功能化纳米SiO_2-聚醚砜/BMI-酚醛环氧树脂复合材料的固化动力学与性能
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摘要
以4,4’-二氨基二苯甲烷(DDM)为固化剂、双马来酰亚胺(BMI)和酚醛环氧树脂(F51)为基体、聚醚砜(PES)为增韧剂、硅烷偶联剂KH560功能化纳米SiO_2(KH-SiO_2)为改性剂,采用原位聚合法制备了KH-SiO_2-PES/BMI-F51复合材料,并通过非等温DSC确定了复合材料的固化工艺及固化反应动力学。根据Kissinger方程和Ozawa方程求得体系的表观活化能分别为96.03kJ/mol和99.18kJ/mol。FTIR测试结果表明:KH-SiO_2改性效果良好,不饱和双键和环氧基特征峰消失,BMI中C■C双键和F51中环氧基在DDM作用下参与了体系的固化反应。SEM结果表明:PES树脂和KH-SiO_2含量适当时,PES树脂和KH-SiO_2在树脂基体中分散均匀,断裂纹不规则杂乱发展,KH-SiO_2-PES/BMI-F51复合材料呈韧性断裂。力学性能测试和热失重测试表明:当PES含量为4wt%,KH-SiO_2含量为1.5wt%时,KH-SiO_2-PES/BMI-F51复合材料的弯曲强度、弯曲模量和冲击强度分别为156.23MPa、4.18GPa和20.89kJ/m2,较BMI-F51基体分别提高了49.7%、29.4%和82.8%;KH-SiO_2-PES/BMI-F51复合材料的热分解温度为393.1℃,残重率为50%时,分解温度高达523.1℃,耐热性十分优异。KH-SiO_2-PES/BMI-F51复合材料的力学性能和耐热性有了较大提高,为拓展F51及BMI的应用范围提供了一定的理论数据。
With 4,4'-diamino diphenyl methane(DDM)as the curing agent,bismaleimide(BMI)and phenolic epoxy resin(F51)as the matrix,polyethersulfone(PES)as the toughening agent and functionalized nano SiO_2 by silane coupling agent KH560(KH-SiO_2)as the modifier,the KH-SiO_2-PES/BMI-F51 composites were prepared by in-situ polymerization method,and the curing process and reaction curing kinetics were determined by nonisothermal DSC. The apparent activation energy of KH-SiO_2-PES/BMI-F51 composites are 96.03 kJ/mol and99.18 kJ/mol according to Kissinger equation and Ozawa equation,respectively.The FTIR results reveal that the surface modification of KH-SiO_2 is favourable,the characteristic peaks of unsaturated double bond and epoxy group disappear,and the C■C double bond in BMI and epoxy group in F51 are involved in the curing reaction of KHSiO_2-PES/BMI-F51 composites under the effect of DDM.The SEM images exhibit that PES resin and KH-SiO_2 uniformly disperse in the resin matrix when the content of PES resin and KH-SiO_2 are appropriate,the broken cracks develop irregularly and the material exhibits ductile fracture. The mechanical performances and thermogravimetric properties show that bending strength,bending modulus and impact strength of KH-SiO_2-PES/BMI-F51 composites are 156.23 MPa,4.18 GPa and 20.89 kJ/m2,when the mass fraction of PES and KH-SiO_2 are4 wt% and 1.5 wt%,which are 49.7%,29.4%and 82.8% higher than that of BMI-F51 matrix,respectively.The thermal decomposition temperature of KH-SiO_2-PES/BMI-F51 composites is 393.1℃,and the temperature at the residual mass of 50%reaches 523.1℃,the heat-resistant property is excellent.The mechanical properties and heatresistant properties of KH-SiO_2-PES/BMI-F51 composites are greatly improved,which provides theoretical data for expanding the application range of F51 and BMI.
With 4,4'-diamino diphenyl methane(DDM)as the curing agent,bismaleimide(BMI)and phenolic epoxy resin(F51)as the matrix,polyethersulfone(PES)as the toughening agent and functionalized nano SiO_2 by silane coupling agent KH560(KH-SiO_2)as the modifier,the KH-SiO_2-PES/BMI-F51 composites were prepared by in-situ polymerization method,and the curing process and reaction curing kinetics were determined by nonisothermal DSC. The apparent activation energy of KH-SiO_2-PES/BMI-F51 composites are 96.03 kJ/mol and99.18 kJ/mol according to Kissinger equation and Ozawa equation,respectively.The FTIR results reveal that the surface modification of KH-SiO_2 is favourable,the characteristic peaks of unsaturated double bond and epoxy group disappear,and the C■C double bond in BMI and epoxy group in F51 are involved in the curing reaction of KHSiO_2-PES/BMI-F51 composites under the effect of DDM.The SEM images exhibit that PES resin and KH-SiO_2 uniformly disperse in the resin matrix when the content of PES resin and KH-SiO_2 are appropriate,the broken cracks develop irregularly and the material exhibits ductile fracture. The mechanical performances and thermogravimetric properties show that bending strength,bending modulus and impact strength of KH-SiO_2-PES/BMI-F51 composites are 156.23 MPa,4.18 GPa and 20.89 kJ/m2,when the mass fraction of PES and KH-SiO_2 are4 wt% and 1.5 wt%,which are 49.7%,29.4%and 82.8% higher than that of BMI-F51 matrix,respectively.The thermal decomposition temperature of KH-SiO_2-PES/BMI-F51 composites is 393.1℃,and the temperature at the residual mass of 50%reaches 523.1℃,the heat-resistant property is excellent.The mechanical properties and heatresistant properties of KH-SiO_2-PES/BMI-F51 composites are greatly improved,which provides theoretical data for expanding the application range of F51 and BMI.
