臺灣博碩士論文加值系統

本研究合成之次微米二氧化矽非晶之粒徑以動態光散射介面電位與粒徑分析儀(DLS)鑑定後，其平均粒徑為0.3±0.15 μm，吾人以此二氧化矽為核，先以三甲氧矽烷丙基甲基丙烯酸(MPS)修飾二氧化矽表面，再與高分子單體甲基丙烯酸丁酯(BMA)聚合，製得有機/無機複合粒子(簡稱SMB)。由傅立葉轉換紅外線光譜儀(FT-IR)、固態核磁共振質譜儀(SSNMR)以及熱重與熱差分析儀(TG/DTA)分析得知，二氧化矽表面之MPS修飾量最多為22%，而BMA與MPS的接枝率最高為67%。進一步將SMB作為模板，無水氯化鋁作為鋁前驅物，在SSNMR與化學分析電子儀(ESCA)的分析結果發現，模板SMB與無水氯化鋁改質後，於固態27Al-NMR圖譜發現兩個峰值，分別位於-0.7與12.7 ppm，顯示粒子中含有鋁的成分且鋁是以六配位與五配位的離子形式存在；由ESCA全能譜圖分析，得知有機/無機複合模板上有Al元素之訊號，於Al2p之窄能譜圖得知Al元素鍵結屬於Al2O3鍵。綜合以上兩組分析，顯示吾人自製之有機/無機複合粒子經無水氯化鋁改質後存在鋁離子之鍵結。將此鋁改質模板於空氣氣氛以1000 oC煅燒兩小時，以場發射掃描式電子顯微鏡(SEM)與能量散射光譜儀(EDS)分析，顯示獲得二氧化矽/氧化鋁核殼結構複合粒子，若進一步以氫氟酸移除二氧化矽核，由穿透式電子顯微鏡(TEM)、擇區繞射(SAD) 與X光繞射分析儀(XRD)觀察，吾人獲得γ-氧化鋁中空結構。藉由比表面積及孔徑分析儀(BET)分析，氧化鋁中空結構之BET比表面積為78.6 m2/g，以Horvath-Kawazoe孔徑分佈模型，氧化鋁多孔結構同時具有微孔(1.35 nm)與介孔(2.23 nm)洞。

Submicrometer silica (SiO2) particles with an average diameter of 0.3±0.15 μm determined from the dynamic light-scattering technique (DLS) were grafted by 3-trimethoxysilyl propyl methacrylate (MPS) to form silica/MPS, hereafter termed SM, followed then by polymerization of butyl methacrylate (BMA) to form silica/MPS/BMA, hereafter termed SMB, hybrid particles. The highest MPS and BMA grafting degrees are 22% and 67%, respectively, determined by Fourier-transform infrared spectrometry (FTIR), solid-state nuclear magnetic resonance spectrometry (SSNMR), and thermogravimetric/differential thermal analysis (TG/DTA).
When the SMB hybrid particles were used as a template, anhydrous aluminum chloride as a precursor for alumina (Al2O3), and tetrachloroethylene as a reactive solvent, the SMB particles showed existence of 5- and 6-coordinated aluminum peaks by SSNMR. The aluminum signals were also confirmed by the electron spectroscopy for chemical analysis (ESCA).
Field-emission scanning electron microscopy (FE-SEM) and Energy Dispersive Spectrometry (EDS) showed that SiO2@Al2O3 structure is obtained after calcination at 1000 oC in air atmosphere from the silica/MPS/BMA/Al hybrid particles. Removal of the SiO2 core via acid etching showed hollow Al2O3 structure from transmission electron microscopy (TEM), selective area diffraction (SAD), and X-ray diffraction (XRD). The hollow Al2O3 structure showed a B.E.T. specific surface area of 78.6 m2/g and a mixture of micro- and meso-pores by the Horvath-Kawazoe model.

