以官能化奈米碳球插層於層狀雙氫氧化合物中應用於難燃機能之酚醛環氧樹脂之複合材料的製備與性質探討

Study on the Fire Resistant and Characterization of Novolac Cured Epoxy Nanocomposites with Different Types of LDH Modified by Organo-Carbon Nanocapsules (O-CNCs)

王惠君(Hui-chun Wang)

指導教授 ： 蔡宗燕

中原大學/理學院/奈米科技碩士學位學程/碩士(2011年)

https://doi.org/10.6840/cycu201100846

摘要

本研究主要是利用不同種類的人工層狀雙氫氧化合物(LDH)層板來分散具難燃性的官能化奈米碳球(OCNCs)添加於酚醛環氧樹脂中。研究中所使用的人工層狀雙氫氧化合物分為三種，包括兩種小粒徑的LiAl-LDHs、MgAl-LDHs及大粒徑的的LiAl-LDHs。其中，大小粒徑的LiAl-LDHs是以一次合成的方式使OCNCs插層於LDHs層間；另外，外加碳球於MgAl-LDHs中，並且調配LDHs及OCNCs的比例，探討此三種層狀材料的結搆、粒徑大小及OCNCs添加量對難燃性的影響。本研究利用LDHs的層板結構來阻隔熱的傳導並阻隔可燃氣體的進出；利用LDHs結構所含的結晶水及-OH基受熱過後產生的水氣來吸收燃燒時所產生的熱；同時OCNCs受熱時，豐富的雙鍵會產生許多自由基，可以即時捕捉高分子燃燒時所產生的自由基，以達到三重阻燃的效果。
研究中利用廣角X光繞射儀(WXRD) 得知OCNCs和對氨基苯磺酸(SAS)已插層於LDHs層間，層間距增加8.67Å，以熱重分析儀(TGA)計算OCNCs和有機改質劑之插層量，符合實驗所設計比例。接著，將LDHs-OCNCs與酚醛環氧樹脂單體聚合成奈米複材，由WXRD及穿透式電子顯微鏡(TEM)觀察奈米複材的分散型態，發現LDHs-OCNCs是以島型插層或脫層分散於酚醛環氧樹脂中。在熱性質方面，利用TGA得知奈米複材仍具熱穩定性；以熱機械分析儀(TMA)得知奈米複材的膨脹係數(CTE)提升了26 %。最後，利用極限氧指數儀(LOI)、圓錐量熱儀(Cone calorimeter)來測試奈米複材的難燃性，得知，LOI值由原本純的酚醛環氧樹脂22提升到33；並且由Cone calorimeter得知引燃時間(tign)由原本的23秒增加至150秒以上，最高熱釋放速率(PHRR) 降低了19 %，總熱釋放值(THR) 降低了7 %，因此證實LDHs-OCNCs奈米複材確實具有難燃效果。並將效果最好的組成配方實際應用於銅箔基板，探討其各項基板性質。

關鍵字

層狀雙氫氧化合物 ； 難燃 ； 酚醛環氧樹脂 ； 奈米碳球

並列摘要

In this study, the flam resistant improvement of novolac cured epoxy/LDH nanocomposites is induced by addition of the different ratios of layered double hydroxides (LDHs) and modified carbon nanocapsules (OCNCs). There are three types of LDHs, including small aspect ratio of lithium aluminum (LiAl) and magnesium aluminum (MgAl) types and large aspect ratio of the lithium aluminum type, were applied in this work. There is more coordinated water in MgAl-LDHs, compared with LiAl-LDHs, which induces is more heat absorption in MgAl-LDHs than heat absorption in LiAl-LDHs during the combustion. At the same time, the evaporated water will dilute the concentration of oxygen supply. Another major effect in fire resistant is that the OCNCs could produce the free radical to trap the •H and •OH free radicals, which release from the decomposition of polymer during the combustion process. The other factor of inhibiting combustion in the nanocomposites is the barrier property, provided from the exfoliated dispersion of LDHs layered structure in the polymer matrix, to extend the pathway of thermal conductivity and combustible gases supply during combustion. The dispersion morphology of LDHs and OCNCs in the novolac cured epoxy resin was analyzed by wide-angle X-ray diffraction (WXRD) and transmission electron microscopy (TEM). Thermo-gravimetric analysis (TGA) and dynamic mechanical analysis (DMA) were used to study the thermal and mechanical properties. The flammability was evaluated by limiting oxygen index (LOI) and cone calorimeter test for these nanocomposites.

並列關鍵字

Novolac Cured Epoxy ； LDH ； O-CNCs

參考文獻

[55] 陳韋志， 「研究以不同視徑比的鋰鋁層狀雙氫氧化合物應用於環氧基材之製備與性質」， 中原大學碩士論文 ， 2008，31-33。

[2] S. Komarneni, “Nanocomposites”, J. Mater. Chem., 1992, 2, 1219-1230.

[3] T. Y. Tsai, S. T. Lu, C. J. Huang, J. X. Liu, C. H. Li, L.C. Chen, U. Ray, “ The structure-property relationship of novolac cured epoxy resin / clay nanocomposites. ” Polymer. Eng. Sci., 2008, 48, 467-476

[4] J. H. Park and C. Jana, “The relationship between nano- and micro-structures and mechanical properties in PMMA-epoxy-nano clay composites.” Polymer. 2003, 44, 2091-2100.

[5] M. Zanetti, “Fire Retardant Halogen-Antimony-Clay Synergism in Polypropylene Layered Silicate Nanocomposites. ”Chem. Mater. , 2002, 14, 189-193.