本研究主要主旨著重在氧代氮代苯并環已烷(Benzoxaine)與改質環氧樹脂混摻作為高分子基材主體。之後於高分子基材中添加石墨烯(Graphene)與短碳纖維(Short carbon fiber)之補強材，目的主要是為了探討其奈米尺度跟微米尺度補強材之補強效果，並強化多尺度混摻後之介面特性、以提高機械與疲勞性質。實驗中主要探討下量因素對材料之影響: (1)Benzoxaine對環氧樹脂的添加量、(2)奈米等級石墨烯與微米等級短碳纖維織之添加量、(3)多尺度混摻之複合材料的添加量
高分子複材研究指出添加20wt%Benzoxaine可顯著提高環氧樹脂基材之機械強度:拉伸強度提升21.37%、彎曲強度提升33.45%、彎曲模數提升13.86%，吸濕阻水率提升38.03%，但Benzoxaine屬於硬脆型材料，導致衝擊性質下降了55%。
當20wt%Benzoxaine/環氧樹脂複合材料添加奈米等級石墨烯則指出，0.5wt%GNPs添加量拉伸強度提升14.18%、吸濕阻水率提升22.83%;0.25wt%GNPs添加量彎曲強度提升了2.46%、彎曲模數上升8.05%。另外一方面，添加了微米等級短碳纖維則指出8wt%添加量有最好的機械性質:彎曲強度上升了22.93%，吸濕阻水率上升了9.84%.。
最後研究顯示GNPs-0.5wt%/SF-8wt%/Benzoxazine/環氧樹脂複合材料有最好的提升:拉伸提升22.62%、彎曲強度提升12.2%、衝擊強度提升39.07%、扭轉疲勞壽命提升了3.2到3.8倍，但因短碳纖維在加載過程會在纖維末端產生大量微裂紋，從而降低其延展性，彎曲模數反而下降33.84%。

This study is focuses on the characteristics of the benzoxazine/epoxy copolymer matrix, combined thegraphene and micro-scale short carbon fibers to be reinforcement. In order to investigate the reinforced mechanism of the nano-scale and micro-scale additive, the interfacial properties, mechanical behavior, and fatigue failure would be realized on the mulit-scale reinforced composite. The researches includes: (1) Different contents of benzoxazine resin in Epoxy resin, (2) graphene and Micro-scale short carbon fibers concentration, (3) the interaction of multi-scale reinforcement material concentration
This research aims to discuss the effect of the mixture of nano-scale graphene and micro-scale short carbon fiber, notably intensifies the the mixture of multi-scale interface, improving and increasing both mechanical properties and dynamic fatigue life. The investigation includes:(1)Different Benzoxazine resin concentration in Epoxy,(2)Nano-scale graphene and Micro-scale short carbon fibers concentration.(3)Multi-scale reinforcement material concentration.
In the matrix experiment, the results indicate that the value of mechanical strength increases with the content of benzoxazine increased. From the results, the 20wt% benzoxazine/epoxy significantly improves the mechanical strength up to 21.37% improvement in tensile strength; 33.45% improvement in flexural strength; 13.86% improvement in flexural modulus; 38.03% improvement in resistance of water absorption.
However, because of the property benzoxazine is more brittle than epoxy, the impact strength of benzoxazine/epoxy copolymer reduces about 55%.
The research shows that addition of graphene in the optimum content of 20wt% benzoxazine/epoxy composite 14.18% improvement in tensile strength, 22.83% improvement in the resistance of water absorption by adding the 0.5wt% graphene; 2.46% improvement in flexural strength, and 8.05% improvement in flexural modulus by adding the 0.25wt% graphene.
It is showed that adding 8wt% micro-scale short carbon fiber has the best enhancement to the mechanical properties: increasing 22.93% in flexural strength and 9.84% in the resistance of water absorption.
Finally, the optimum content of GNPs-0.5wt%/SF-8wt%/ Benzoxazine/ Epoxy composites preform the best enhancement to the properties about 22.62% improvement in tensile strength, 12.2% improvement in flexural strength, and 39.07% improvement in impact strength, 3.2-3.8 times improvement in torsion fatigue life. Because of the reason of short carbon fiber will produce a lot of micro-cracks in the fiber-end, the stress concentration would influence the ductility and lead to cracks propagation. In the result, the flexural tests reveal about 33.84% downtrend in flexural modulus.

[1] 梁麗娜，國立清華大學化學工程系論文, 馬振基教授指導，2007.
[2] 陳帄、王德中編著，「環氧樹脂及其應用」，化學工業出版社，北京，2004.
