臺灣博碩士論文加值系統

本研究主要在探討以環氧樹脂為基質，添加不同的石墨烯或石墨烯-聚苯胺(graphene-PANI)複合物之後的機械性質和抗腐蝕能力。我們使用化學改質或高分子分散劑使石墨烯較好的分散在水中，並在其上合成PANI，之後使用元素分析、XRD、拉曼光譜、FT-IR、XPS 分析其表面性質，並利用SEM 觀測複合物的形態，由分析結果確認我們成功的將聚苯胺以不同的方式合成在石墨烯上，其中化學改質後合成聚苯胺的樣品稱為a-NP，以高分子分散後聚合聚苯胺的樣品稱為P-P/N。之後我們將上述合成的複合物與環氧樹脂及其固化劑混合，利用DSC 研究其固化反應放熱量以估算固化程度，並且以複合物的斷面來觀察環氧樹脂與填料的相容性。實驗結果發現a-NP 的分散性最好，P-P/N 和N002 的分散性較差。接下來我們利用拉伸測試(Tensile test)和動態機械分析儀(DMA)測量複合物在post curing 前後不同的機械性質，發現epoxy/a-NP 在post curing 前機械性質較佳，epoxy/P-P/N 在postcuring 之後則具有非常好的韌性。抗腐蝕性質的部分，以環氧樹脂複合物薄膜塗佈在碳鋼片上，經過post curing 之後我們採用電化學測試來模擬腐蝕的情形，而抗腐蝕的效果則是以epoxy/a-NP 最佳，而這是因為此種複合物填料的分散性最好，使的石墨烯和聚苯胺都發揮良好的抗腐蝕功效。另外我們也針對不同的複合物進行抵抗黃化的評估，我們選用FT-IR 來分析環氧樹脂在經過照射之後內部化學結構的變化，並以carbonyl index 來分析結果。結果顯示a-NP 和N002 作為填料的複合物抗黃化效果最佳。總結而言，我們成功製造出兩種不同的環氧樹脂/石墨烯-聚苯胺複合物薄膜，兩者在post curing 前後的機械性質各有優劣，並且都有良好的抗腐蝕性能，未來應能在抗腐蝕塗料和高強度環氧樹脂的材料領域有所應用。

In this work, polyaniline/graphene oxide composites were fabricated via in situ redox polymerization on the surface of PSS-dispersed graphene oxide or p-phenelene diamine-modified graphene oxide. The results of EDX and EA as well as the characteristic peaks in FT-IR and XRD spectrum all pointed out that the surface of graphene oxide platelets was covered by PANI. P-P/N, a-NP and pristine graphene oxide (N002) were then blended separately with bisphenol-A type epoxy and a curing agent at different loadings. Analyzed by DSC, DMA, tensile test and TMA, the thermal and mechanical properties of epoxy composites revealed that a-NP and P-P/N platelets were more compatible in epoxy matrix than N002 after the post curing process, upon which the PANI on the surface of a-NP and P-P/N platelets was allowed to participate in the curing reaction of epoxy resin. The enhanced filler-matrix interface and the stiffness provided by graphene oxide platelets improved the toughness of post cured epoxy/P-P/N by 154% for 0.5 wt. % compared to that of pristine epoxy. Moreover, in potentiodynamic polarization analysis, the presence of N002 filler in epoxy coatings reduce the corrosion current density by increasing the tortuosity of diffusion pathways for gas and ions, whereas the specimens with epoxy/ a-NP epoxy/P-P/N coatings exhibited even higher corrosion potentials and lower corrosion rates. The XPS spectrum of the carbon steel surface also confirmed the existence of Fe2O3/Fe3O4 layer, which was ascribed to the passivation of carbon steel surface by PANI. The superior anticorrosion performance of epoxy/P-P/N coatings were ascribed to the more compact filler-matrix interface and the presence of passivation layer. In summary, the incorporation of a-NP and P-P/N in epoxy composites enhanced the mechanical properties of epoxy and provided promising potential in anticorrosion applications.

