臺灣博碩士論文加值系統

摘要
聚丙烯（Polypropylene，PP）為眾所週知之泛用塑膠，其原料豐富，生產成本低，易加工成型，機械性質強韌且抗酸鹼腐蝕等多項優點。而其缺點為易燃，易造成火災。
本研究旨在國際綠色法規RoHS及WEEE之規範下，研發含添加型阻燃劑之PP。以臺灣地區產量豐富而含有大量阻燃成分二氧化矽的農業廢棄物稻殼灰(Rich husk ash，RHA) 為基礎，研究搭配無鹵阻燃劑聚磷酸銨(APP)、硼酸鋅(ZB)之阻燃配比。利用場發電子顯微鏡(Field Emission Scanning Electron Microscope，SEM)、拉曼光譜(Raman spectrum)分析材料定性結構鑑定，利用熱重量分析儀(TGA)測詴分析熱性質並經由積分程序分解溫度(IPDT)及Ozawa方法計算阻燃複合材料活化能，瞭解阻燃材料之熱穩定性。
經由難燃性測詴得知，純聚丙烯其極限氧指數LOI由18提升到32(PP30%/PP30%/PP30%/PP30%/PP30%/PP30%/RHARHARHA14%/ APPAPPAPP-ZB56%ZB56%ZB56%ZB56%ZB56%)；另由UL-94難燃等級判別測詴，由易燃等級(純聚丙烯)提升為V-0難燃等級。不僅顯示稻殼灰等阻燃劑添加於塑膠後，可有效提昇PP塑膠的阻燃效果，使PP塑膠的運用面更廣。更可發揮稻殼的廢棄物再利用的實用價值。
關鍵字:稻殼灰、硼、磷、矽、難燃劑、複合材料

Abstract
Polypropylene(PP) is well known general purpose plastics due to the abount of materials source , low price , easily processing , mechanical properties , acid corrosion resistance and many other advantages. But one of the disadvantages is flammable,and it will lead to fire damage easily .
This study aims of this research which is under the international RoHS and WEEE regulations to developone kind of additive flame retardant for PP matrix. The rice husk ash (RHA) which was large amount of agricultural waste in Taiwan was used as flame retardant due to high content of silica. The hybrid flame retardants were composed of RHA,ammonium polyphosphate (APP) and zinc borate(ZB).
The field emission electron microscope (SEM) ,raman and thermal gravimetric analyzer (TGA) were used to investigate the structure and thermal properties of the composites. Integral procedural decomposition temperature (IPDT) and Ozawa's method which was used to calculate activation energy thermal degradation，were used to thermal stability of the flame retardant material.
The value of limiting oxygen index (LOI) value for pure PP is only 18 % , indicating it was very flammable , and it is increased to 32% for PP 30/RHA14/APP-ZB56 which was flame retardant.
Pristine pp was classified into flammable level and PP 30/RHA14/APP-ZB56 increased to V-0 level by UL-94 test . It means that hybrid flame retardants containing RHA can improve the flame retardant property of the plastic and application developmentof rice husk recycling.
Keywords:Rice husk ash，Zinc Borate，Ammonia Polyphosphate，Polyproplne，flame retardant，composites

