KH-SiO_2/PES/MBMI-EP复合材料的制备与性能
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摘要
为了提高双马来酰亚胺树脂(MBMI)的综合性能,扩大其应用范围,以双酚A型环氧树脂(EP)为改性剂,4,4’-二氨基二苯甲烷(DDM)为固化剂,聚醚砜(PES)为增韧剂,硅烷偶联剂KH-550改性后的纳米SiO_2作为无机填料,采用原位聚合法制备了KH-SiO_2/PES/MBMI-EP复合材料,并研究了复合材料的微观形貌、力学性能及耐热性能。红外光谱结果显示:改性后的纳米SiO_2在1555cm~(-1)处出现了N-H弯曲振动吸收峰,证明硅烷偶联剂已接枝到SiO_2表面。SEM结果表明:树脂基体加入PES与纳米SiO_2后,形成了一种多相结构,PES与纳米SiO_2可以协同增韧树脂基体,材料由脆性断裂转变为韧性断裂。力学性能测试表明:随着纳米SiO_2含量的增加,其力学性能呈现先上升后下降的趋势,当纳米SiO_2含量为1.5%时,复合材料的冲击强度及弯曲强度分别达到20.79kJ/m~2和157.23MPa,比树脂基体分别提高了102.2%和53.5%。热失重分析表明:纳米SiO_2的加入有利于提高复合材料的热分解温度,当SiO_2含量为1.5%时,复合材料的热分解温度达到411.3℃,比树脂基体提高了15.8℃。
In order to improve the overall performance of bismaleimide(MBMI) resin matrix composites and expand its application range, the KH-SiO_2/PES/MBMI-EP composites were prepared by in-situ polymerization with the bisphenol A type epoxy resin as a modifier, the 4,4'-diamin-odiphenylmethane(DDM) as a curing agent, the polyether sulfone(PES) as a toughening agent, and the silane coupling agent KH-550 modified nano SiO_2 as an inorganic filler. The micro-morphology, mechanical properties and heat resistance of the composites were studied. The results of FTIR showed that the peak of modified nano SiO_2 at 1555cm~(-1) was the bending vibration absorption peak of N-H bond, it demonstrated that the silane coupling agent had grafted on the surface of SiO_2. It could be found from SEM images that a multiphase structure was formed after adding the PES resin and nano SiO_2 to the resin matrix. The PES resin and nano SiO_2 could synergistically toughen the resin matrix, and the material changed from brittle fracture to ductile fracture. The mechanical properties of the composites showed that the mechanical properties of the composites increased firstly and then decreased with the increase of nano SiO_2 content. When the nano SiO_2 content was 1.5%, the impact strength and bending strength of the composites reached 20.79kJ/m~2 and 157.23 MPa respectively, increased by 102.2% and 53.5% than that of the matrix resin. The thermogravimetric analysis showed that the addition of nano SiO_2 was beneficial to raising the thermal decomposition temperature of the composites. When the nano SiO_2 content was 1.5%, the thermal decomposition temperature of the composite reached 411.3℃, which was 15.8°C higher than that of the matrix resin.
In order to improve the overall performance of bismaleimide(MBMI) resin matrix composites and expand its application range, the KH-SiO_2/PES/MBMI-EP composites were prepared by in-situ polymerization with the bisphenol A type epoxy resin as a modifier, the 4,4'-diamin-odiphenylmethane(DDM) as a curing agent, the polyether sulfone(PES) as a toughening agent, and the silane coupling agent KH-550 modified nano SiO_2 as an inorganic filler. The micro-morphology, mechanical properties and heat resistance of the composites were studied. The results of FTIR showed that the peak of modified nano SiO_2 at 1555cm~(-1) was the bending vibration absorption peak of N-H bond, it demonstrated that the silane coupling agent had grafted on the surface of SiO_2. It could be found from SEM images that a multiphase structure was formed after adding the PES resin and nano SiO_2 to the resin matrix. The PES resin and nano SiO_2 could synergistically toughen the resin matrix, and the material changed from brittle fracture to ductile fracture. The mechanical properties of the composites showed that the mechanical properties of the composites increased firstly and then decreased with the increase of nano SiO_2 content. When the nano SiO_2 content was 1.5%, the impact strength and bending strength of the composites reached 20.79kJ/m~2 and 157.23 MPa respectively, increased by 102.2% and 53.5% than that of the matrix resin. The thermogravimetric analysis showed that the addition of nano SiO_2 was beneficial to raising the thermal decomposition temperature of the composites. When the nano SiO_2 content was 1.5%, the thermal decomposition temperature of the composite reached 411.3℃, which was 15.8°C higher than that of the matrix resin.
引文
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[15] LUO D H, WU C, YAN M. Incorporation of the Fe3O4and SiO2nanoparticles in epoxy-modified silicone resin as the coating for soft magnetic composites with enhanced performance[J].JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS,2018, 452:5~9.
