Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体/氰酸酯-环氧树脂复合材料的制备和性能
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摘要
采用水热法合成Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体,并应用于氰酸酯-环氧树脂(CE-EP)复合材料的增韧改性,研究Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体对CE-EP固化反应、力学性能及热稳定性的影响。XRD和SEM结果表明,所合成的Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体结晶性好、纯净、呈块状,粒径约为20nm。性能研究表明,Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体的加入对CE和EP间的固化反应速度影响不大,且不会改变树脂基体的固化反应机制。与纯CE-EP树脂体系相比,Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体/CE-EP复合材料在保持CE-EP玻璃化转变温度(Tg)的基础上明显改善了其韧性,当Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体质量分数为3wt%时,其冲击强度和弯曲强度达到最大值,较纯CE-EP树脂基体分别提高了65%和30.3%;但其热分解温度略有降低,可能是由于Ni_(0.5)Co_(0.5)Fe_2O_4铁氧体对CE-EP树脂基体高温分解的催化作用造成的。
Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite nanopowders prepared by the hydro-thermal method were used to toughen cyanate ester-epoxy resin(CE-EP).The effect of Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite on the curing reaction,mechanical properties and thermal stability of the CE-EP resins was studied.The XRD and SEM results indicate that the synthesized Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite has good crystallinity,purity and block shape,and its particle size is about 20 nm.The performance study shows that the addition of Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite has little effect on the curing reaction speed between CE and EP,and does not change the curing mechanism of the resin matrix.Compared with the pure resin system,the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite/CE-EP composites obviously improve their toughness on the basis of maintaining the glass transition temperature(Tg)of the CE-EP resins.When the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite content is 3 wt%,the impact strength and the bending strength of Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite/CE-EP composites reach the maximum,which are increased by 65% and 30.3%compared with the pure resin matrix,respectively.However,the thermal decomposition temperature of the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite/CE-EP composites decreases slightly,which may be due to the catalytic effect of the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite on the decomposition of the resin matrix.
Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite nanopowders prepared by the hydro-thermal method were used to toughen cyanate ester-epoxy resin(CE-EP).The effect of Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite on the curing reaction,mechanical properties and thermal stability of the CE-EP resins was studied.The XRD and SEM results indicate that the synthesized Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite has good crystallinity,purity and block shape,and its particle size is about 20 nm.The performance study shows that the addition of Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite has little effect on the curing reaction speed between CE and EP,and does not change the curing mechanism of the resin matrix.Compared with the pure resin system,the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite/CE-EP composites obviously improve their toughness on the basis of maintaining the glass transition temperature(Tg)of the CE-EP resins.When the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite content is 3 wt%,the impact strength and the bending strength of Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite/CE-EP composites reach the maximum,which are increased by 65% and 30.3%compared with the pure resin matrix,respectively.However,the thermal decomposition temperature of the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite/CE-EP composites decreases slightly,which may be due to the catalytic effect of the Ni_(0.5)Co_(0.5)Fe_2O_4 ferrite on the decomposition of the resin matrix.
引文
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[21] UDAY B S,VIJAYAKUMAR Y,VENKATA R R M.Structural,electrical and magnetic characteristics of nickel substituted cobalt ferrite nano particles,synthesized by self combustion method[J].Journal of Magnetism and Magnetic Materials,2015,374:376-380.
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[23]祝保林.表面接枝TiO2/CE基复合材料固化动力学及耐热性能研究[J].化工新型材料,2016,44(9):181-183.ZHU B L.Property test of curing kinetics and heat resistance by grafting modification onto anatase TiO2and its effect on dispersion property of CE composite material[J].New Chemical Materals,2016,44(9):181-183(in Chinese).
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[2] SU L N,ZENG X L,HE H P,et al.Preparation of functionalized kaolinite/epoxy resin nanocomposites with enhanced thermal properties[J].Applied Clay Science,2017,148:103-108.
[3] LI J Y,CHEN P,YU Q,et al.Influence of cyanate content on the morphology and properties of epoxy resins with phenolphthalein poly(ether ketone)[J].Journal of Applied Polymer Science,2011,121(1):598-603.
[4]霍小平,黄健.石墨烯/环氧树脂改性氰酸酯复合材料的微波吸收性能[J].中国胶黏剂,2015,24(1):17-20.HUO X P,HUANG J.Microwave absorption properties of grapheme/epoxy resin modified cyanate ester composites[J].China Adhesives,2015,24(1):17-20(in Chinese).
[5] ZENG M,LU C,WANG B,et al.Free volume hole size of cyanate eater resin/epoxy resin interpenetrating networks and its correlations with physical properties[J].Radiation Physics and Chemistry,2010,79(9):966-975.
[6]欧秋仁,嵇培军,肖军,等.环氧树脂改性双酚A型氰酸酯树脂的性能研究[J].功能材料,2015,46(s2):129-134.OU Q R,JI P J,XIAO J,et al.Studied on properties of bisphenol A cyanate ester modified by epoxy resin[J].Journal of Functional Materials,2015,46(s2):129-134(in Chinese).
[7] TOLDY A,SZLANCSIK A,SZOLNOKI B.Reactive flame retardancy of cyanate ester/epoxy resin blends and their carbon fibre reinforced composites[J].Polymer Degradation and Stability,2016,128:29-38.