目錄
摘要…………………………………………………………………….. I
Abstract…………………………………………………………………. II
謝誌…………………………………………………………………….. III
目錄…………………………………………………………………….. VI
表目錄………………………………………………………………….. XI
圖目錄…………………………………………………………………... XIII
第一章緒論……………………………………………………………. 1
第二章理論基礎與文獻回顧………………………………………… 4
2-1 燃燒理論………………………………………………………. 4
2-1-1燃燒的定義…………………………………………………… 4
2-1-2 燃燒的機制………………………………………………….. 4
2-1-3 火災造成的危害…………………………………………….. 6
2-1-3-1火災對人體、身家性命的危害………………………….. 6
2-1-3-2火災對建築設施結構的危害…………………………….. 8
2-2 高分子燃燒理論……………………………………………….. 9
2-2-1高分子燃燒原理……………………………………………… 10
2-2-2高分子燃燒理論……………………………………………… 11
2-2-2-1 高分子巨觀燃燒機制…………………………………….
2-2-2-2高分子微觀燃燒機制…………………………………… 11
12
2-3 高分子難燃劑介紹……………………………………………… 15
2-3-1 高分子難燃劑緣起………………………………………….. 15
2-3-2 難燃劑的作用……………………………………………….. 15
2-3-3 難燃劑的分類……………………………………………….. 17
2-3-4 難燃劑的協成效應………………………………………….. 21
2-5 綠色法規………………………………………………………… 23
2-6阻燃劑用於高分子塑膠複合材料之反應機制及文獻回顧......... 30
2-6-1 Polypropylene………………………………………………… 30
2-6-1-1 聚丙烯之優缺點…………………………………………. 30
2-6-1-2聚丙烯成型方法和用途………………………………….. 30
2-6-2 硼酸鋅(zinc borate)難燃劑之相關文獻回顧…………….. 31
2-6-2-1 硼酸鋅阻燃機制…………………………………………. 31
2-6-2-2 硼酸鋅的合成方法…………………………………... 31
2-6-2-3 硼酸鋅的阻燃機制文獻回顧………………………... 34
2-6-3 聚磷酸銨阻燃劑之相關文獻回顧……………………... 38
2-6-3-1 聚磷酸銨之阻燃研發……………………………………. 38
2-6-3-2 聚磷酸銨(APP)阻燃機制………………………………... 39
2-6-3-2聚磷酸銨(APP)阻燃機制文獻回顧……………………... 41
2-6-4 稻殼灰(二氧化矽) …………………………………………... 47
第三章研究目的與內容……………………………………………... 56
3-1 研究目的………………………………………………………… 56
3-2 研究內容………………………………………………………… 57
第四章實驗步驟與流程……………………………………………... 58
4-1實驗藥品………………………………………………………….. 58
4-1-1 Polyproplne…………………………………………………. 58
4-1-2 Rice Husk Ash (RHA；碳化稻殼) ………………………… 58
4-1-3 Ammonia Polyphosphate (APP；聚磷酸銨) ………………. 59
4-1-4 Zinc Borate (ZB；硼酸鋅) ………………………………… 59
4-2 實驗儀器及測試方法………………………………………… 61
4-2-1塑譜儀……………………………………………………… 61
4-2-2 熱壓成型機………………………………………….……… 61
4-2-3 極限需氧指數測定儀……………………………………… 62
4-2-4 垂直燃燒試驗儀…………………………………….……… 64
4-2-5熱重量分析儀……………………………………………… 65
4-2-6能量散射光譜儀.… ………………………..……………. 67
4-2-7電子能譜儀…………………………………………………. 67
4-2-8冷場發射掃描式電子顯微鏡………………………………. 68
4-2-9 萬能拉伸彎曲試驗機……………………………………… 68
4-2-10 萬能耐衝擊試驗機………………………………………... 69
4-3實驗流程圖……………………………………………………… 70
4-4 實驗步驟…………………………………….………………… 71
第五章結果與討論……………………………………….…………… 73
5-1 PP/RHA/APP-ZB 複合材料熱性質分析………..…………… 73
5-1-1不同溫升速率下熱裂解曲線……………………..………… 73
5-1-1-1熱重量分析……………………………………………… 73
5-1-2熱解速率分析……………………………..………………… 75
5-1-3積分程序裂解溫度………………………………...………… 77
5-1-4 不同溫升速率下熱裂解動力學Ozawa method………….. 78
5-1-4-1 Flynn-well-Ozawa動力學模型數學模式推導………… 78
5-1-4-2PP/ RHA/APP-ZB熱裂解動力學Ozawa method 分析 81
5-1-4-3 Kissinger 模式………………………………………….. 86
5-1-4-4 熱裂解動力學Kissinger method 分析……………... 87
5-2難燃性分析………………………...…………………………… 92
5-2-1 UL-94、LOI…………………………………………………… 92
5-3 難燃機制分析…………………………………………………... 96
5-3-1 EDS…………………………………………………………... 96
5-3-2 XPS…………………………………………………………… 98
5-3-3 Raman………………………………………………………… 112
5-4 靜態機械性質分析……………………………………………... 115
5-5 形態學…………………………………………………………. 119
5-5-1 SEM………………………………………………………….. 119
5-6難燃性複合材料兼顧綠色環保及經濟效益之評估…………... 121
5-6-1 PP/RHA/APP-ZB難燃性材料價格評估………….……… 121
5-6-2 PP/RHA/APP-ZB難燃性材料兼顧綠色環保訴求….…… 123
第六章結論……………………………………………….…………….. 125
第七章參考文獻…………………………………………...…………… 127

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