研究生: |
王妤榛 Yu-Jhen Wang |
---|---|
論文名稱: |
矽烷偶合劑接枝之氧化石墨烯及熱脫層氧化石墨烯之合成及探討奈米級及次微米級核殼型橡膠添加劑、無機二氧化矽核殼型顆粒、氧化石墨烯及熱脫層氧化石墨烯及反應型微膠顆粒對乙烯基酯樹脂之體積收縮、機械性質、微觀型態結構及X光散射特性之影響 Synthesis of silane-grafted graphene oxide (sg-GO) and silane-grafted thermally reduced graphene oxide (sg-TRGO), and effects of nano-scale and submicron-scale core-shell rubber additives, inorganic silica nanoparticles, GO, TRGO, and reactive microgel particle on the volume shrinkage, mechanical properties, cured sample morphology, and X-ray scattering characteristics for vinyl ester resins |
指導教授: |
黃延吉
Yan-Jyi Huang |
口試委員: |
邱文英
Wen-Yen Chiu 陳崇賢 Chorng-Shyan Chern |
學位類別: |
碩士 Master |
系所名稱: |
工程學院 - 化學工程系 Department of Chemical Engineering |
論文出版年: | 2016 |
畢業學年度: | 104 |
語文別: | 中文 |
論文頁數: | 243 |
中文關鍵詞: | 氧化石墨烯 、熱還原氧化石墨烯 、矽烷接枝之氧化石墨烯 、矽烷接枝之熱脫層氧化石墨烯 、聚合固化 、接枝效率 |
外文關鍵詞: | graphene oxide, silane-grafted graphene oxide, thermally reduced graphene oxide, silane-grafted thermally reduced graphene oxide, curing, grafting efficiency |
相關次數: | 點閱:425 下載:8 |
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本文探討添加氧化石墨烯(GO)、低接枝密度之矽烷接枝氧化石墨烯(LD-sg-GO)、高接枝密度之矽烷接枝氧化石墨烯(HD-sg-GO)、熱脫層氧化石墨烯(TRGO)以及矽烷接枝之熱脫層氧化石墨烯(sg-TRGO)等數種特用添加劑的合成及其對苯乙烯(St)/乙烯基酯(VER)/特用添加劑三成份系統於120 oC恆溫固化之微觀型態結構、體積收縮特性及機械性質的影響。
熱脫層氧化石墨烯(TRGO)是將氧化石墨烯(GO)置於1050 oC的高溫爐中30 sec合成而得;後者,則是將平均粒徑為2至15微米的天然石墨粉以改良的Hummers法製得。矽烷接枝氧化石墨烯(sg-GO)係以帶有壓克力不飽和C=C雙鍵的矽烷偶合劑,即甲基丙烯酰氧丙基三甲氧基矽烷(MPS),做為表面改質劑,在GO/MPS/溶劑三者的重量比於1:5:94下,並在不同反應溫度(60 oC-100 oC)及時間(1.5 hr-48 hr)、不同使用溶劑(如甲苯、乙醇以及二甲基甲醯胺)及不同反應次數下(一或三次反應,以進行GO之表面處理),對氧化石墨烯(GO)進行表面處理而得。兩種矽烷接枝氧化石墨烯,包刮低接枝密度(LD-sg-GO)及高接枝密度(HD-sg-GO)。吾人以傅立葉轉換紅外光分析儀(FTIR)的定量測得之接枝密度分別為112 mmole MPS/100 g GO及492 mmole MPS/100 g GO。至於矽烷接枝熱脫層氧化石墨烯(sg-TRGO),吾人以FTIR所測得之接枝密度為83 mmole MPS/ 100 g TRGO。
視GO的種類及添加量(GO及sg-GO之添加量為0.5 wt%-5.0 wt%,而TRGO及sg-TRGO之添加劑為0.5 wt%-1.0 wt%),添加GO於VER樹脂中,其聚合固化後之體積收縮會有不同程度的降低效果。通常,添加GO量愈大,聚合固化後之體積收縮亦愈小。在本研究的四種不同添加劑中,包括GO、sg-GO、TRGO以及sg-TRGO,在固定的添加量下,以sg-TRGO及TRGO為添加劑的抗體積收縮效果最好,sg-GO系次之,GO系則是最差。5.0 wt% GO系及0.5 wt% sg-GO系,其抗體積收縮的表現相近,而0.5 wt% sg-TRGO系及0.5 wt% TRGO系,其抗體積收縮效果較0.5 wt% sg-GO系為佳。本研究中,吾人發現添加0.5 wt% TRGO、0.5 wt% sg-TRGO或1.0 wt% sg-TRGO這三個系統,其在St/VER(n=2)/添加劑三成份係於120 oC聚合固化之體積收縮控制的效果最佳。而這三個系統中,以添加1.0 wt% sg-TRGO三成份系的機械性質表現最佳,其楊氏模數與純VER(n=2)樹脂系相較,增加10%,抗張強度僅減小5%,而耐衝擊強度大增100%。
The effects of graphene oxide (GO), low grafting density silane-grafted graphene oxide (LD-sg-GO), high grafting density silane-grafted graphene oxide (HD-sg-GO), thermally reduced graphene oxide (TRGO), and silane-grafted thermally reduced graphene oxide (sg-TRGO) as special addities on the cured sample morphologies, volume shrinkage characteristics and mechanical properties for low-shrink vinyl ester resins (VER) cured at 120 oC were investigated.