第一章 緒論…………………………………………………1
1-1 前言…………………………………………………1
1-2 研究動機……………………………………………1
第二章 文獻回顧……………………………………………3
2-1 溶膠凝膠法概論……………………………………3
2-2 利用溶膠凝膠法製備有機無機混合物……………3
2-2-1 次微米二氧化矽……………………………………3
2-2-2 矽烷耦合劑…………………………………………3
2-2-3 矽烷耦合劑與二氧化矽表面之反應………………4
2-3 矽烷耦合劑在水解-縮合反應中主要影響因素……5
2-3-1 pH值的影響…………………………………………5
2-3-2 水含量的影響………………………………………6
2-3-3 溶劑比例的影響……………………………………6
2-3-4 烷氧基(Alkoxy Group)的影響……………………6
2-3-5 誘導效應(Inductive Effect)之影響……………7
2-4 分散聚合法的歷史發展……………………………7
2-5 分散聚合法之反應與成核機制……………………8
2-6 影響分散聚合因素之探討…………………………9
2-6-1 起始劑的影響………………………………………9
2-6-2 穩定劑的影響………………………………………9
2-6-3 溫度的影響…………………………………………9
2-6-4 溶劑的影響…………………………………………10
2-7 以有機模板合成無機氧化物………………………10
2-8 以不同種類之硬模板合成氧化鋁中空球…………11
2-8-1 以PS球為合成氧化鋁中空球之模板………………11
2-8-2 以碳球為合成氧化鋁中空球之模板………………12
2-8-3 以商用聚苯乙烯微球為合成無機氧化物之模板…13
第三章 實驗流程與分析儀器介紹…………………………22
3-1 實驗藥品……………………………………………22
3-2 製程設備……………………………………………23
3-3 以自製有機無機複合模板合成氧化鋁空心結構之一貫實驗流程………………………………………………………………24
3-4 Stöber法合成silica之實驗流程…………………25
3-5 以2.26 M甲基磺酸改質二氧化矽之實驗流程……26
3-6 合成二氧化矽與MPS之混合物(SM)實驗流程………27
3-7 合成二氧化矽、MPS與BMA之混合物(SMB)實驗流程…29
3-8 以SMB合成二氧化矽/氧化鋁核殼結構與氧化鋁中空結構30
3-9 分析儀器……………………………………………31
第四章 結果與討論…………………………………………33
4-1 次微米二氧化矽球之晶相與顯微結構分析………33
4-1-1 次微米二氧化矽球之晶相分析(XRD)………………33
4-1-2 次微米二氧化矽球之顯微結構分析(SEM)…………34
4-1-3 次微米二氧化矽球之粒徑分析(DLS)………………34
4-2 經MPS表面修飾之二氧化矽(SM)之物理化學性質分析…35
4-2-1 改變pH值對MPS接枝量的影響………………………35
4-2-2 改變反應溫度對MPS接枝量的影響…………………38
4-2-3 改變MPS添加濃度對MPS接枝量的影響………………40
4-2-4 MPS在二氧化矽表面修飾的SSNMR分析………………45
4-3 SM與BMA的聚合之物理化學性質分析………………46
4-3-1 二氧化矽表面的FTIR官能基分析……………………46
4-3-2 二氧化矽表面的SSNMR官能基分析…………………48
4-3-3 SMB之表面顯微結構分析……………………………49
4-4 二氧化矽/氧化鋁核殼結構與氧化鋁中空結構……51
4-4-1 無水氯化鋁改質後有機/無機複合粒子SMB之SSNMR鋁離子結構分析…………………………………………………………51
4-4-2 無水氯化鋁改質後有機/無機複合粒子SMB之ESCA分析…51
4-4-3 二氧化矽/氧化鋁核殼結構…………………………53
4-4-4 氧化鋁中空結構………………………………………55
4-4-5 氧化鋁中空微球之比表面積分析(BET)……………57
4-5 試作氧化鐵中空結構可行性分析……………………59
第五章 結論……………………………………………………62
參考文獻 …………………………………………………………63

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