、70/30、85/15於280～300oC皆為相分離。

　　利用WAXD判斷sPS/iPS以及sPS/iPS/aPS=50/25/25系統在250oC一階段以及250/175oC兩階段熔融結晶之晶型，結果顯示sPS晶型皆為b型；兩階段熔融結晶只有sPS/iPS=30/70以及sPS/iPS=50/50中的iPS會於175oC結晶，利用TEM觀察其微結構，發現iPS的結晶存在於sPS lamellar stack之間的domain，為interfibrillar結構。

　　Syndiotactic polystyrene/isotactic polystyrene blends were prepared in this study. It is to investigate the miscibility behavior by using enthalpy relaxation, OM and SEM. Based on enthalpy relaxation results, phase separation takes place in the sPS/iPS=30/70 and sPS/iPS=50/50 at 300oC. According to the FTIR results, the cold crystallization peaks are related to sPS crystallization. OM and SEM images show that phase separation occurs at 280~320oC in sPS/iPS=30/70、50/50、70/30、85/15 systems.

　　Based on WAXD diffraction patterns, b-form sPS crystals were always obtained from one and two-step melt-crystallization. In two-step crystallization, iPS crystals can only be found in sPS/iPS=30/70 and sPS/iPS=50/50 systems. From TEM images the iPS crystals exist between sPS lamellar stacks.

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