本研究利用photo-DSC研究氧化鋯(ZrO2)/ hydroxyethyl methacrylate(HEMA)厚膜在UV(365nm)光照射下的光聚合反應，發現反應速率會受到ZrO2含量影響。我們採用Kamal 方程式作為動力學模式並可求得轉化率隨反應時間的變化曲線，研究發現Kamal方程式在玻璃化現象發生前能良好描述實驗結果。依據組成的不同，厚膜的玻璃轉移溫度由88℃上升至95℃，而藉由TGA所量測的5%重量損失溫度由300℃提升到333℃。我們進一步使用photo-DSC搭配藍光LED (450nm)，研究光起始劑Irgacure 819濃度對HEMA單體光聚合影響，並採用Kamal 方程式作為反應動力學模式。結果顯示Irgacure 819濃度越高會導致反應速率加快及厚膜玻璃轉移溫度降低，由85.4℃降至77.4℃。

Kinetics of photopolymerization of ZrO2/hydroxyethyl methacrylate (HEMA) thick films were investigated by photo-differential scanning calorimetry (DSC) under UV irradiation (365 nm). It was found that the reaction rate was affected by the ZrO2 fillers. Kamal equation was proposed to descrip the conversion profile dependent on the UV irradiation time. It showed an excellent agreement with the experimental results before vitrification. The glass transition temperature of the thick films were from about 88 to 95oC, and the temperature at 5% weight loss determined by a TGA were from 300 to 333oC, which were dependent on the composition.The photo- DSC was further coupled with a blue light LED (450nm) to study the photopolymeriz ation of the HEMA monomers under different amounts of photoinitiator: Irgacure 819. The Kamal equation was adopted for the kinetic model of the photopolymerization under blue light irradiation.

摘要 i
Abstract ii
誌謝 iii
目錄 iv
圖目錄 vi
表目錄 xi
第一章 緒論 1
1.1前言1
1.2 研究動機4
第二章 文獻回顧 5
2.1光聚合樹脂主要成分5
2.1.1活性寡聚物(Reactive oligomer) 5
2.1.2活性單體(Reactive monomer) 7
2.1.3光起始劑(photoinitiator) 8
2.1.3.1光起始劑原理8
2.1.3.2光起始劑種類9
2.1.3.3 光起始劑AIBN簡介13
2.1.3.4光起始劑Ciba®Irgacure 819簡介13
2.1.4填充劑14
2.2氧氣的抑制作用14
2.3快速成型技術簡介15
2.4光聚合動力學之相關文獻16
2.5光聚合動力學模式之相關文獻26
2.6光聚合動力學簡介33
2.6.1動力學模式33
2.6.2光起始自由基聚合反應機構模式36
2.6.3凝膠效應38
2.6.4 自由基聚合反應41
2.6.4.1 線性系統41
2.6.4.2 交聯系統43
第三章 實驗方法 46
3.1實驗藥品46
3.2實驗儀器48
3.3實驗流程50
3.4樣品製備51
3.5測試方法51
第四章 結果與討論 55
4.1 傅立葉轉換紅外光譜儀分析55
4.2 光聚合動力學分析56
4.2.1 氧化鋯含量及光起始劑濃度對光聚合反應之影響58
4.2.2 光聚合動力學模式分析60
4.3 後硬化厚膜熱性質分析61
4.4 硬化厚膜SEM形態分析62
4.5 熱穩定性質分析63
第五章 結論 92
符號表 93
參考文獻 94
附錄A 102
附錄B 106

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