改性环氧树脂的导热、耐热及光学性能研究
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摘要
环氧树脂是一种用途非常广泛的热固性树脂,在电子行业作为封装材料使用。环氧树脂吸湿性好、热膨胀系数小、耐化学腐蚀,但其导热性、光学性能、热稳定性尚有不足之处,因而作为封装村料受到了一定限制。本文采用二氧化硅、纳米氧化镁对环氧树脂进行改性,以期用于发光二极管(LED)封装材料。
本文采用高分子保护沉淀法制备了纳米氧化镁。以氯化镁为原料,碳酸钠作沉淀剂,聚乙烯醇(PVA)为高分子保护剂,制备出氧化镁的前驱物,经离心、真空干燥,在973K下锻烧,制得了纳米氧化镁粉体,平均粒径为40～50nm,面心立方结构,基本呈球形,分散性较好。
本文通过填充SiO_2提高了固化物的导热率和耐热性。采用导热仪和热分析仪研究对其导热性、耐热性能进行了表征。实验结果表明,SiO_2的体积分数的增加,固化物导热增加,当SiO_2的体积分数达到50%时,导热率达到0.677 W·m~(-1)·K~(-1),约为未添加SiO_2的2.5倍。同时耐热性有所提高,其中初始分解温度提14K,终止分解温度提高了19K。研究了环氧树脂的组分、固化剂、稀释剂、热氧稳定剂及工艺温度对固化物透明性的影响,得到了光学性能很好的固化物。
采用纳米氧化镁对环氧树脂AB胶进行填充改性,实验证实,固化反应后的产物,导热、耐热及光学透明性能均有所增加。随MgO的含量增加,固化物的热导率相应增加;透光性能随MgO含量的增加呈现极值变化,填充量为0.2%时,固化物的透光率最大,继续提高MgO的含量固化物的透光率下降;添加MgO填料同时改善了热稳定性,初始分解温度提高。
Epoxide resin is one of the thermosetting resins that has been widely applied in various areas,especially in the electronic packaging materials.It has a low coefficient of thermal expansion,good moisture absorption,and strong resistance from chemical corrosion.However,some of disadvantages such as low thermal conductivity and instability as well as optical property have limited its applications in large power LED devices.To solve this problem,this work focused on developing a modification method to improve the performance of epoxide resin so as to use it as a packaging material for LED devices.
In this work,nano-MgO was prepared by using a PVA protection precipitation method.At first,MgCl_2 was used as a raw material,Na_2CO_3 as a precipitating agent,water as a reaction media and the PVA as protection reagent to produce a precursor of magnesium carbonate.Then,magnesium oxide nanoparticles were prepared by calcinating the magnesium hydroxide at 973K after being dehydrated by means of multi-freeze centrifugal and vacuum drying at a given constant temperature.The as-prepared products were spherical particles with average crystalline size about 40-50nm and had a good crystallinity and high dispersibility.
The solidified product after modification was characterized using a laser diffraction heat conductivity coefficient instrument and a TG analyzer.When the volume fraction of SiO_2 was 50%,the coefficient of heat conductivity was 0.677 W·m~(-1)·K~(-1),about 2.5 times that without adding SiO_2.Meanwhile,its decomposition temperature increased by 14K at the initial point,and 19K at the end point.
The thermal conductivity,heat resistance,and optical transparence of nano-MgO modify epoxide resin were measured.It was found that heat conductivity of AB glue increased with increasing MgO percentage.When the mass fraction of MgO was 0.2%,the luminousness of solidified products reached the maximum,and then the luminousness decreased with further increasing MgO content.Meanwhile,adding MgO also improved the heat stability and increased the decomposition temperature of epoxide resin.
