多壁奈米碳管-纖維強化乙烯基樹脂複合材料之製備及其機械性質之研究

Preparation and Mechanical Properties of Multiwalled Carbon nanotube-fiber Reinforced Vinyl Ester Composites

蔡運邦(Yun-Pang Tsai)

指導教授 ： 馬振基

國立清華大學/工學院/化學工程學系/碩士(2012年)

摘要

本研究旨在探討多壁奈米碳管(MWCNT)與氧化石墨烯(GO)對於玻璃纖維/乙烯酯樹脂(GF/VE)及碳纖維/乙烯酯樹脂(CF/VE)在機械強度上的影響，並比較多壁奈米碳管經不同表面改質方法後，於高分子材料中的相容性。
將P-MWCNT、TEVOS-MWCNT及Allyl-MWCNT加至玻璃纖維/乙烯酯纖維複合材料當中，玻璃纖維強化乙烯酯複合材料的拉伸強度由227.5MPa提升為254.06MPa (1phr MWCNT/GF/VE)、 258.55MPa (1phr TEVOS-MWCNT/GF/VE)與275.45MPa (1phr Allyl-MWCNT/GF/VE)；玻璃纖維強化乙烯酯複合材料的破裂韌性由0.76kJ/m2，降為0.73kJ/m2 (1phr P-MWCNT/GF/VE)，而改質碳管的強度分別提升為0.94kJ/m2 (1phr TEVOS-MWCNT/GF/VE)與1.07kJ/m2 (1phr Allyl-MWCNT/GF/VE)，因具有官能基與樹脂有較好的界面作用力，可以提升纖維層與層之間的強度，使材料的裂縫成長速度下降，提升材料的破裂韌性。
玻璃纖維強化乙烯酯複合材料玻璃轉移溫度(Tg)由89.05oC，提升為106.78oC (1phr P-MWCNT/GF/VE)、107.70oC (1phr TEVOS-MWCNT/GF/VE)及109.70oC (1phr Allyl-MWCNT/GF/VE)。多壁奈米碳管可以阻礙材料之高分子鏈段運動， Allyl-MWCNT及TEVOS-MWCNT除了能阻斷的高分子鏈運動外，與樹脂間具有較強的界面作用力，提高纖維與樹脂之間之界面相容性，故能夠大幅提昇複合材料系統的熱穩定性。
將P-MWCNT、TEVOS-MWCNT、Allyl-MWCNT及GO加至碳纖維/乙烯酯纖維複合材料當中，碳纖維強化乙烯酯複合材料的拉伸強度由369.45MPa，提升為448.68MPa (1phr P-MWCNT/CF/VE)、465.15MPa (1phr TEVOS-MWCNT/CF/VE)、476.45MPa (1phr Allyl-MWCNT/CF/VE)及，505.04MPa(1phr GO/CF/VE)，加入1phr氧化石墨烯的碳纖維強化乙烯酯複合材料有最佳強度。碳纖維複合材料的抗折強度為272.45MPa，當加入1phr P-MWCNT時，其強度會提昇至501.53MPa，而加入1phr的TEVOS-MWCNT與Allyl-MWCNT時，其強度分別為511.45MPa與521.56MPa，而最佳表現值為加入1phr氧化石墨烯，其值為558.07MPa。碳纖維強化乙烯酯複合材料的破裂韌性由0.80kJ/m2，提升為0.91kJ/m2 (1phr P-MWCNT/CF/VE)、1.04kJ/m2 (1phr TEVOS-MWCNT/CF/VE)及1.07kJ/m2 (1phr Allyl-MWCNT/CF/VE)。碳纖維強化乙烯酯複合材料玻璃轉移溫度(Tg)由98.18oC，提升為114.33oC (1phr P-MWCNT/CF/VE)、 115.67oC (1phr TEVOS-MWCNT/CF/VE)與116.67 oC (1phr Allyl-MWCNT/CF/VE)。

關鍵字

碳纖維 ； 玻璃纖維 ； 多壁奈米碳管 ； 乙烯酯樹脂 ； 纖維強化複合材料

並列摘要

In this study, Multi-walled carbon nanotube(MWCNT) was modified with different methods. The Allyl-MWCNTs were prepared via free radical reaction with allylamine, which contains the ethylene groups for increase interaction between MWCNTs and vinyl ester (VE). The TEVOS was grafted on the MWCNTs surface to prepare MWCNT-TEVOS.
From the mechanical properties study, the tensile strength of glass fiber/vinyl ester was increased from 227.5MPa to 254.06MPa when 1phr P-MWCNT content was added to neat GF/VE composite. The tensile strength of GF/VE composites was increased to 258.55 MPa (with 1phr TEVOS-MWCNT) and to 275.45MPa (with 1phr Allyl-MWCNT). Modified MWCNT can improve the tensile strength of the GF/VE than that was added with unmodified MWCNT. The fracture toughness (GIC) of GF/VE composites was increased from 0.76 kJ/m2 (neat GF/VE) to 0.83kJ/m2 (with 0.25 phr MWCNT) and to 0.94 kJ/m2 (with 1.0phr TEVOS-MWCNT) and to 1.07 kJ/m2 (with 1.0phr Allyl-MWCNT). Allyl-MWCNT possesses the best interface bonding between fiber and matrix that exhibits best fracture toughness of these three kinds of composites. The Tg of GF/VE composite was 89.05℃. The GF/VE composite with 1phr TEVOS-MWCNT and Allyl-MWCNT shows the Tg which was 107.70℃, and 109.70℃ respectively. It indicated that thermal stability of composite can be improved even when a small quantity of functionalized MWCNTs was added

From the mechanical properties study, the tensile strength of carbon fiber/vinyl ester was increased from 369.45MPa to 448.68MPa when 1phr P-MWCNT content was added to neat CF/VE composite. The tensile strength of CF/VE composites increased to 465.15MPa (with 1phr TEVOS-MWCNT) and to 476.45MPa (with 1phr Allyl-MWCNT). Modified MWCNT can improve the tensile strength of the CF/VE than that of unmodified MWCNT/CF/VE composite. The GO/CF/VE composites show the best tensile strength, which were 505.04MPa with 1 phr filler content. The flexural strength of CF/VE composites was increased from 272.45MPa (neat GF/VE) to 501.53 MPa (with 1.0 phr MWCNT) and to 511.45MPa (with 1.0phr TEVOS-MWCNT) and to 521.56MPa (with 0.5phr Allyl-MWCNT).Allyl-MWCNT/CF/VE composite possesses better flexural strength than that of unmodified MWCNT/CF/VE. The GO/CF/VE composites show the best flexural strength, which was 558.07MPa with 1 phr filler content. The fracture toughness (GIC) of CF/VE composites increased from 0.80 kJ/m2 (neat CF/VE) to 0.95kJ/m2 (with 0.5 phr MWCNT) and to 1.04 kJ/m2 (with 1.0phr TEVOS-MWCNT) and to 1.07 kJ/m2 (with 1.0phr Allyl-MWCNT). Allyl-MWCNT/CF/VE exhibits the best fracture toughness due to the improvement of interface bonding between fiber and matrix. The Tg of CF/VE composite was 98.18℃. The CF/VE composite with 1phr TEVOS-MWCNT and Allyl-MWCNT shows the Tg which was 115.67℃, and 116.67℃respectively. It indicated that thermal stability of composite can be improved even when a small quantity of functionalized MWCNTs was added.

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