- 學位論文
新型天然黏土之結構鑑定及 其在酚醛環氧基板之性能探討
Studies on the Structure identification of a New Nature Clay and Characterization of Novolac Cured Epoxy/Clay Nanocomposites
摘要
天然黏土為地球上重要的礦產，在遠古時代主要用於陶瓷業。由於天 然黏土具有獨特的層狀結構及孔洞，因此現今也逐漸被使用在吸附劑、脫 色劑、離子交換和分子篩催化。而隨著二十一世紀奈米科技時代來臨，天 然黏土逐漸受到重視，廣泛被使用於製備高分子/黏土奈米複材中的無機奈 米填充物。故本研究將新型天然黏土(CL128)進行純化後，再將其製備成酚 醛環氧樹脂/黏土奈米複合材料。CL128 藉由離子交換反應純化，藉由不同 的物理技術檢測，即廣角X 光繞射儀(WAXD)、陽離子交換當量(Cationic Exchange Capacity，CEC) 、固態核磁共振光譜儀(Solid State NMR)、 感應 耦合電漿質譜儀(Inductively Coupled Argon Plasma Atomic Emission Spectrometry， ICP-AES) 、熱重分析儀(TGA)及紅外線光譜儀(FT-IR)等檢 測設備，鑑定出天然黏土(CL128)結構式。CL128 純化後，藉由陽離子交換 法將有機改質劑進行離子置換後，藉由廣角X 光繞射儀(WAXD)、熱重分析 儀(TGA)及紅外線光譜儀(FT-IR)檢測，確認有機改質劑已置換到黏土層間。 接著將有機改質黏土加入酚醛環氧樹脂中，藉由網狀交聯的聚合反應製備 出酚醛環氧樹脂奈米複合材料。以廣角X 光繞射儀(WAXD)觀察有機化黏 土在酚醛環氧樹脂中的層間距，再藉由熱重分析儀(TGA)、動態機械分析儀 (DMA)的檢測來了解複合材料的熱性質，並以穿透式電子顯微鏡(TEM)觀察 實際的分散型態。針對非鹵素型酚醛環氧樹脂進行難燃性測試，利用氧氣 測定儀(Oxygen Index)、圓錐熱量儀(cone calorimeter)、UL94 檢測此類複合 材料的難燃性。提升材料難燃性除了藉由添加少量黏土於高分子中達到良 好分散外，也可藉由C60-O 捕捉氫自由基和氫氧自由基(燃燒時產生)來達難 燃效果。根據上述測量結果，將其應用在印刷電路板，可得較佳之熱性質、 機械性質和銅箔剝離強度。
並列摘要
The natural clays belong to important minerals on earth which had been used mainly in pottery and ceramics since primitive age. Today clays are used as adsorbents, decoloration agents, ion exchangers, and molecular sieve catalysts due to its special layered structure and porosity. In the 21’st century, clay minerals, especially smectite clays, have attracted a great deal of attention in the field of nanotechnology. Smectite clays are used as inorganic nanofiller in the preparation of polymer/clay nanocomposites. In this study, we developed the purification and characterization of natural clay (CL128) and then prepare the novolac cured epoxy/clay nanocomposites. CL128 is purified by ion exchange reactions. The purified clay is characterized by different physical techniques viz. wide angle X-ray diffraction (WAXD), Fourier transform infrared spectroscopy (FT-IR), Cationic exchange capacity (CEC), Solid state nuclear magnetic resonance spectrometer (Solid State NMR) and Inductively Coupled Argon Plasma Atomic Emission Spectrometry (ICP-AES) and then the structure of natural clay (CL128) is identified. After purification of CL128, the clay is modified by organic compounds. The modified clay was characterized by X-ray diffraction (WAXD), Thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR) to confirm the inclusion of modified agent into clay layers. The novolac cured epoxy nanocomposites are prepared with this modified clay by cross-linking polymerization reaction. Wide-angle X-ray diffraction (WAXD) is used to measure the d-spacing of modified CL128 and dispersion morphology of the nanocomposites. Thermo-gravimetric analysis (TGA) and Dynamic mechanical analysis (DMA) were used to characterize the thermal properties of the nanocomposites. The morphology of the nanocomposites is investigated by using transmission electron microscopy (TEM) techniques. The flame retardant property was measured by limiting oxygen index (LOI)、cone calorimeter and UL94. The increasing properties of flame retardant were not only due to the addition of small amount of clay dispersing well into the polymer matrices, but also for the addition of C60-O which acts as hydrogen and hydroxyl free radical (produced during combustion) capture. According to the measurement, these novolac cured epoxy-clay nanocomposites have been shown the significant improvement in the thermal, mechanical and barrier properties that may be applied to the printed circuit board (PCB).