本文采用高分子保护沉淀法制备了纳米氧化镁。以氯化镁为原料,碳酸钠作沉淀剂,聚乙烯醇(PVA)为高分子保护剂,制备出氧化镁的前驱物,经离心、真空干燥,在973K下锻烧,制得了纳米氧化镁粉体,平均粒径为40～50nm,面心立方结构,基本呈球形,分散性较好。
本文通过填充SiO_2提高了固化物的导热率和耐热性。采用导热仪和热分析仪研究对其导热性、耐热性能进行了表征。实验结果表明,SiO_2的体积分数的增加,固化物导热增加,当SiO_2的体积分数达到50%时,导热率达到0.677 W·m~(-1)·K~(-1),约为未添加SiO_2的2.5倍。同时耐热性有所提高,其中初始分解温度提14K,终止分解温度提高了19K。研究了环氧树脂的组分、固化剂、稀释剂、热氧稳定剂及工艺温度对固化物透明性的影响,得到了光学性能很好的固化物。
采用纳米氧化镁对环氧树脂AB胶进行填充改性,实验证实,固化反应后的产物,导热、耐热及光学透明性能均有所增加。随MgO的含量增加,固化物的热导率相应增加;透光性能随MgO含量的增加呈现极值变化,填充量为0.2%时,固化物的透光率最大,继续提高MgO的含量固化物的透光率下降;添加MgO填料同时改善了热稳定性,初始分解温度提高。
Epoxide resin is one of the thermosetting resins that has been widely applied in various areas,especially in the electronic packaging materials.It has a low coefficient of thermal expansion,good moisture absorption,and strong resistance from chemical corrosion.However,some of disadvantages such as low thermal conductivity and instability as well as optical property have limited its applications in large power LED devices.To solve this problem,this work focused on developing a modification method to improve the performance of epoxide resin so as to use it as a packaging material for LED devices.
In this work,nano-MgO was prepared by using a PVA protection precipitation method.At first,MgCl_2 was used as a raw material,Na_2CO_3 as a precipitating agent,water as a reaction media and the PVA as protection reagent to produce a precursor of magnesium carbonate.Then,magnesium oxide nanoparticles were prepared by calcinating the magnesium hydroxide at 973K after being dehydrated by means of multi-freeze centrifugal and vacuum drying at a given constant temperature.The as-prepared products were spherical particles with average crystalline size about 40-50nm and had a good crystallinity and high dispersibility.
The solidified product after modification was characterized using a laser diffraction heat conductivity coefficient instrument and a TG analyzer.When the volume fraction of SiO_2 was 50%,the coefficient of heat conductivity was 0.677 W·m~(-1)·K~(-1),about 2.5 times that without adding SiO_2.Meanwhile,its decomposition temperature increased by 14K at the initial point,and 19K at the end point.
The thermal conductivity,heat resistance,and optical transparence of nano-MgO modify epoxide resin were measured.It was found that heat conductivity of AB glue increased with increasing MgO percentage.When the mass fraction of MgO was 0.2%,the luminousness of solidified products reached the maximum,and then the luminousness decreased with further increasing MgO content.Meanwhile,adding MgO also improved the heat stability and increased the decomposition temperature of epoxide resin.
引文
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[38]周益明,忻新泉.低温固相合成化学[J].无机化学学报,1999,15(3):273-292.
[39]汪国忠,程素芳,何国良,等.纳米级MgO粉体的合成[J].合成化学,1996,4(4):300.
[40]酒金婷,李立平,葛钥,等.用高分子保护的纳米MgO的合成[J].无机化学学报,2001,17(3):361-365.
[41]朱亚光,曾人杰,刘新锦,等.MgO纳米粉制备及表征[J].厦门大学学报(自然科学版),2001,40(6):1256-1259.
[42]孟明,林培琐,伏义路.小同焙烧气氛对氧化镁表面碱性的影响[J].催化学报,2000,21(3):286-288.
[43]王路明.石灰卤水法制备超细氧化镁的[J]海湖盐与化工,2001,30(1):21-24.
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[2]Kuntman A,KuntmanA H.Study on dielectric properties of a new polyimide film suitable forinterlayer dielectric material in microelectronics applications[J].Microelectronics Journal,2000,31:629-634.
[3]Xu J M.Plastic electronics and future trends in microelectron-ies[J].Synthetic metals,2000,115:1-3.
[4]Rimdusit S,Ishida H.Development of new class of electronic packaninn materials based on ternary systems of benzoxazine,epoxy,and phenolic resins[J].Polymer,2000,41:7941-7949.
[5]马华宪,尹维英,任敏利,等.电子塑封料的研制与开发[J].化工科技,2000,8(1):12-16
[6]王经武,塑料改性技术[M].北京:化学工业出版社,2004.419-420,480-491.
[7]成兴明,绿色封装环氧塑封料研究[J].半导体技术,29(8):4
[8]阳范文,赵耀明.电子封装用环氧树脂的研究现状与发展趋势[J].电子工艺技术,2001,22(6):238-241.
[9]孙勤良.环氧树脂在封装材料中的应用概况[J].热固性树脂,2000,15(1):47-51.
[10]宋谦.环氧灌注材料在电子器件上的应用及发展动向[J].电子工艺技术,2001,22(2):47-50.
[11]王伟.环氧树脂固化技术及其固化剂研究进展[J].热固性树脂,2001,16(3):29-33.
