聚酰亚胺/纳米Al_2O_3三层复合薄膜的研究
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摘要
近年来,聚酰亚胺(PI)/无机纳米复合材料得到了广泛研究,SiO2、Al_2O_3、TiO2等纳米氧化物的加入在改善PI薄膜电性能、热稳定性的同时造成了PI薄膜力学性能的下降,这对制备综合性能良好的PI薄膜提出了新的要求。
本文以均苯四甲酸二酐(PMDA)及4, 4′-二氨基二苯醚(ODA)为原料,N, N-二甲基乙酰胺(DMAc)为溶剂经逐步缩聚反应制备聚酰胺酸(PAA),采用机械共混法将经硅烷偶联剂改性的纳米Al_2O_3粉体,借助超声波以一定的方式加入到PAA中,经其在玻璃板上逐层涂膜及不同热亚胺化制备了一系列PI/纳米Al_2O_3三层复合薄膜。分析了各种单因素(一、二层成膜温度及时间和未掺杂层与单层掺杂层厚度比)对力学性能的影响,设计了三因素三水平的正交试验,并对其进行了分析,结果表明制备力学性能最佳的PI三层复合薄膜的工艺条件是:温度180℃,时间90min,厚度比2:1。根据该工艺制备了不同Al_2O_3含量及不同偶联剂种类的PI复合薄膜。
采用扫描电子显微镜(SEM)及红外光谱(FT-IR)对PI薄膜的微观形貌及结构进行了表征。扫描电镜分析表明PI复合薄膜具有明显的三层结构,纳米Al_2O_3的含量和偶联剂的种类对三层结构和分散状态影响较大。
测试了PI薄膜的紫外-可见光透过率、力学性能、热稳定性和电击穿场强。紫外-可见光光谱分析表明PI复合薄膜的透光性比掺杂薄膜提高了7.2%(波长为600nm),不同Al_2O_3含量及不同偶联剂种类的PI薄膜的透光性存在明显差异,其中使用硅烷偶联剂KH560的PI薄膜的透光性最好,并比未改性薄膜提高了8.8%(波长为600nm);热重分析表明PI复合薄膜的热分解温度(T10)分别比纯膜及掺杂薄膜提高了28.1℃和17.4℃,随着纳米Al_2O_3含量的增加薄膜热分解温度随之增加,偶联剂种类对其影响很小;力学性能分析表明PI复合薄膜的拉伸强度分别比纯PI膜及掺杂薄膜提高了8.4%和11.9%,断裂伸长率比掺杂薄膜提高了43.6%,但略高于纯膜。其中使用硅烷偶联剂KH550的PI复合薄膜的力学性能最好,拉伸强度和断裂伸长率分别为119.1MPa和19.1%,分别比未改性的PI复合薄膜提高了14.2%和78.5%;电击穿场强分析表明PI复合薄膜的击穿场强均高于纯膜及掺杂薄膜,偶联剂的种类对PI薄膜的击穿场强影响较小,随着掺杂量的增加,击穿场强先增加后减小,当纳米Al2O3含量为6 wt%时击穿场强最高,为284kV/mm。
In recent years, increasing attention had been paid to the polyimide/inorganic nanocomposite materials. It has been proved that the thermal and electrical properties of PI films can be improved, however, mechanical properties of PI films decreased by incorporation of fillers such as silica, alumina and titania into the pristine polyimide matrix. It put forward the requirements for preparation of PI films with good comprehensive properties.
In this paper, a series of polyimide(PI)/nano-Al_2O_3 three-layer composite films were prepared with thermal imiditation after pure poly(amic acid) or Al_2O_3/poly(amic acid) solution was cast on glass plate step by step, poly(amic acid) were synthesized by step-polycondensation of 4, 4′-oxydianiline(ODA) and pyromellitic dianhydride(PMDA) in the solution of N, N-dimethylacetamide (DMAc), Al_2O_3/poly(amic acid) solution was prepared by the addition of the nano-Al_2O_3 which had been treated by coupling agent into the poly(amic acid) solution by ultrasonic wave through the ultrasonic-mechanical method. The influence of film forming temperature and time of the first and second layer and thickness ratio of pure layer and single hybrid layer on the mechanical properties of PI composite films was analyzed. On this basis, a scheme of orthogonal test, which included three factors and three levels, was used and analyzed. The result showed that the optimal preparation condition of PI composite film with good mechanical properties was conculuded as that film forming temperature 180℃, film forming time 90min, the thickness ratio of pure layer and hybrid layer 2:1.