[3] May, C. A., 1998, "Epoxy resins: chemistry and technology: CRC".
[4] 王春山，「環氧樹脂簡介與最近的發展(一)~(四) 」，化工技術，第二卷，第十期，第54頁，1994；第二卷，第十一期，第120頁1994.
[5] 馬振基、趙珏著，「高分子複合材料下冊、製程、檢測與應用」，華香園出版社，台北，2005.
[6] 王國書, 2007, “奈米碳管/高分子預浸材積層板複合材料之機械與電性質研究,” 國立清華大學動力機械工程學系碩士論文.
[7] Holly, F. W. and Cope, A. C., 1944, "Condensation Products of Aldehydes and Ketones with o-Aminobenzyl Alcohol and o-Hydroxybenzylamine," Journal of the American Chemical Society, 66(11), pp. 1875-1879.
[8] 游俊盟, 2005, ”馬來醯胺-氧代氮代苯并環已烷之合成、聚合及硬化樹脂研究,” 中原大學化學工程學系碩士論文.
[9] Agag, T. and Takeichi, T., 2001, “Novel benzoxazine monomers containing p-phenylpropargyl ether: Polymerization of monomers and properties of polybenzoxazines”, Macromolecules, Vol. 34, pp. 7257-7263.
[10] Brunovska, Z., Lyon, R. and Ishida, H., 1999, “Thermal properties of phthalonitrile functional polybenzoxazines”, Journal of Thermochim Acta, Vol357-358, pp.195-203.
[11] Ishida, H. J. and Allen, D. J., 1996 “Physical and mechanical characterization of near-zero shrinkage polybenzoxazines”, Polym. Sci B: Polym. Phys., Vol. 34 (6), pp.1019-1030.
[12] Low, H. Y. and Ishida, H., 1997, “A Study on the Volumetric Expansion of Benzoxazine-Based Phenolic Resin,” Macromolecules, vol.30, pp. 1099.
[13] Kim, H. J., Brunovska, Z. and Ishida, H., 1999, "Molecular characterization of the polymerization of acetylene-functional benzoxazine resins," Polymer, Vol. 40, pp. 1815-1822.
[14] Nair, C. P. R., 2004, "Advances in addition-cure phenolic resins," Prog. Polym. Sci., Vol. 29, pp. 401-498.
[15] Ning, X. and Ishida, H., 1994, "Phenolic materials via ring-opening polymerization: Synthesis and characterization of bisphenol-A based benzoxazines and their polymers," Journal of Polymer Science Part A: Polymer Chemistry, Vol. 32, pp. 1121-1129.
[16] Ishida, H. and Rodriguez, Y., 1995, "Curing kinetics of a new benzoxazine-based phenolic resin by differential scanning calorimetry," Polymer, Vol. 36, pp. 3151-3158.
[17] Xiang, H., Ling, H., Wang, J., Song, L. and Gu, Y., 2005, "A novel high performance RTM resin based on benzoxazine," Polymer Composites, Vol. 26(5), pp. 563-571.
[18] Xu, M., Yang, X., Zhao, R. and Liu, X., 2013, "Copolymerizing behavior and processability of benzoxazine/epoxy systems and their applications for glass fiber composite laminates," Journal of Applied Polymer Science, Vol. 128, pp. 1176-1184.
[19] Chanchira, J., Tsutomu, T., Salim, H. and Sarawut, R., 2008, "High performance wood composites based on benzoxazine-epoxy alloys,"Bioresource Technology, vol. 99, pp.8880-8886
[20] Novoselov, K. S., Geim, A. K., Morozov, S. V., Jiang, D., Zhang, Y., Dubonos, S. V., Grigorieva, I. V. and Firsov, A. A., 2004, "Electric Field Effect in Atomically Thin Carbon Films," Science, Vol. 306, pp. 666-669.
[21] “Graphene,” Http://zh.wikipedia.org/, 2011.
[22] 蕭慕柔, 2012, “電解剝落法之石墨表面性質探討,” 國立中央大學化學工程與材料工程學系碩士論文.
[23] Lee, C., Wei, X., Kysar, J. W. and Hone, J., 2008, "Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene," Science, Vol. 321, pp. 385-388.
[24] Li, W., Dichiara, A. and Bai, J., 2012, “Carbon nanotube–graphene nanoplatelet hybrids as high-performance multifunctional reinforcements in epoxy composites”, Composites Science and Technology, Vol. 74, pp.221-227.
[25] Bortz, D. R., Heras, E. G. and Martin-Gullon, I., 2011, "Impressive Fatigue Life and Fracture Toughness Improvements in Graphene Oxide/Epoxy Composites," Macromolecules, Vol. 45, pp. 238-245.
