為了解基材tacticity效應對流變性質的影響，本研究首先量測不同分子量對位聚苯乙烯(sPS, Mw=134-1160 kg/mol)在不同溫度下(270-310 oC)之動態流變性質，藉此可得糾結分子量(Me)與流動活化能(Ea)，另研究四個不同分子量的亂排聚苯乙烯(aPS, Mw=215-862 kg/mol)與一個同位聚苯乙烯(iPS, Mw=247 kg/mol)來評估tacticity效應及其相關性質。以280 oC為參考溫度且依據時間-溫度重疊原理建立動態儲存模數與消散模數的精通曲線。藉由積分法，可得sPS與aPS的Me分別為14500與17900 g/mol，其值低於iPS藉由經驗方程式所得之Me (約為27200 g/mol)。按照Arrhenious曲線圖，可得sPS之Ea為53±5 kJ/mol，此值低於iPS與aPS之Ea(90-107 kJ/mol)。
添加相同結構但不同長徑比的奈米碳管(CNT)與奈米碳球(CNC)進入半結晶性sPS基材中可形成均勻的奈米複材，以電子顯微鏡確認CNT與CNC在複材中的分散狀態。經由複材的流變與導電特性研究，了解添加物長徑比對於複材性質的影響。非晶相aPS亦添加入CNT，藉此研究基材tacticity效應。將percolation指數次方理論應用於此一研究中，並決定出複材不同特性之threshold濃度與percolation指數次方，研究發現複材流變與導電度分別遵循不同的精通曲線。藉由廣角X光繞射、傅立葉轉換紅外線光譜儀、微差熱掃描卡計和穿透式電子顯微鏡探討添加物對sPS結晶行為的影響。
實驗發現長徑比較大的奈米碳材對於sPS複材不論是在流變或導電上，皆可以在較低濃度形成網狀結構；且複材的流變threshold遠小於導電threshold。由於sPS/CNT複材具有穿晶效應，使得sPS/CNT複材之導電threshold比aPS/CNT複材高出四倍之多。因CNT對於半結晶高分子基材有高成核能力，使sPS複材熔體經由液態氮淬冷後仍有晶體存在；然而進一步在升溫冷結晶過程中，sPS晶體成長卻以晶型為主，不受晶體存在影響。在熔融結晶條件下，複材內添加入CNT(或者CNC)，容易形成sPS之晶型；且不論是動態結晶或等溫結晶，添加CNT與CNC會使得sPS整體結晶速率變快。逐步增加CNT含量，sPS的結晶速率先上升後達到一穩定值，這是由於高濃度CNT的添加使得高分子鏈運動度降低。Avrami指數在低CNT含量時為2.8，當CNT濃度達到流變threshold形成高分子-CNT混成網路結構時，Avrami指數轉變成2.0。藉由TEM的觀察，複材結晶變快機制是由於CNT的高成核性，使得sPS在CNT表面結晶，進而形成穿晶層。

To reveal the tacticity effect of matrix on viscoelastic properties, attention is focused on the viscoelastic properties of syndiotactic polystyrene (sPS) with different molecular weights (Mw=134-1160 kg/mol) measured in a wide achievable temperature range (270-310 oC) to determine the entanglement molecular weight (Me), and flow activation energy (Ea). In addition, four atactic polystyrene (aPS, Mw=215-862 kg/mol) and one isotactic polystyrene (iPS, Mw=247 kg/mol) are also studied. Using a reference temperature of 280 oC, the master curves of dynamic storage and loss modulus are constructed according to the time-temperature superposition principle. Based on the classical integration method, the Me values are detemined to be 14500 and 17900 g/mol for the sPS and aPS, respectively, which are significantly lower than that for the iPS, ~27200 g/mol, derived form the Wu’s empirical equation. According to the Arrhenius plots, the determined Ea for the sPS is 53±5 kJ/mol, which is apparently lower than that for the other two isomers possessing a similar value of 90-107 kJ/mol.
Semicrystalline sPS composites with carbon nanotubes (CNTs) and carbon nanocapsules (CNCs) are prepared and good filler dispersion is confirmed by electron microscopy. Their rheological and electrical properties are investigated to reveal the effect of filler aspect ratio. Amorphous aPS is also used to prepare composites filled with CNTs to elucidate the effect of matrix tacticity. Percolation scaling laws are applied and the threshold concentration and exponent are determined. Master curves are obtained provided that an appropriate percolation function is selected. In addition, the filler effect on the crystallization of sPS is studied as well using Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, differential scanning calorimetry, and transmission electron microscopy (TEM).
Results show that a lower CNT content is found than the CNC filler to reach the percolation, either in the rheology or in the conductivity, due to the possession of a higher aspect ratio. Due to the transcrystallization effect in the sPS composites, its conductivity threshold is four time larger than that of CNT-filled aPS composites. Composites melt-quenched by liquid nitrogen contain the -form crystals because of the high nucleating ability of CNTs; however, subsequent cold crystallization produces the -form crystal despite the presence of the -form. When crystallized from the melted state, however, the formation of the -form is always favored after CNT (or CNC) addition regardless of crystallization conditions (isothermal or non-isothermal). With a gradual increase in CNT loading, the sPS crystallization initially increases but then reaches a plateau value at high CNT concentrations because of the reduction in chain mobility. Moreover, the Avrami exponent is changed from 2.8 for samples at low filler contents to 2.0 for samples, in which the rheological threshold is approached and polymer-CNT hybrid network is formed. The enhanced crystallization kinetics is attributed to the high nucleating ability of CNTs to induce a transcrystalline layer at its surface, as revealed by TEM.

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