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研究生： 劉明政
Ming-Cheng Liu
論文名稱： 改質矽酸奈米顆粒對環氧樹脂/SiO2混成材料結構及性質探討
The Effect of Modified Polysilicic Acid on the Structure and Properties of Epoxy/ SiO2 hybrids
指導教授： 許應舉
Ying-Gev Hsu
口試委員: 陳信龍
none
洪伯達
Po-Da Hong
學位類別： 碩士
Master
系所名稱： 工程學院 - 材料科學與工程系
Department of Materials Science and Engineering
論文出版年： 2005
畢業學年度： 93
語文別： 中文
論文頁數： 89
中文關鍵詞： 奈米顆粒 、環氧樹脂
外文關鍵詞： CLNs, IPNs
相關次數： 點閱：323  下載：7 
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    • 將聚矽酸奈米顆粒 (polysilicic acid nanoparticles, PN)表面之矽醇基(Si-OH)與含有矽氧烷類基團【-Si(OR)3】的改質劑(modifier)－3-glycidoxypropyltrimethoxysilane (GPTS)及3-(trimethoxysilyl) propyl- methacrylate (TPA)進行反應，將PN顆粒表面改質成含有-CH-CH2及-C-C(CH3)=CH2基團之改質PN，並分別以G-PN與T-PN稱之。
    G-PN及T-PN分別與環氣樹脂DGEBA(diglycidyl ether bisphenol A)、硬化劑MDA(4,4’-methylenedianiline)混合均勻，並調配成透明之粘稠液(分別以G-epoxy和T-epoxy稱之)。G-epoxy 與T-epoxy在熱硬化處理後，形成之有機－無機混成材料為架橋結構(cross-linked networks, CLNs)；然而，T-epoxy在BPO(benzoyl peroxide)的存在下，經熱處後，則形成有機無機相互穿梭網絡結構(interpenetrating networks, IPNs)。以各種儀器如FT-IR、DSC、TMA、SAXS、DMA、分析材料之相間作用力、微細構造、彎曲模數、動態機械與熱性質，並進而評估材料結構對硬化收縮及內應力之影響。實驗結果發現，相較於CLNs結構，IPNs結構之混成材料具有較低的硬化收縮率及內應力，且在不犠牲材料Tg的情況下有更好的機械性質。

    The 3-glycidoxypropyltrimethoxysilane (GPTS) and 3-(trimethoxysilyl) propyl- methacrylate (TPA) modified polysilicic acid nanoparticles (PN), G-PN and T-PN, were mixed, respectively, with the solution of DGEBA and 4,4’-methy-lenedianiline (MDA), DGEBA/MDA, to prepare homo- -geneous resins called, G-epoxy and T-epoxy. When G-epoxy and T-epoxy were heat cured, they crosslinked, respectively, with the matrix, DGEBA/MDA, to afford the hybrids, DGEBA/MDA/G-PN and DGEBA/MDA/T-PN, of cross-linked networks (CLNs) structures. However, when T-epoxy was heated in the presence of peroxide (e.g., BPO), the structure of the cured hybrid, DGEBA/MDA/T-PN-B, became an structure of interpenetrating networks (IPNs). It was found that the DGEBA/MDA/T-PN-B hybrid of IPN structure had lower curing shrinkage and internal stress than that of the cured DGEBA/MDA and DGEBA/MDA/T-PN and DGEBA/MDA/G-PN hybrids of CLNs structure without sacrificing the Tg ,thermal ,and mechanical properties of the material.