致謝 ------------------------------------------------------------------------------------------------------ I
摘要 ------------------------------------------------------------------------------------------------------ II
ABSTRACT -------------------------------------------------------------------------------------------- III
目錄 ------------------------------------------------------------------------------------------------------ IV
圖目錄 --------------------------------------------------------------------------------------------------- VII
表目錄 --------------------------------------------------------------------------------------------------- X
第一章 研究介紹及文獻回顧---------------------------------------------------------------------- 1
1.1. 環氧樹脂的簡介與應用------------------------------------------------------------------ 1
1.1.1. 環氧樹脂簡介--------------------------------------------------------------------- 1
1.1.2. 環氧樹脂的固化反應------------------------------------------------------------ 4
1.1.3. 環氧樹脂的應用------------------------------------------------------------------ 5
1.2. 金屬腐蝕------------------------------------------------------------------------------------ 7
1.2.1. 金屬腐蝕原理--------------------------------------------------------------------- 7
1.2.2. 腐蝕防治方法--------------------------------------------------------------------- 8
1.2.3. 抗腐蝕能力評估------------------------------------------------------------------ 10
1.3. 聚苯胺--------------------------------------------------------------------------------------- 15
1.3.1. 聚苯胺簡介------------------------------------------------------------------------ 15
1.3.2. 聚苯胺的合成--------------------------------------------------------------------- 16
1.3.3. 聚苯胺的聚合機制--------------------------------------------------------------- 17
1.3.4. 聚苯胺的應用--------------------------------------------------------------------- 19
1.4. 石墨烯的研究發展------------------------------------------------------------------------ 22
1.4.1. 石墨烯/氧化石墨烯簡介-------------------------------------------------------- 22
1.4.2. 石墨烯/氧化石墨烯的製備----------------------------------------------------- 22
1.4.3. 石墨烯的應用--------------------------------------------------------------------- 25
第二章 實驗方法------------------------------------------------------------------------------------- 29
2.1. 實驗藥品------------------------------------------------------------------------------------ 29
2.2. 實驗流程------------------------------------------------------------------------------------ 32
2.3. Polystyrene sulfonate-Polyaniline/N002 (P-P/N) 複合物製備----------------- 33
2.4. Amine-functionalized-N002/Polyaniline (a-NP) 複合物製備------------------ 33
2.5. 環氧樹脂複合物製備--------------------------------------------------------------------- 34
2.6. 環氧樹脂複合物固化特性評估--------------------------------------------------------- 34
2.7. 石墨烯/聚苯胺複合物性質-------------------------------------------------------------- 34
2.8. 環氧樹脂複合物機械性質與熱性質分析-------------------------------------------- 35
2.9. 環氧樹脂塗層的抗腐蝕性質------------------------------------------------------------ 35
2.10. 環氧樹脂黃化評估---------------------------------------------------------------------- 38
第三章 結果與討論---------------------------------------------------------------------------------- 39
3.1. 材料性質鑑定------------------------------------------------------------------------------ 39
3.1.1. N002, a-N002, a-NP and P-P/N 複合材料之表面型態分析--------------- 39
3.1.2. N002, a-N002, P-P/N and a-NP 性質鑑定------------------------------------ 42
3.2. 環氧樹脂複合物性質分析--------------------------------------------------------------- 52
3.2.1. 環氧樹脂複合物的固化性質--------------------------------------------------- 52
3.2.2. 環氧樹脂複合物的斷面影像--------------------------------------------------- 58
3.2.3. 環氧樹脂複合物的機械性質--------------------------------------------------- 64
3.3. 環氧樹脂複合物的表面保護能力----------------------------------------------------- 83
3.3.1. 水接觸角--------------------------------------------------------------------------- 83
3.3.2. 百格附著試驗--------------------------------------------------------------------- 84
3.3.3. 電化學測定------------------------------------------------------------------------ 85
3.3.4. 鹽霧測試--------------------------------------------------------------------------- 91
3.4. 環氧樹脂複合物黃化評估--------------------------------------------------------------- 93
第四章 結論 ------------------------------------------------------------------------------------------- 96
附錄 ------------------------------------------------------------------------------------------------------ 99
參考文獻 ------------------------------------------------------------------------------------------------ 106

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