[12]张知方.微电子用高纯度环氧树脂和酚醛树脂[J].热固性树脂,1998(1):59-60.
[13]李仙会,胡晓丹,陈瑞珠.环氧树脂改性研究进展[J].热固性树脂,2003,18(3):14
[14]杨其,李光宪,黄亚江,等.环氧树脂/聚氨酯共混体系相行为研究[J].高分子学报,2003(1):68-72.
[15]韦春,谭松庭,刘敏娜,等.环氧树脂/液晶聚合物体系的形态、力学性能和热稳定性[J].高分子学报,2002(2):187-49
[16]阳范文,赵耀明.电子封装用环氧树脂的研究现状与发展趋势[J].电子工艺技术,2001,22(6):239-240.
[17]Jansen B L J,Tamnminga K Y,Meijer H E H et al,Preparation of themoset rubbery epoxy particles as novel tougheningmodi-fiers for glassy epoxy resins[J].Polymer,1999,40:5601-5607.
[18]Kmmann X,Linbderg H,Berglund L A.Synthesis of epoxy-clay anocomposites:influence of the nature of the clay on structure[J].Polymer,2001,(42):4493-4499.
[19]Janis M B,David Curliss.Effects of specimen size and sample aspectratio on the elastic stiffness of graphite/epoxy laminates[J].ChemMater,2000,(12):3376-3384.
[20]KimJ S,Reneker D H.Interfacial Aspects of Electrodeposited CarbonFiber-Reinforced.Epoxy composites Using Monomeric and PolymericCoupling Agents[J].The Institute of Polymer Science,1999(35):8-12.
[21]Ruiz Hitkhy E.Through-thickness failure of laminated carbon/ epoxycomposites under combined stress[J].Advanced Materials,1995(2):180-184.
[22]伍敏扬.日本封装材料用环氧树脂动向[J].化工新材料,27(3):22-25.
[23]吴良义.耐热、耐湿环氧树脂及其组成物的国外开发趋势[J].热固性树脂,2000,15(4):30-40.
[24]付中林,吴璧耀.电子塑封材料用环氧树脂的进展[J].武汉化工学院学报,2003,25(14):48
[25]郝玉龙.低应力环氧灌封料的研制及应用[J].混合微电子技术,1998,9(1):54 59.
[26]左瑞霖,常鹏善,解云川,等.液晶环氧树脂研究进展[J].高分子材料科学与工程,2002,18(4):69.
[27]李军,王文广,高雯.塑料的透明改性[J].塑料科技,1999(1):22-24.
[28]王从曾,刘会亭.材料性能学[M].北京:北京工业大学出版社,2001.151-158.
[29]何昌洪.纳米Mg(OH)_2与MgO的制备及研究.哈尔滨工程大学硕士学位论文.2004.20-21,40-41,51-52.
[30]胡章文,饶丹丹,杨保俊,等.高纯纳米氧化镁制备工艺研究[J].矿冶工程,2006,26(5):68.
[31]张伟,王宝和纳米氧化镁粉体制备技术的研究进展[J].中国粉体技术,2004(2):40-44.
[32]Watari Takanori,Sakayoshi,kazumi.Akio Preparation of suhmicron magnesium oxide powders by vapor-phase reaction of mabncsium and oxygen[J].Joumal of the Chemical Society of,Japan,I984(6):1075-1076.
[33]宋士涛等.纳米氧化镁的制备与表征[J].无机盐工业,2005,37(12):35.
[34]王志奎,杨荣臻.[J].功能材料,1990,30(5):557-558.
[35]梁桂勇,翟学良,秦冀广.超细粉末的液相制备技术及其比较[J].河北师范大学学报(自然科学版)1999,23(1):97-101
[36]Chhor K,Boocquet,J F,Pommicr C.Syntheses of suhmicron magnesium oxide powders [J].Materials Cheistrv and Physics,1995,40(1):63-68.
[37]王海霞.纳米氧化镁的制备及其表面改性的研究,硕士学位论文,华东师范大学.2006
[38]周益明,忻新泉.低温固相合成化学[J].无机化学学报,1999,15(3):273-292.
[39]汪国忠,程素芳,何国良,等.纳米级MgO粉体的合成[J].合成化学,1996,4(4):300.
[40]酒金婷,李立平,葛钥,等.用高分子保护的纳米MgO的合成[J].无机化学学报,2001,17(3):361-365.
[41]朱亚光,曾人杰,刘新锦,等.MgO纳米粉制备及表征[J].厦门大学学报(自然科学版),2001,40(6):1256-1259.
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