聚胺基甲酸酯(Polyurethane, PU)具有優良的堅韌性質與耐衝擊性質，其質地柔軟且易於生產製造，故在工業上為良好的彈性體高分子材料；然而，雖然具有良好的性質與廣泛的用途，但卻因其機械性質與耐燃性不佳，而使得應用範圍受到限制。酚醛樹脂(Phenol-Formaldehyde Resin, PFR)則具有較優異的耐燃性質，其質地堅硬且亦容易生產製造，故在工業上亦是良好的高分子材料。
本研究利用具有耐燃特性的酚醛樹脂(PFR)、磷化物改質的酚醛樹脂(P-PFR)及硼化物與磷化物改質的酚醛樹脂(B,P-PFR)來改質PU，製備出不同比例的PU/PFR、PU/P-PFR及PU/B,P-PFR複合材料，藉以改善其熱性質、機械性質及耐燃性，做為火箭發動機阻燃層膠合劑，另以旋轉塗佈法將上述複合材料披覆在鋁合金(AA-6061-T6)上，做為耐燃防腐蝕塗料。同時藉由紅外線光譜儀(FTIR)、凝膠滲透層析儀(GPC)、原子力顯微鏡(AFM)、掃描式電子顯微鏡(SEM)、熱重損失分析儀(TGA)、極限氧指數(L.O.I.)、氫氧焰燒蝕測試、動態機械分析儀(DMA)、熱機械分析儀(TMA)、電化學交流阻抗頻譜(EIS)及鹽霧試驗，探討PU/PFR、PU/P-PFR及PU/B,P-PFR複合材料的光譜特性、熱性質、機械性質、耐腐蝕性等，期望能成為一種新型阻燃層膠料及航空器防蝕材料。

A series of polyurethane/phenol-formaldehyde resin (PU/PFR), polyurethane/phosphonic-modified phenol-formaldehyde resin (PU/P-PFR) and polyurethane/boron, phosphonic-modified phenol-formaldehyde resin (PU/B,P-PFR) composites were prepared through a copolymerization technique and then curing. The objective of the study was to develop and evaluate a unique polyurethane elastomer containing PFR molecules as molecular reinforcements in the hard segment that acted as binder of insulator for rocket motor. Hydroxy-terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), PFR, P-PFR and B,P-PFR were used as precursors for these composites. The effects induced by the media material structure, type and ratio on the thermal, mechanical properties, flame resistance and burn resistance of composites were investigated. The FTIR spectra suggested successful bonding of PFR and PU. The homogeneous dispersion of PFR in the PU matrices was evidenced by scanning electronic microscopy (SEM) and atomic force microscopy (AFM). Thermal and mechanical properties of these PU/PFR composites have been improved over the pure PU analyzed by dynamic mechanical analysis (DMA), Limit Oxygen Index (L.O.I.), thermomechanical analysis (TMA) and thermal gravimetric analysis (TGA). Moreover, these composite films were deposited via spin coating onto aluminum alloy (6061-T6) in order to improve the corrosion protection. Potentio-dynamic and salt-spray analysis revealed that the composite films provided an exceptional barrier and corrosion protection in comparison with PU and untreated aluminum alloy substrates.

誌謝 ii
摘要 iii
ABSTRACT iv
目錄 iv
表目錄 vii
圖目錄 vii
1. 緒論 1
1.1 前言 1
1.2 文獻探討 2
1.2.1聚胺基甲酸酯發展起源 2
1.2.2聚胺基甲酸酯之熱性質 6
1.2.3 聚胺基甲酸脂之相分離 7
1.2.4 聚胺基甲酸脂之原料 7
1.2.5 聚胺基甲酸脂之應用 11
1.2.6 HTPB膠燃料簡介 12
1.2.7 酚醛樹脂 14
1.2.8阻燃層 20
1.3 研究動機及目的 29
2. 實驗 31
2.1 實驗材料 31
2.2 實驗儀器及裝置 33
2.3 鑑定儀器 33
2.4 實驗架構與流程 34
2.5 鋁合金試片前處理與塗層製備 35
2.6 材料特性鑑定方法與原理 40
3. 結果與討論 43
3.1 結構及型態分析 43
3.2 熱性質分析 51
3.4 動態機械性質分析(DMA)及熱機械性質分析(TMA) 56
3.5 機械性質分析 59
3.6 電化學測試 60
3.7 鹽霧試驗 67
4. 結論 69
參考文獻 71
自傳 78

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