引文
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[2]SUN T,FAN H Y,ZHUO Q,et al.Covalent incorporation of aminated carbon nanotubes into epoxy resin network[J].High Performance Polymers,2014,26(8):892-899.
[3]沈小军,孟令轩,付绍云.石墨烯-多壁碳纳米管协同增强环氧树脂复合材料的低温力学性能[J].复合材料学报,2015,32(1):21-26.SHEN X J,MENG L X,FU S Y.Cryogenic mechanical properties of epoxy composites synergistically reinforced by graphene-multi-walled carbon nanotubes[J].Acta Materiae Compositae Sinica,2015,32(1):21-26(in Chinese).
[4]CHEN B H,YUAN L,GUAN Q B,et al.Preparation and mechanism of shape memory bismaleimide resins with high transition temperature,high toughness and good processability[J].Journal of Materials Science,2018,53(15):10798-10811.
[5]HOU T H,MILLER S G,WILLIAMS T S,et al.Out-ofautoclave processing and properties of bismaleimide composites[J].Journal of Reinforced Plastics and Composites,2014,33(2):137-149.
[6]ZUO Z,YANG Y L,SONG L Z,et al.Miscibility analysis of polyethersulfone and polytetrafluoroethylene using the molecular dynamics method[J].Fibers and Polymers,2015,16(3):510-521.
[7]ZHANG X G,LIU Z J,ZHANG X Y,et al.High-adhesive superhydrophobic litchi-like coatings fabricated by in-situ growth of nano-silica on polyethersulfone surface[J].Chemical Engineering Journal,2018,343:699-707.
[8]ZHANG L Q,MA N,WANG Y Y,et al.Study on the reinforcing mechanisms of nano silica to cement-based materials with theoretical calculation and experimental evidence[J].Journal of Composite Materials,2016,50(29):4135-4146.
[9]WANG T,WANG J,HUO S,et al.Preparation and flame retardancy of DOPO-based epoxy resin containing bismaleimide[J].High Performance Polymers,2016,28(9):1090-1095.
[10]李鸿岩,刘宁,费明,等.双马来酰亚胺改性环氧/二氨基二苯甲烷固化体系的性能研究[J].绝缘材料,2012,45(6):46-50.LI H Y,LIU N,FEI M,et al.Properties study of epoxy/diamio diphenylmethane curing system modified by bismaleimide[J].Insulating Materials,2012,45(6):46-50(in Chinese).
[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.Nation Bureau of Technical Supervision.Standard environment for state regulation and testing of plastic samples:GB/T 2918-1998[S].Beijing:China Standards Press,1998(in Chinese).
[12]国家质量监督检验检疫总局.树脂浇铸体性能试验方法:GB/T 2567-2008[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine.Test methods for properties of resin casting boby:GB/T 2567-2008[S].Beijing:China Standards Press,2008(in Chinese).
[13]KISSINGER H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(11):1702-1706.
[14]OZAWA A.Kinetics analysis of derivative curves in thermal analysis[J].Journal of Thermal Analysis,1970,2(3):301-324.
[15]白孟瑶.聚醚砜/纳米二氧化硅改性环氧树脂胶黏剂的制备及性能研究[D].哈尔滨:哈尔滨理工大学,2011.BAI M Y.Preparation and study on properties of epoxy resin modified by poly(ether sulfone)/nano-silica[D].Harbin:Harbin University of Science and Technology,2011(in Chinese).
[16]LI S P,LIN Q,HOU H J,et al.Mechanical characterization of epoxy composites with glass fibers grafted by hyperbranched polymer with amino terminal groups[J].Polymer Bulletin,2016,73(11):2947-2960.
[17]LIU M,MEYER A S,FERNANDO D,et al.Effect of pectin and hemicellulose removal from hemp fibres on the mechanical properties of unidirectional hemp/epoxy composites[J].Composites Part A:Applied Science and Manufacuring,2016,90:724-735.
[18]HASHEMI S A,MOUSAVI S M.Effect of bubble based degradation on the physical properties of single wall carbon nanotube/epoxy resin composite and new approach in bubbles reduction[J].Composites Part A:Applied Science and Manufacuring,2016,90:457-469.
[19]RAHMANIAN S,SURAYA A R,ROSHANRAVAN B,et al.The influence of multiscale fillers on the rheological and mechanical properties of carbon-nanotube-silica-reinforced epoxy composite[J].Materials&Design,2015,88:227-235.
[20]GUNEYISI E,GESOGLU M,AZEZ O A,et al.Physicomechanical properties of self-compacting concrete containing treated cold-bonded fly ash lightweight aggregates and SiO2nano-particles[J].Construction and Buiding Materials,2015,101:1142-1153.
[21]SATO K,LSHII K,OAKI Y,et al.Polymer-assisted shapeable synthesis of porous frameworks consisting of silica nanoparticles with mechanical property tuning[J].Polymer Journal,2017,49(12):825-830.
[22]陈宇飞,代起望,滕成君,等.超临界氧化铝/聚醚砜-BMI-BBA-BBE复合材料的微观结构与耐热性[J].复合材料学报,2015,32(3):665-672.CHEN Y F,DAI Q W,TENG C J,et al.Microstructure and heat-resistance of SCE-Al2O3/PES-MBAE composite[J].Acta Materiae Compositae Sinica,2015,32(3):665-672(in Chinese).
[23]AGRAWAL A,SATAPATHY A.Thermal and dielectric behavior of epoxy composites filled with ceramic micro particulates[J].Journal of Composite Materials,2014,48(30):3755-3769.
[24]YUAN Z K,YU J H,HE Z H,et al.Improved thermal properties of epoxy composites filled with thermotropic liquid crystalline epoxy grafted aluminum nitride[J].Fibers and Polymers,2014,15(12):2581-2590.