The micro-morphology and structure of PI films were studied by scanning electronic microscope(SEM) and fourier transform infrared spectrum(FT-IR). SEM analysis showed that there was clear three-layer structure in the PI composite films, and the silane coupling agents varieties and the nano-Al_2O_3 content had much effect on the dispersion of nano-Al_2O_3 particles in the PI composite films.
The transmittance of UV-Vis, thermal stability, mechanical properties and electric breakdown strength of PI films were tested. UV-Vis transmittance analysis revealed that the transmittance of PI composite films was 7.2% higher than hybrid film at the wavelength of 600nm, and the silane coupling agents varieties and the nano-Al_2O_3 content had obvious effect on the transmittance of the PI composite films. In these four kinds of composite films, the transmittance of PI/nano-Al_2O_3 composite film with KH560 was the best, which was higher 8.8% than unmodified film at the wavelength of 600nm. TGA analysis showed that the decomposition temperature of PI composite film was 28.1℃higher than pure PI film and 17.4℃higher than hybrid film at 10% weight loss respectively. The decomposition temperature of PI composite films increased with increase of nano-Al_2O_3 content, but the silane coupling agents varieties had less effect on the thermal stability of PI composite films. The tensile strength of PI composite film was 8.4% higher than pure PI film and 11.9% higher than hybrid film respectively, the elongation at break of PI composite film was 43.6% higher than hybrid film, but was slightly higher than pure PI film. The mechanical properties of PI/nano-Al_2O_3 composite film with KH550 were the best. The tensile strength and elongation at break of PI composite film were 119.1Mpa and 19.1%, which were 14.2% and 78.5% higher than unmodified PI composite film respectively. PI composite films had improved electric breakdown strength in comparison with pure PI film and hybrid film. The silane coupling agents varieties had less effect on the electric breakdown strength of PI composite films. When the nano-Al_2O_3 content was low, electric breakdown strength of PI composite films rised with increase of nano-Al_2O_3 content. However, further increase in the nano-Al_2O_3 content lead to a gradual decrease in the electric breakdown strength. The electric breakdown strength of PI composite films with nano-Al_2O_3 content 6wt% was 284kV/mm, which was the best in the PI composite films with different nano-Al_2O_3 content.
本文以均苯四甲酸二酐(PMDA)及4, 4′-二氨基二苯醚(ODA)为原料,N, N-二甲基乙酰胺(DMAc)为溶剂经逐步缩聚反应制备聚酰胺酸(PAA),采用机械共混法将经硅烷偶联剂改性的纳米Al_2O_3粉体,借助超声波以一定的方式加入到PAA中,经其在玻璃板上逐层涂膜及不同热亚胺化制备了一系列PI/纳米Al_2O_3三层复合薄膜。分析了各种单因素(一、二层成膜温度及时间和未掺杂层与单层掺杂层厚度比)对力学性能的影响,设计了三因素三水平的正交试验,并对其进行了分析,结果表明制备力学性能最佳的PI三层复合薄膜的工艺条件是:温度180℃,时间90min,厚度比2:1。根据该工艺制备了不同Al_2O_3含量及不同偶联剂种类的PI复合薄膜。
采用扫描电子显微镜(SEM)及红外光谱(FT-IR)对PI薄膜的微观形貌及结构进行了表征。扫描电镜分析表明PI复合薄膜具有明显的三层结构,纳米Al_2O_3的含量和偶联剂的种类对三层结构和分散状态影响较大。
测试了PI薄膜的紫外-可见光透过率、力学性能、热稳定性和电击穿场强。紫外-可见光光谱分析表明PI复合薄膜的透光性比掺杂薄膜提高了7.2%(波长为600nm),不同Al_2O_3含量及不同偶联剂种类的PI薄膜的透光性存在明显差异,其中使用硅烷偶联剂KH560的PI薄膜的透光性最好,并比未改性薄膜提高了8.8%(波长为600nm);热重分析表明PI复合薄膜的热分解温度(T10)分别比纯膜及掺杂薄膜提高了28.1℃和17.4℃,随着纳米Al_2O_3含量的增加薄膜热分解温度随之增加,偶联剂种类对其影响很小;力学性能分析表明PI复合薄膜的拉伸强度分别比纯PI膜及掺杂薄膜提高了8.4%和11.9%,断裂伸长率比掺杂薄膜提高了43.6%,但略高于纯膜。其中使用硅烷偶联剂KH550的PI复合薄膜的力学性能最好,拉伸强度和断裂伸长率分别为119.1MPa和19.1%,分别比未改性的PI复合薄膜提高了14.2%和78.5%;电击穿场强分析表明PI复合薄膜的击穿场强均高于纯膜及掺杂薄膜,偶联剂的种类对PI薄膜的击穿场强影响较小,随着掺杂量的增加,击穿场强先增加后减小,当纳米Al2O3含量为6 wt%时击穿场强最高,为284kV/mm。
In recent years, increasing attention had been paid to the polyimide/inorganic nanocomposite materials. It has been proved that the thermal and electrical properties of PI films can be improved, however, mechanical properties of PI films decreased by incorporation of fillers such as silica, alumina and titania into the pristine polyimide matrix. It put forward the requirements for preparation of PI films with good comprehensive properties.