The TRGO was produced by placing the GO in a high-temperature furnace kept at 1050 oC for 30 s, which was synthesized from natural graphites with average particle size of 2 to 15 μm by a modified Hummers method. The sg-GO was synthesized by using the silane coupling agent bearing acrylic C=C bonds, namely, γ-methacryloxy propyl trimethoxy silane (MPS), as a surface modifier for the surface treatment of GO at varied reaction temperatures (60 oC-100 oC) and reaction times (1.5 hr-48 hr), with different times of reaction for surface treatment between GO and MPS (n=1 or 3), using different reagents, such as toluene, ethanol and dimethyl formamide, as the solvent and with a fixed weight ratio of GO/MPS/solvent at 1:5:94, where the grafting density was 112 mmole MPS/100 g GO and 492 mmole MPS/100 g GO for low grafting density of silane-grafted GO (LD-sg-GO) and high grafting density of silane-grafted GO (HD-sg-GO), respectively, as measured by FTIR. As for the silane-grafted TRGO (sg-TRGO), the grafting density was 83 mmole MPS/100 g TRGO, as measured by FTIR.
Depending on the type of GO and their contents (0.5 wt% to 5.0 wt% for GO and sg-GO, and 0.5 wt% to 1.0 wt% for TRGO and sg-TRGO) added, the GO could lead to a reduction of volume shrinkage after the cure to differing degrees. In general, a higher content of GO may result in a lower volume shrinkage after cured. Among the four additives studied in this work, namely, GO, sg-GO, TRGO, and sg-TRGO at a fixed content of additive, sg-TRGO and TRGO would result in the best volume shrinkage control, followed by sg-GO and GO. The performance of volume shrinkage control was quite close to each other for the 5.0 wt% GO and the 0.5 wt% sg-GO systems, whereas the 0.5 wt% sg-TRGO system and 0.5 wt% TRGO system could lead to a better volume shrinkage control than the 0.5 wt% sg-GO system. In this work, it has been found that adding 0.5 wt% of TRGO, 0.5 wt% of sg-TRGO or 1.0 wt% sg-TRGO as the LPA for the St/VER(n=2)/additive ternary system during the cure at 120 oC is the best recipe for a good volume shrinkage control, which exhibited a fractional volume shrinkage of 2.6%, about one half of that for the neat VER cured system. However, the 1.0 wt% sg-TRGO ternary system would possess the best mechanical properties, exhibiting a slight increase of 10% in Young’s modulus, and a slight decrease of 5% in tensile strength, and a 100% increase in impact strength, when compared with that of neat VER(n=2) cured system.
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