    中文摘要………………………………………………………………I 英文摘要………………………………………………………………II 誌謝……………………………………………………………………III 目錄……………………………………………………………………IV 附圖索引………………………………………………………………VII 附表索引………………………………………………………………IX 第一章前言--------------------------------------------1 第二章文獻回顧----------------------------------------4 2-1環氧樹脂低硬化收縮研究與發展--------------------4 2-2環氧樹脂的IPNs結構------------------------------8 2-3SAXS於IPNs結構的應用---------------------------11 第三章基本原理---------------------------------------13 3-1溶膠-凝膠法的製程------------------------------13 3-2PN法的製程-------------------------------------18 3-3PN表面改質法的製程-----------------------------20 3-4體積收縮率的測試原理---------------------------21 3-5內應力的測試原理-------------------------------22 3-5.1 決定內應力的參數-----------------------------22 3-5.2線性熱膨脹係數---------------------------------23 3-5.3三點彎曲試驗-----------------------------------24 3-6SAXS應用於IPN結構的基本原理--------------------26 3-6.1 測量intraparticle的距離-------------------------26 3-6.2 測量interparticle的距離-------------------------28 第四章 實驗------------------------------------------29 4-1 實驗藥品------------------------------------------29 4-2 PN顆粒之合成--------------------------------------31 4-3 PN顆料之表面改質----------------------------------32 4-3.1 PN表面之-OH基團測定---------------------------35 4-4 混成材料試料製備----------------------------------35 4-4.1 DGEBA/MDA 系統----------------------------------36 4-4.2 DGEBA/MDA/M-PNs 系統----------------------------37 4-5 混成材料測試--------------------------------------39 4-5.1 收縮率的測試----------------------------------40 4-5.2 FT-IR-----------------------------------------41 4-5.3 內應力測試------------------------------------42 4-5.4 SAXS測試--------------------------------------44 4-5.5 DMA熱機械性質測試-----------------------------45 4-5.6 DSC熱性質測試---------------------------------46 第五章 結果與討論-----------------------------------47 5-1 Si-OH濃度之測定----------------------------------47 5-2 PN顆粒之改質-------------------------------------48 5-3 混成材料之製備-----------------------------------51 5-4 混成材料之收縮效應-------------------------------54 5-5 模型反應探討反應機制-----------------------------58 5-5.1 結構分析模擬試驗---------------------------------62 5-6 混成材料硬化之內應力-----------------------------65 5-7 SAXS研討混成材料之IPNs結構-----------------------69 5-8 DMA研討混成材料之動態機械性質--------------------74 5-9 DSC研討混成材料之熱性質--------------------------78 第六章結論-------------------------------------------84 第七章參考文獻---------------------------------------86 附圖索引 圖3-1 溶膠-凝膠法製備混成複材之流程圖-------------------14 圖3-2 PN法製備混成複材之流程圖--------------------------19 圖3-3 線性熱膨脹係數之測試原理--------------------------23 圖3-4 三點彎曲試驗(3-Point Blend Flexural test)測試條件24 圖3-5 文獻36Debye plot of I-1/2 versure S2-------------27 圖3-6 文獻36Guinier plot of ln I versure S2------------28 圖4-1 DGEBA與MDA之反應機構-----------------------------36 圖4-2 混成材料之製備流程圖-----------------------------38 圖4-3 混成材料樣品測試流程圖---------------------------39 圖5-1 DGEBA/MDA基材與PN顆粒相間氫鍵結合之結構----------48 圖5-2 PN顆粒表面改質之反應機制-------------------------49 圖5-3 PN, G-PN與T-PN之FT-IR光譜圖----------------------50 圖5-4 DGEBA/MDA基材與三種不同混成材料之FT-IR光譜比較圖-53 圖5-5 各混成材料系統在不同PN含量下體積收縮率的比較圖---54 圖5-6 混成材料在不同(Modifier)/PN比例下體積收縮率的比較56 圖5-7 MDA/T-PN混合液中不加起始劑及加入起始劑加熱前後之FT-IR光譜圖--------------------------------------------60 圖5-8 DGEBA/MDA/G-PN、DGEBA/MDA/T-PN及DGEBA/ MDA/T-PN-B系統之反應機制圖-----------------------------61 圖5-9 T-PN2/S-PN2、T-PN4/S-PN4、T-PN8/S-PN8，加熱硬化後之之FT-IR光譜圖----------------------------------------------------64 圖5-10 各混成材料之內應力比較圖------------------------------------67 圖5-11 各混成材料之內應力與體積收縮率對照圖------------------68 圖5-12 DGEBA/MDA/PN及DGEEBA/MDA/T-PN-B系列之Debye -Bueche plot-------------------------------------------------------69 圖5-13 DGEBA/MDA/PN及DGEEBA/MDA/T-PN-B系列之Guinier plot--------------------------------------------------------70 圖5-14 DGEBA/MDA/PN及T-PN-B系統之IPNs結構模擬----73 圖5-15 基材DGEBA/MDA及各混成材料系，經熱處理硬化後之DMA試驗---------------------------------------75 圖5-16 基材DGEBA/MDA及T-PN-B系統(IPNs結構)混成材料，經熱處理硬化後之DMA試驗--------------77 圖5-17 DGEBA/MDA/G-PN系統各成份之DSC圖------------------81 圖5-18 DGEBA/MDA/T-PN系統各成份之DSC圖------------------82 圖5-19 DGEBA/MDA/T-PN-B系統各成份之DSC圖--------------83 附表索引 表4-1 固定[GPTS]/PN比例與改變 PN含量下混成林料之配方表--33 表4-2 固定[TPA]/PN比例與改變 PN含量下混成林料之配方表----33 表4-3 固定 PN含量與改變[GPTS]/PN比例下混成林料之配方表--34 表4-4 固定PN含量與改變[TPA]/PN比例下混成林料之配方表---34 表5-1 不同改質劑比例下PN表面Si-OH含量(mM / g)--------------47 表5-2 混成材料在不同改質劑存在下之樣品名稱---------------------51 表5-3 各系列混成材料中抗收縮效果最佳之(Modifier)/PN比例---57 表5-4 各混成材料之彎曲模數(Er)、熱膨脹係數(α1)與內應力參數(S)之值------------------------------------------------------------------66 表5-5 經由SAXS所得二相之間的相關參數---------------------------71 表5-5 各混成材料系統之Tg值-------------------------------------------80

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