氮化铝改性含硅芳炔树脂的导热性能
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摘要
将不同粒径氮化铝(AlN)颗粒与高耐热含硅芳炔树脂(PSA)混合制得了AlN/PSA;同时用铝酸酯偶联剂对AlN颗粒进行表面改性制得mAlN,并将其与PSA混合制备了mAlN/PSA。随后将树脂进行固化,并探究树脂固化物导热性能的影响因素,以及树脂固化物的电性能。通过差示扫描量热法(DSC)探究改性树脂的固化工艺,利用红外光谱(FT-IR)表征偶联剂的改性效果,通过热重(TG)、动态热机械分析(DMA)研究树脂固化物的热性能,通过扫描电镜(SEM)、X射线能谱(EDS)观察树脂固化物的断面形貌。结果表明,当AlN粒径为45μm、偶联剂的质量分数为3%、AlN添加的体积分数为24%时,mAlN/PSA固化物的导热系数高达2.36 W/(m·K),同时其耐热性能得到提升,介电和绝缘性能良好。在10Hz～1 MHz,mAlN/PSA固化物的介电常数低于3.8,电阻率高于10~8Ω·cm。
Due to its excellent heat resistance,the silicon-containing aryacetylene(PSA)resin showed highly potential application in the aerospace field.However,the low thermal conductivity of PSA resin limited its further development and application.Aluminum nitride(AlN)particles were used as the filler to modify PSA resin to improve the thermal conductivity of PSA resin.Then,the aluminate coupling agent was used to modify the surfaces of the AlN particles.The surface-modified AlN particles were mixed with PSA resin to prepare the modified AlN/PSA composite resin.The effects of AlN content,particle size,and surface modification on the thermal conductivity of cured resin were investigated.The electrical properties of cured resin were also studied.The curing process of the resin was investigated by differential scanning calorimetry(DSC).The modification effect of the coupling agent was characterized by infrared spectroscopy(FT-IR).The thermal properties of cured AlN/PSA were investigated by thermogravimetric(TG)analysis and dynamic thermo-mechanical analysis(DMA).Scanning electron microscopy(SEM)was used to observe the cross-sectional morphology of cured resin.X-ray energy dispersive spectroscopy(EDS)was used to observe the elemental distribution of the fracture surface.Results show that when AlN particle size,mass fraction of coupling agent and volume fraction of AlN are 45μm,3%,and 24%,respectively,the thermal conductivity of the cured mAlN/PSA reaches 2.36 W/(m·K).At the same time,the heat resistance of the cured mAlN/PSA is improved.The cured mAlN/PSA has good dielectric and insulating properties,in which the dielectric constant is lower than 3.8 and the electrical resistivity is higher than 10~8Ω·cm in the range of 10 Hz to 1 MHz.
Due to its excellent heat resistance,the silicon-containing aryacetylene(PSA)resin showed highly potential application in the aerospace field.However,the low thermal conductivity of PSA resin limited its further development and application.Aluminum nitride(AlN)particles were used as the filler to modify PSA resin to improve the thermal conductivity of PSA resin.Then,the aluminate coupling agent was used to modify the surfaces of the AlN particles.The surface-modified AlN particles were mixed with PSA resin to prepare the modified AlN/PSA composite resin.The effects of AlN content,particle size,and surface modification on the thermal conductivity of cured resin were investigated.The electrical properties of cured resin were also studied.The curing process of the resin was investigated by differential scanning calorimetry(DSC).The modification effect of the coupling agent was characterized by infrared spectroscopy(FT-IR).The thermal properties of cured AlN/PSA were investigated by thermogravimetric(TG)analysis and dynamic thermo-mechanical analysis(DMA).Scanning electron microscopy(SEM)was used to observe the cross-sectional morphology of cured resin.X-ray energy dispersive spectroscopy(EDS)was used to observe the elemental distribution of the fracture surface.Results show that when AlN particle size,mass fraction of coupling agent and volume fraction of AlN are 45μm,3%,and 24%,respectively,the thermal conductivity of the cured mAlN/PSA reaches 2.36 W/(m·K).At the same time,the heat resistance of the cured mAlN/PSA is improved.The cured mAlN/PSA has good dielectric and insulating properties,in which the dielectric constant is lower than 3.8 and the electrical resistivity is higher than 10~8Ω·cm in the range of 10 Hz to 1 MHz.
引文
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[2] YU H,LI L L,GUO F,et al.Thermal and insulating properties of epoxy/aluminum nitride composites used for thermal interface material[J].Journal of Applied Polymer Science,2011,124(1):669-677.