[26] Shen, X. J., Pei, X. Q., Fu, S. Y and Klaus, F., 2012, “Significantly modified tribological performance of epoxy nanocomposites at very low graphene oxide content,” Polymer, Vol. 54, pp.1234-1242
[27] Shen, X. J., Pei, X. Q., Liu, Y. and Fu, S. Y., 2013, "Tribological performance of carbon nanotube–graphene oxide hybrid/epoxy composites," Composites: Part B, Vol. 57 , pp.120-125
[28] Zaman, I., Tam, T. P., , Hsu, C. K., Qing, S. M., Bao La, L. T., Lee, L., Youssf, O. and Ma, J., 2011, "Epoxy/graphene platelets nanocomposites with two levels of interface strength," Polymer, Vol. 52, pp. 1603-1611.
[29] Kimura, H., Ohtsuka, K. and Matsumoto, A., 2010, "Performance of graphite filled composite based on benzoxazine resin," Journal of Applied Polymer Science, Vol. 117, pp. 1711-1717.
[30] Rahmanian, S., Suraya, A. R., Shazed, M. A., Zahari, R. and Zainudin, E. S., 2014, "Mechanical characterization of epoxy composite with multiscale reinforcements: Carbon nanotubes and short carbon fibers," Materials and Design, vol. 60 , pp.34-40
[31] Suvarna, R., Arumugam, V., Bull, D. J., Chambers, A. R. and Santulli, C., 2014 "Effect of temperature on low velocity impact damage and post-impact flexural strength of CFRP assessed using ultrasonic C-scan and micro-focus computed tomography," Composites: Part B, vol. 66, pp.58-64.
[32] Etaati, A., Pather, S., Fang, Z. P. and Wang, H., 2013, " Tensile and thermomechanical properties of short carbon fiber reinforced polyamide 6 composites," Composites: Part B, vol. 51, pp.270-275.
[33] Mechakra, H., Nour, A., Lecheb, S. and Chellil, A., 2015, "Mechanical characterizations of composite material with short Alfa fibers reinforcement", Composites Structures, vol. 124, pp.152-162.
[34] Talreja, R., 1987, "Fatigue of composite materials," Pennsylavania U.S.A.: Technomic.
[35] Harris, B., Reiter, H., Adam, T., Dickson, R. F. and Fernando, G., 1990, "Fatigue behaviour of carbon fibre reinforced plastics," Composites, Vol. 21, pp. 232-242.
[36] Paris, P. and Erdogan, F., 1963, "A Critical Analysis of Crack Propagation Laws," Journal of Fluids Engineering, Vol.85, pp. 528-533.
[37] Hwang, W. and Han, K. S., 1986, “Fatigue of Composites Fatigue Modulus Concept and Life Prediction,” Journal of Composite Materials, vol. 20, pp.154–165.
[38] Ferrari, A. C., Meyer, J. C., Scardaci, V., Casiraghi, C., Lazzeri, M., Mauri, F., Piscanec, S., Jiang, D., Novoselov, K. S., Roth, S. and Geim, A. K., 2006, "Raman Spectrum of Graphene and Graphene Layers," Physical Review Letters, Vol. 97, pp. 187401(1)-187401(4).
[39] ASTM D638-10, 2010, “Standard Test Method for Tensile Properties of Plastics,” Annual Book of ASTM Standards.
[40] ASTM D3039/D3039M-14, 2014, “Standard Test Method forTensile Properties of Polymer Matrix Composite Materials,” Annual Book of ASTM Standards.
[41] ASTM D790-10, 2010, “Flexural Test Methods for Flexural Properties of Unreinforced and Reinforced Plastics and Electrical Insulating Materials,” Annual Book of ASTM Standards.
[42] ASTM D256-10, 2010, “Standard Test Methods for Determining the Izod Pendulum Impact Resistance of Plastics,” Annual Book of ASTM Standards.
[43] ASTM D7136/D7136M-12, 2012, “Standard Test Method for Measuring the Damage Resistance of a Fiber-Reinforced Polymer Matrix Composite to a Drop-Weight Impact Event,” Annual Book of ASTM Standards.
[44] ASTM D570-98, 2010, “Standard Test Method for Water Absorption of Plastics,” Annual Book of ASTM Standards.
[45] 林秀臨, 2015, “多壁奈米碳管/石墨烯微片/氧代氮代苯并環已烷/環氧樹脂碳纖維積層板複合材料之機械性質暨疲勞壽命研究,” 國立清華大學動力機械工程學系碩士論文.