臺灣博碩士論文加值系統

摘要
以各種不同含量的polyphenylene oxide (PPO)與epoxy-cyanate ester 硬化系統摻合,來探討硬化反應機構及摻合體與複合材料之機械性質。由FTIR及NMR 分析得知，特性官能基的反應隨PPO之增加而加速且有coreaction產生，例如cyanate-hydroxyl addition (imidocarbonate)，epoxy-cyanate addition (oxazolidinone) 及epoxy-amine addition 等。這些coreaction產生的原因是由於PPO末端OH基及系統中的水氣會與cyanate ester產生反應，其生成物imidocarbonate與carbomate進而再與epoxy及cyanate ester反應，產生epoxy開環與triazine之結構物。摻合體與克維拉纖維製成複合材料，其層間剪切力(ILSS) 及T型剝離力(T-peel)強度隨PPO加入量的增加而增加。在PPO含量為50phr時其層間剪切應力提升了1.6倍；T型剝離力提升了2.9倍之多。此外在不含PPO之複材中，纖維若經過氨氣電漿30Ｗ（0.15torr）五分鐘處理後其層間剪切力(ILSS)提升了30％；T型剝離力提升了23％。

Abstract
Epoxy/PPO blends were cured with multifunctional cyanate ester resin . The effects of PPO content on cure behavior and thermal stability in the cyanate ester cured epoxy were investigated with FTIR,NMR and TMA . Cure reaction in the epoxy/PPO blends is faster than that of the neat epoxy system . FTIR and NMR analysis reveal that the functional group reactions are accelerated by adding PPO and indicate that several coreactions occured , such as cyanate-hydroxyl addition , epoxy-cyanate addition and epoxy-amine addition . This may be caused by the reaction of cyanate ester with aryl phenol and water yields imidocabonate and carbamate intermediate which can react with epoxy resin and cyanate ester . TMA shows the thermal stability of the epoxy/PPO blends is improved by adding PPO .
Futher , the mechanical properties of epoxy/PPO/Kevlar fiber composites , as measured by the short-beam test and T-peel test , are also improved by adding PPO and surface plasma treatment of fiber.

目 錄
第 一 章 前 言‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥1
第 二 章 文獻回顧‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥4
2.1環氧樹脂的改質‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥4
2.2韌化的機構‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥6
2.3複合材料的改質系統介紹‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥7
2.4熱塑性塑膠聚氧化二甲苯(PPO)之回顧探討‥‥‥‥‥‥‥‥12
2.5聚醯胺纖維‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥12
2.6電漿纖維表面改質‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥12
第 三 章 實 驗‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥18
3.1化學藥品‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥18
3.2儀器設備‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥19
3.3實驗流程‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥21
(A) 基材之實驗流程‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥21
(B) 複材之實驗流程‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥22
3.4基材動力學試片之製作程序‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥23
3.4.1FTIR傅立葉轉換紅外光譜分析試片之製作‥‥‥‥‥‥‥‥23
3.4.2Solid NMR試片之製作‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥23
3.4.3熱性質分析(TGA)‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥24
3.5複合材料製作程序‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥24
3.5.1纖維的前處理‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥24
3.5.2纖維之化學處理‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥25
3.5.3纖維之氣體電漿蝕刻處理‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥25
3.6熱壓成形法製試片‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥26
(a) ILSS(interlaminar shear strength) 試片‥‥‥‥‥‥29
(b) T-Peel strength試片‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥29
3.7Epoxy/Cynate/PPO/kevlar複合材料的機械測試‥‥‥‥‥‥31
(a) 層間剪切力強度的測試法‥‥‥‥‥‥‥‥‥‥‥‥‥‥31
(b) T型剝離力的測試法‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥31
(c) 動態機械性質之測量‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥33
3.8破壞撕裂面的觀察‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥34
第 四 章 結 果 與 討 論‥‥‥‥‥‥‥‥‥‥‥35
4.1基材反應性之探討‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥35
4.1.1Epoxy/cynate ester/PPO基材反應性之FTIR探討‥‥‥‥35
4.1.2 Epoxy/cynate ester/PPO基材反應性之Solid NMR探討‥52
4.2 Epoxy/cynate ester/PPO熱性質測試‥‥‥‥‥‥‥‥59
4.3 Epoxy/cynate ester/PPO摻合體之熱性質探討‥‥‥63
4.4 Epoxy/cynate ester/PPO摻合體之動態黏彈分析探討‥‥65
4.5機械性質之探討‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥66
4.5.1Epoxy/PPO/Kevlar複合材料之層間剪切應力(ILSS)機械性質
的探討 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥66
4.5.2 Epoxy/PPO/Kevlar複合材料之T型剝離力(T-Peel strength)
機械性質的探討‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥67
4.5.3纖維布磺酸化處理及氨氣電漿處理層間剪切應力(ILSS)之結
果‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥70
4.5.4纖維布磺酸化處理及氨氣電漿處理T 型剝離力之結果 ‥72
第 五 章 結 論 ‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥‥74
第 六 章 參 考 文 獻‥‥‥‥‥‥‥‥‥‥‥‥‥76

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