臺灣博碩士論文加值系統

本研究之目的在尋找具高燃速與高抗壓強度之高分子膠料，以做為未來進一步開發推進劑藥柱之可燃模心時之參考。所採之高分子膠料為硬質聚氨基甲酸酯泡綿/過氯酸銨系統。實驗結果証實經由適當的調整配方中所含二元醇/三元醇之含量比、混合催化劑之組成及發泡劑之種類及用量，可以獲得發泡良好且抗壓強度(＞2kg/㎝2)滿足需求之泡綿。此外，以第三丁醇來取代水做為發泡劑，除可避免在製作易燃性泡綿時具吸濕性的氧化劑與水作用外，亦能製得性能相當的泡綿。以烘烤方式製備之多孔性過氯酸銨的比表面積與真密度等物性受烘烤溫度與烘烤時間影響，烘烤溫度愈高與烘烤時間愈長，得到多孔性過氯酸銨的比表面積與真密度愈大。就多孔性過氯酸銨之熱分解而言，示差熱分析結果顯示其無論第一尖峰分解溫度與第二尖峰分解溫度均較過氯酸銨為低，意謂多孔性過氯酸銨與過氯酸銨相比可在較低之溫度即行分解，故以多孔性過氯酸銨取代泡綿中部份過氯酸銨，將有助於泡綿之熱分解進行，提高泡綿之燃速。此外，選擇對發泡物性及增燃效果有利的Butacene及Alex組合做為燃速促進劑，得到的易燃性泡綿燃速為傳統推進劑燃速的5倍。另再以經矽烷偶合劑包覆之超微粒過氯酸銨製作含50%氧化劑的易燃性泡綿，不但燃速可達傳統推進劑的10倍，並有更好的拌製物性。燃速亦受發泡密度影響，泡綿密度愈高，其燃速則愈慢，故採模具澆注發泡控制密度在0.21∼0.23g/㎝3。此等易燃性泡綿之燃速壓力指數值均僅約0.2左右，遠低於傳統推進劑之壓力指數值。

In order to develop a high burning rate material for further using in rocket motor fabrication, a series of rigid polyurethane (PU) / ammonium perchlorate (AP) foam were made in this study. The characteristics of these PU/AP foams were also investigated. Our results show that the PU foam which has the required compressive strength (> 2kg/cm2) can be made by adjusting the relative amount of binary alcohol to ternary alcohol, the composition of the mixed catalyst and by changing the kind and amount of the blowing agent. The burning rate of PU foam is dependent on the foaming density, oxidizer and burning rate catalyst. The higher the density of PU foam is, the lower the burning rate it has. Replacing part of AP with porous AP or ultra-fine AP enhances the burning rate of PU foam. Particularly, the burning rate of PU foam increases tremendously when using a catalyst system composed of Butacene and ultra-fine aluminum powder (ALEX) as well as silane treated ultra-fine AP. The pressure exponents of burning rate for these flammable foams are only about 0.2 which is much lower than that of the traditional propellant.

誌謝ii
摘要iii
ABSTRACTv
目錄vi
表錄x
圖錄xii
1.前 言…………………………………………………………………1
2.文獻回顧………………………………………………………………3
3.理論背景………………………………………………………………12
3.1.硬質發泡材料製造………………………………………………12
3.1.1.聚醇(Polyol)…………………………………………………13
3.1.2.二異氰酸酯(Diisocyanate)…………………………………14
3.1.3.發泡劑(Blowing Agent) ……………………………………16
3.1.4.催化劑(Catalyst)……………………………………………16
3.1.5.界面活性劑(Surfactant)……………………………………17
3.2.易燃材質製造……………………………………………………18
3.2.1.泡綿燃燒………………………………………………………18
3.2.2.氧化劑…………………………………………………………18
3.2.3.燃速調節劑……………………………………………………20
3.2.4.燃燒化學………………………………………………………22
4.實驗部份………………………………………………………………28
4.1.實驗材料及葯品…………………………………………………28
4.2.儀器設備…………………………………………………………29
4.3.硬質PU發泡製作…………………………………………………30
4.3.1.聚醇除水………………………………………………………30
4.3.2.PU發泡…………………………………………………………30
4.3.3.熟化……………………………………………………………31
4.4.多孔性過氯酸銨(PAP)製作 ……………………………………31
4.5.超細粒徑過氯酸銨(VFAP)表面改質……………………………32
4.6.易燃性泡綿製作…………………………………………………32
4.7.含燃速促進劑易燃性泡綿製作…………………………………32
4.8.物性測試…………………………………………………………33
4.8.1.含燃速促進劑葯漿黏度量測…………………………………33
4.8.2.尺寸收縮率量測………………………………………………33
4.8.3.密度、抗壓強度測試…………………………………………33
4.8.4.永久變形率及硬度測試………………………………………34
4.8.5.燃速測試………………………………………………………34
5.結果與討論……………………………………………………………35
5.1.硬質PU泡綿配方…………………………………………………35
5.2.硬質PU泡綿物性與機械性質量測………………………………36
5.3.PAP製作 …………………………………………………………38
5.3.1.PAP比表面積、真密度及顯微攝影 …………………………38
5.3.2.PAP熱分析 ……………………………………………………44
5.4.易燃性泡綿測試…………………………………………………47
5.4.1.配方選擇………………………………………………………47
5.4.2.易燃性泡綿物性分析…………………………………………48
5.4.3.易燃性泡綿熱分析測試………………………………………49
5.4.4.燃速測試結果…………………………………………………54
5.5.含燃速促進劑易燃性泡綿測試…………………………………57
5.5.1.配方選擇………………………………………………………57
5.5.2.含燃速促進劑易燃性泡綿物性分析…………………………59
5.5.3.含燃速促進劑易燃性泡綿熱分析測試………………………64
5.5.4.含燃速促進劑易燃性泡綿燃速測試結果……………………71
6. 結 論 ……………………………………………………………………75
參考文獻………………………………………………………………………77
自 傳…………………………………………………………………………87

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