[3] YANG C K,TSAI H Y,WANG S F,et al.Dielectric and thermal studies of inorganic microfillers on polymer microwave substrates-metallocene cyclic olefin copolymers(COC)[J].Composites Science and Technology,2002,62(5):655-661.
[4] SATO K,HORIBE H,SHIRAI T,et al.Thermally conductive composite films of hexagonal boron nitride and polyimide with affinity-enhanced interfaces[J].Journal of Materials Chemistry,2010,20(14):2749-2752.
[5] IM H,KIM J.Thermal conductivity of a graphene oxide-carbon nanotube hybrid/epoxy composite[J].Carbon,2012,50(15):5429-5440.
[6] ZHOU S T,YU L,SONG X,et al.Preparation of highly thermally conducting polyamide 6/graphite composites via lowtemperature in situ expansion[J].Journal of Applied Polymer Science,2013,131(1):1-15.
[7]董斯堃,袁荞龙,黄发荣.芳基二炔丙基醚改性含硅芳炔树脂的性能[J].华东理工大学学报(自然科学版),2019,45(3):417-425.
[8] OHKITA T,LEE S H.Crystallization behavior of poly(butylene succinate)/corn starch biodegradable composite[J].Journal of Applied Polymer Science,2005,97(3):1107-1114.
[9] AGRAWAL A,SATAPATHY A.Epoxy composites filled with micro-sized AlN particles for microelectronic applications[J].Particulate Science and Technology,2015,33(1):2-7.
[10] HU Y,DU G P,CHEN N.A novel approach for Al2O3/epoxy composites with high strength and thermal conductivity[J].Composites Science and Technology,2016,124:36-43.
[11] KIM K,KIM J.Magnetic aligned AlN/epoxy composite for thermal conductivity enhancement at low filler content[J].Composites Part B:Engineering,2016,93:67-74.
[12] PROGELHOF R C,THRONE J L,RUETSCH R R.Methods for predicting the thermal conductivity of composite systems:A review[J].Polymer Engineering and Science,1976,16:615-625.
[13]秦明礼,曲选辉,林健凉,等.氮化铝陶瓷研究和进展[J].稀有金属材料与工程,2002,31(1):8-12.
[14] WU S Y,HUANG Y L,MA C,et al.Mechanical,thermal and electrical properties of aluminum nitride/polyetherimide composites[J].Composites Part A:Applied Science and Manufacturing,2011,42(11):1573-1583.
[15]凌伟.电子封装用氢酸酯树脂基复合材料的研究[D].江苏苏州:苏州大学,2009.
[16] ITOH M,MITSUZUKA M,IWATA k,et al.A novel synthesis and extremely high thermal stability of poly[(phenylsilylene)ethynylene-1,3-phenyl eneethynylene][J].Macromolecules,2002,27(26):7917-7919.
[17] WANG F,ZHANG J,HUANG J X,et al.Synthesis and characterization of poly(dimethylsilyleneethynylenephenyleneethynylene)terminated with phenylacetylene[J].Polymer Bulletin,2006,56(1):19-26.
[18] JIANG Z Y,ZHOU Y,HUANG F R,et al.Characterization of a modified silicon-containing arylacetylene resin with POSS functionality[J].Chinese Journal of Polymer Science,2011,29(6):726-731.
[19] WANG C F,HUANG F R,JIANG Y,et al.Oxidation behavior of carbon materials derived from a carborane-and silicon-incorporated polymer[J].Ceramics International,2012,38(4):3081-3088.
[20] BU X J,ZHOU Y,HUANG F R.The strengthening and toughening effects of a novel octa(propargyl propyl sulfide)POSS(OPPSP)on silicon-containing arylacetylene(PSA)resin[J].Materials Letters,2016,174:21-23.
[21]周晓辉,黄发荣,唐均坤,等.耐高温端乙炔基聚醚酰亚胺改性含硅芳炔树脂[J].功能高分子学报,2017,30(3):296-305.
[22] CHEN H G,XIN H,LU J R,et al.Synthesis and properties of poly(dimethyl silylene-ethynylene-phenoxyphenoxyphenylene-ethynylene)[J].High Performance Polymers,2017,29(5):595-601.
[23] RAMAJO L,REBOREDO M,CASTRO M.Dielectric response and relaxation phenomena in composites of epoxy resin with BaTiO3particles[J].Composites Part A:Applied Science and Manufacturing,2005,36(9):1267-1274.
[24] SANADA K,TADA Y,SHINDO Y.Thermal conductivity of polymer composites with close-packed structure of nano and micro fillers[J].Composites Part A:Applied Science and Manufacture,2009,40(6):724-730.