[8] JIANG D Y,ZHOU Q,FAN Q,et al.Curing behavior and thermal performance of cyanate ester resin modified by poly(methyl-benzene diethynylbenzene)siliane[J].Polymer Bulletin,2015,72(9):2201-2214.
[9] WANG G,WANG R G,FU G,et al.Study on phenolphthalein poly(ether sulfone)modified cyanate ester resin and epoxy resin blends[J].Polymer Engineering and Science,2015,55(11):2591-2602.
[10]李俊燕,张小苗,毛娜,等.高性能复合泡沫材料的制备与性能研究[J].热固性树脂,2017,32(6):22-25.LI J Y,ZHANG X M,MAO N,et al.Study on preparation and properties of high-performance syntactic foams[J].Thermosetting Resin,2017,32(6):22-25(in Chinese).
[11]郑伟峰,周来水,袁铁军,等.颗粒Al2O3增强环氧树脂复合材料的微波固化动力学及性能[J].高分子材料科学与工程,2017,33(10):65-71.ZHENG W F,ZHOU L S,YUAN T J,et al.Kinetic analysis and characterization of microwave curing process of epoxy resins reinforced with Al2O3particles[J].Polymer Materials Science&Engineering,2017,33(10):65-71(in Chinese).
[12]祝保林.CE/Nd2O3纳米复合材料的制备及其性能研究[J].应用化工,2017,46(3):513-515.ZHU B L.Preparation of nano Nd2O3/CE composite materials and its performance study[J].Applied Chemical Industry,2017,46(3):513-515(in Chinese).
[13] LI P B,LI T H,YAN H X.Mechanical,tribological and heat resistant properties of fluorinated multi-walled carbon nanotube/bismaleimide/cyanate resin nanocomposites[J].Journal of Materials Science&Technology,2017,33(10):1182-1186.
[14]程圣,张沛红,邵琦.纳米SiO2/环氧桐马酸酐黏合剂的力学特性和老化特性[J].复合材料学报,2017,34(3):582-587.CHENG S,ZHANG P H,SHAO Q.Mechanical and aging properties of nano-SiO2/epoxy tung-maleic anhydride adhesive[J].Acta Materiae Compositae Sinica,2017,34(3):582-587(in Chinese).
[15] APHESTEGUY J C,DAMIANI A,DIGIOVANNI D,et al.Microwave-absorbing characteristics of epoxy resin composites containing nanoparticles of NiZn-and NiCuZn-ferrites[J].Physica B:Condensed Matter,2009,404(18):2713-2716.
[16] PHAN C H,MARIATTI M,KOH Y H.Electromagnetic interference shielding performance of epoxy composites filled with multiwalled carbon nanotubes/manganese zinc ferrite hybrid fillers[J].Journal of Magnetism and Magnetic Materials,2016,401:472-478.
[17] WEN J,WANG C G,ZANG Q J.Wear-resistant and electromagnetic absorbing behaviors of oleic acid post-modified ferrite-filled epoxy resin composite coating[J].Journal of Magnetism and Magnetic Materials,2015,378:261-266.
[18] BOON M S,SERENA W P,MARIATTI S M.Magnetic,dielectric and thermal stability of Ni-Zn ferrite-epoxy composite thin films for electronic application[J].Journal of Magnetism and Magnetic Materials,2012,324:755-760.
[19]国家技术监督局.树脂浇注铸体弯曲性能试验方法:GB/T2570—1995[S].北京:中国标准出版社,1996.State Bureau of Technical Supervision.Test method for flexural properties of resin casting body:GB/T 2570—1995[S].Beijing:China Standards Press,1996(in Chinese).
[20]国家技术监督局.树脂浇注铸体冲击试验方法:GB/T2571—1995[S].北京:中国标准出版社,1996.State Bureau of Technical Supervision.Test method for impact resistance of resin casting body:GB/T 2571—1995[S].Beijing:China Standards Press,1996(in Chinese).
[21] UDAY B S,VIJAYAKUMAR Y,VENKATA R R M.Structural,electrical and magnetic characteristics of nickel substituted cobalt ferrite nano particles,synthesized by self combustion method[J].Journal of Magnetism and Magnetic Materials,2015,374:376-380.
[22]李金焕,王瑞海,王堂洋,等.石墨烯/氰酸酯-环氧树脂复合材料的制备和性能[J].复合材料学报,2014,31(5):1154-1159.LI J H,WANG R H,WANG T Y,et al.Preparation and properties of graphene/cyanate ester-epoxy composites[J].Acta Materiae Compositae Sinica,2014,31(5):1154-1159(in Chinese).
[23]祝保林.表面接枝TiO2/CE基复合材料固化动力学及耐热性能研究[J].化工新型材料,2016,44(9):181-183.ZHU B L.Property test of curing kinetics and heat resistance by grafting modification onto anatase TiO2and its effect on dispersion property of CE composite material[J].New Chemical Materals,2016,44(9):181-183(in Chinese).
[24]吴广磊,寇开昌,晁敏,等.Nano-TiO2/BMI/CE共聚物固化动力学及介电性能的研究[J].航空材料学报,2011,31(2):79-84.WU G L,KOU K C,ZHAO M,et al.Investigation on curing kinetics and dielectric properties of nano-TiO2/BMI/CE composites[J].Journal of Aeronautical Materials,2011,31(2):79-84(in Chinese).
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