[16] HE P G, HUANG M Y, YU B, et al. Effects of nano-silica contents on the properties of epoxy nanocomposites and Ti-epoxy assembles[J]. COMPOSITES SCIENCE AND TECHNOLOGY,2016, 129:46~52.
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[19] KIM T, KIM S, LEE D G, et al. Preparation of a branched amine and physical and thermal studies of epoxy compositions including the amine compound[J]. JOURNAL OF APPLIED POLYMER SCIENCE, 2018, 135(19):46233.
[20] CIVIDANES L S, SIMONETTI E A N, CAMPOS T M B, et al.Anomalous behavior of thermal stability of amino-carbon nanotube-epoxy nanocomposite[J]. JOURNAL OF COMPOSITE MATERIALS, 2015, 49(24):3067~3073.
[2] QIU J, WANG Z M, JIN L, et al. Preparation and mechanical properties of MWCNT and carbon fiber reinforced bismaleimide resin composite[J]. Carbon, 2012, 27(5):362~369.
[3]宋盛菊,杨法杰,褚庭亮,等.环氧树脂增韧方法及增韧剂的研究进展[J].中国印刷与包装研究, 2013, 5(5):9~24.
[4] JIANG T, KUILA T, KIM N H, et al. Enhanced mechanical properties of silanized silica nanoparticle attached graphene oxide/epoxy composites[J]. Composites Science&Technology, 2013, 79:115~125.
[5] SPLENDORE R, DOTTI F, CRAVELLO B, et al. Thermo-physiological comfort of a PES fabric with incorporated activated carbon Part II:wear trials[J]. International Journal of Clothing Science and Technology, 2011, 23(5):283~293.
[6] KHORSHIDI B, HAJINASIRI J, MA G, et al. Thermally resistant and electrically conductive PES/ITO nanocomposite membrane[J]. Journal of Membrane Science, 2016, 500:151~160.
[7] YANG J P, FENG Q P, CHEN Z K, et al. Superiority of Nanosized Over Microsized Hyperbranched Polymer Second Phase in Modifying Brittle Epoxy Resin[J]. Journal of Applied Polymer Science, 2011, 119(2):863~870.
[8] ZHANG G L, KE Y C, QIN M R, et al. Preparations and Tribological Properties of COPNA Copolymer Materials[J]. Procedia Engineering, 2015, 102:615~624.
[9]吴寅,张秋禹,陈营,等.聚醚酮改性双马来酰亚胺树脂的研究[J].材料导报, 2013, 27(1):65~67.
[10]苏醒.偶联剂非水解基团对改性SiO2/PDMS膜性能影响的研究[D].哈尔滨:东北林业大学, 2017.
[11]国家质量技术监督局.塑料试样状态调节和试验的标准环境:GB/T 2918-1998[S].北京:中国标准出版社, 1998.
[12]陈和生,孙振亚,邵景昌.八种不同来源二氧化硅的红外光谱特征研究[J].硅酸盐通报, 2011, 30(4):934~937.
[13] HAN H L, LI H Q, LIU M Y, et al. Effect of“bridge”on the performance of organic-inorganic crosslinked hybrid proton exchange membranes via KH550[J]. JOURNAL OF POWER SOURCES,2017, 340:126~138.
[14]陈宇飞.聚合物基复合材料[M].北京:化学工业出版社,2010.
[15] LUO D H, WU C, YAN M. Incorporation of the Fe3O4and SiO2nanoparticles in epoxy-modified silicone resin as the coating for soft magnetic composites with enhanced performance[J].JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS,2018, 452:5~9.
[16] HE P G, HUANG M Y, YU B, et al. Effects of nano-silica contents on the properties of epoxy nanocomposites and Ti-epoxy assembles[J]. COMPOSITES SCIENCE AND TECHNOLOGY,2016, 129:46~52.
[17] ROSTAMIYAN Y, FEREIDOON A, REZAEIASHTIYANI M, et al. Experimental and optimizing flexural strength of epoxybased nanocomposite:Effect of using nano silica and nano clay by using response surface design methodology[J]. MATERIALS&DESIGN, 2015, 69:96~104.
[18] LEE D H, LEE N, PARK H. Role of silica nanoparticle in multi-component epoxy composites for electrical insulation with high thermal conductivity[J]. JOURNAL OF THE AMERICAN CERAMIC SOCIETY, 2018, 101(6):2450~2458.
[19] KIM T, KIM S, LEE D G, et al. Preparation of a branched amine and physical and thermal studies of epoxy compositions including the amine compound[J]. JOURNAL OF APPLIED POLYMER SCIENCE, 2018, 135(19):46233.
[20] CIVIDANES L S, SIMONETTI E A N, CAMPOS T M B, et al.Anomalous behavior of thermal stability of amino-carbon nanotube-epoxy nanocomposite[J]. JOURNAL OF COMPOSITE MATERIALS, 2015, 49(24):3067~3073.