Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3615
標題: 規則樹枝狀聚合物-多立面倍半矽氧烷寡聚體有機無機奈米混成材料的製備、分析與形態鑑定
Synthesis, Characterization and Morphology Study of Dendrimer-Polyhedral Oligomeric Silsesquioxane (POSS) Organic-Inorganic Nanohybrids
作者: 張耕培
Chang, Gung-Pei
關鍵字: Organic-inorganic nanohybrids
有機無機奈米混成材料
Dendrimer
POSS
Morphology study.
規則樹枝狀聚合物
多立面半倍矽氧烷寡聚體
形態學
出版社: 化學工程學系所
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摘要: 本研究是以Azetidine-2,4-dione與脂肪族一級胺的開環加成反應來製備新穎啞鈴形結構的Dendrimer-POSS有機無機奈米混成材料,有機dendrimer的末端結構分別為苯環(Phenyl/Malonamide Dendrimer-POSS)以及長碳鏈(Decyl/Malonamide Dendrimer-POSS)。Dendrimer-POSS奈米混成材料經傅立葉紅外光譜儀、質子核磁共振光譜儀、質譜儀、凝膠滲透層析儀、元素分析與能量分散式X-ray光譜儀等儀器分析證明其結構正確。 在溶解度方面,由於POSS的導入,降低Dendrimer-POSS奈米混成材料的極性,因此對低極性溶劑有優良溶解度,如氯仿、甲苯與正己烷。 Dendrimer-POSS奈米混成材料經由紅外光譜的分析,顯示具有分子間氫鍵的存在,而此二次鍵結造成PM-G1-POSS的玻璃轉移溫度高於PM-G1,但其他Dendrimer-POSS奈米混成材料受到結構因素(分子結構對稱性或分歧程度)影響,其玻璃轉移溫度則低於相對的有機dendrimer。除了玻璃轉化態,DM-G1-POSS具有再結晶態與熔化態,顯示POSS有促於其結晶形成。Dendrimer-POSS奈米混成材料的熱穩定性則因分子結構(分歧程度與分子量)及有機無機分子間交互作用力的綜合影響下,顯得較無趨勢。 Dendrimer-POSS奈米混成材料的形態分析透過廣角X-ray繞射儀、場發射掃描式電子顯微鏡、高解析穿透式電子顯微鏡與原子力顯微鏡。WAXD顯示Dendrimer-POSS奈米混成材料具有POSS的部分結晶特性,但其結晶程度則隨著有機dendrimer代數增加而下降。FE-SEM顯示PM-G1-POSS與DM-G1-POSS的膜表面形態較為粗糙,而PM-G2-POSS與DM-G2-POSS則為緻密平滑的膜表面形態。HR-TEM顯示PM-G1-POSS與DM-G1-POSS皆會形成奈米層板結構。 Dendrimer-POSS奈米混成材料於矽晶圓上的表面形態則取決於塗布溶劑的種類,以質子型高極性溶劑異丙醇(IPA)為塗布溶劑,Dendrimer-POSS奈米混成材料在矽晶圓上形成球形顆粒的表面形態;以次極性醚類溶劑四氫呋喃(THF)為塗布溶劑則可得到類似蜂窩狀的規則孔洞表面,而後將試片回火處理(Annealing process),其規則孔洞消失,PM-G2-POSS形成規則排列;以低極性溶劑甲苯(Toluene)則可將部分樣品平坦的塗布於矽晶圓上,顯示Dendrimer-POSS奈米混成材料可透過溶劑的選擇與後續的回火處理進而控制其表面形態。
Novel dumbbell shape dendrimer-POSS organic-inorganic nanohybrids were prepared in this study by ring-opening addition reaction of azetidine-2,4-dione and aliphatic primary amine. The periphery structures of organic dendrimer were phenyl ring (Phenyl/Malonamide Dendrimer-POSS) and long alkyl chain (Decyl/Malonamide Dendrimer-POSS) respectively, and the structures were also confirmed by FT-IR, 1H NMR, MS, GPC, elementary analysis (EA) and energy dispersive X-ray (EDX). These dendrimer-POSS nanohybrids showed good solubility in common organic solvents such as chloroform, toluene and n-hexane. Intermolecular hydrogen bonding interactions were observed in dendrimer-POSS nanohybrids through FT-IR analyses. Such secondary bonding would upgrade the Tg of PM-G1-POSS as compared to that of PM-G1. However, other organic-inorganic nanohybrids did not exhibit similar thermal behavior because of the structural effect. In particular, DM-G1-POSS possessed re-crystalized state and a melting point was observed nearby the glass transition state in DSC analysis. It is believed that POSS would promote the re-crystalization of DM-G1-POSS. In morphology study, for PM-G1-POSS and DM-G1-POSS, the diminished characteristic diffraction peaks of POSS were present in WAXD. The degree of diminishing characteristic diffraction peak was increased with increasing dendritic generation. The FE-SEM micrographs of fractured surfaces of PM-G1-POSS and DM-G1-POSS showed rougher morphology than those of the higher generation of dendrimer-POSS nanohybrids. The two-dimensional multilayered structures were also observed for PM-G1-POSS and DM-G1-POSS in HR-TEM images. The surface morphology of dendrimer-POSS nanohybrids on silicon wafer was highly dependent on spin-coating solvent type. Spherical aggregations were observed when IPA was used as the spin-coating solvent. Regular porous surfaces were induced when THF was used as the solvent. In addition, the spin-coated films of PM-G2-POSS were capable of self-assembling into regular shape after annealing. On the other hand, flat dense films on silicon wafer were obtained for PM-G1-POSS and DM-G1-POSS, but porous surface were acquired for DM-G2-POSS, when toluene was used as the solvent. Therefore, it is believed that morphology could be tailored through selection of solvents for spin-coating process, or annealing process.
URI: http://hdl.handle.net/11455/3615
其他識別: U0005-0608200713553000
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