In this paper, a series of polyimide(PI)/nano-Al_2O_3 three-layer composite films were prepared with thermal imiditation after pure poly(amic acid) or Al_2O_3/poly(amic acid) solution was cast on glass plate step by step, poly(amic acid) were synthesized by step-polycondensation of 4, 4′-oxydianiline(ODA) and pyromellitic dianhydride(PMDA) in the solution of N, N-dimethylacetamide (DMAc), Al_2O_3/poly(amic acid) solution was prepared by the addition of the nano-Al_2O_3 which had been treated by coupling agent into the poly(amic acid) solution by ultrasonic wave through the ultrasonic-mechanical method. The influence of film forming temperature and time of the first and second layer and thickness ratio of pure layer and single hybrid layer on the mechanical properties of PI composite films was analyzed. On this basis, a scheme of orthogonal test, which included three factors and three levels, was used and analyzed. The result showed that the optimal preparation condition of PI composite film with good mechanical properties was conculuded as that film forming temperature 180℃, film forming time 90min, the thickness ratio of pure layer and hybrid layer 2:1.
The micro-morphology and structure of PI films were studied by scanning electronic microscope(SEM) and fourier transform infrared spectrum(FT-IR). SEM analysis showed that there was clear three-layer structure in the PI composite films, and the silane coupling agents varieties and the nano-Al_2O_3 content had much effect on the dispersion of nano-Al_2O_3 particles in the PI composite films.
The transmittance of UV-Vis, thermal stability, mechanical properties and electric breakdown strength of PI films were tested. UV-Vis transmittance analysis revealed that the transmittance of PI composite films was 7.2% higher than hybrid film at the wavelength of 600nm, and the silane coupling agents varieties and the nano-Al_2O_3 content had obvious effect on the transmittance of the PI composite films. In these four kinds of composite films, the transmittance of PI/nano-Al_2O_3 composite film with KH560 was the best, which was higher 8.8% than unmodified film at the wavelength of 600nm. TGA analysis showed that the decomposition temperature of PI composite film was 28.1℃higher than pure PI film and 17.4℃higher than hybrid film at 10% weight loss respectively. The decomposition temperature of PI composite films increased with increase of nano-Al_2O_3 content, but the silane coupling agents varieties had less effect on the thermal stability of PI composite films. The tensile strength of PI composite film was 8.4% higher than pure PI film and 11.9% higher than hybrid film respectively, the elongation at break of PI composite film was 43.6% higher than hybrid film, but was slightly higher than pure PI film. The mechanical properties of PI/nano-Al_2O_3 composite film with KH550 were the best. The tensile strength and elongation at break of PI composite film were 119.1Mpa and 19.1%, which were 14.2% and 78.5% higher than unmodified PI composite film respectively. PI composite films had improved electric breakdown strength in comparison with pure PI film and hybrid film. The silane coupling agents varieties had less effect on the electric breakdown strength of PI composite films. When the nano-Al_2O_3 content was low, electric breakdown strength of PI composite films rised with increase of nano-Al_2O_3 content. However, further increase in the nano-Al_2O_3 content lead to a gradual decrease in the electric breakdown strength. The electric breakdown strength of PI composite films with nano-Al_2O_3 content 6wt% was 284kV/mm, which was the best in the PI composite films with different nano-Al_2O_3 content.
引文
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