PI/Al_2O_3杂化薄膜Al含量分析方法、电晕老化及热老化寿命研究
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摘要
聚酰亚胺具有优良的力学、化学、耐辐射、电气性能及高低温使用性能,被广泛应用于电气绝缘、微电子工业和航空航天等领域。随着电力电子技术的发展,变频调速技术在电机中的应用越来越广泛,这项技术的应用可以使电机节电大约25%～30%,其节能效果相当显著。传统的聚酰亚胺耐局部放电性能已满足不了变频调制的使用要求,因此开展耐电晕PI杂化薄膜的研究显得大为重要,目前研究工作主要集中在杂化薄膜的制备工艺、纳米材料的分散性、热稳定性、绝缘性能等方面。但其电晕老化机理、热老化寿命的预测、杂化薄膜中无机组分的分析方法等问题尚有许多工作需要解决。
以自制PI/Al2O3杂化薄膜(纳米氧化铝直接掺杂法制备)、本课题组提供的系列PI/Al2O3纳米杂化薄膜(异丙醇铝溶胶-凝胶法制备)为研究对象,首次使用电感耦合等离子体原子发射光谱(ICP-AES)、X射线荧光光谱(XRF),结合傅立叶变换红外光谱(FT-IR)、X射线能量色散谱(EDS)、重量法、热失重(TG)等测试方法,对系列杂化亚胺薄膜的无机组分进行了定性、定量分析。结果表明：FT-IR和EDS技术可用于杂化薄膜的定性分析,FT-IR通过对材料的官能团进行分析,进而推断材料的结构和组成；而EDS则主要分析材料表面所含元素的含量。TG和EDS方法对杂化薄膜成分进行分析,其实测值和理论值相差较大,相对标准偏差(RSD)较大,TG和EDS方法只能进行半定量分析；而ICP-AES和重量法的实测值和理论值相差较小,重量法的RSD小于0.8%；ICP-AES的RSD小于0.6%,加标回收率为103.24%。最终建立了ICP-AES分析PI/Al2O3杂化薄膜中Al含量的分析方法。
利用扫描电子显微镜(SEM)、原子力显微镜(AFM)测定了系列杂化薄膜的微观结构。研究结果表明：在聚集态结构上,与PI/Al2O3杂化薄膜相比,PI/Al2O3纳米杂化薄膜中Al2O3粒径较小且分布均匀；随A1203含量的增加,杂化薄膜中Al2O3无机相由孤立球形粒子逐渐形成网络结构。
本文利用自制的电晕老化装置对DuPont耐电晕聚酰亚胺薄膜(Kapton100-CR)进行了10小时电晕老化处理。采用扫描电镜(SEM)、原子力显微镜(AFM)和能谱(EDS)等测试方法对电晕前后薄膜结构、成分进行分析,依据薄膜微观结构和元素含量的变化趋势,对耐电晕薄膜的电晕老化击穿机理进行了探讨。分析认为：薄膜为三层结构,外面两层含有大量的铝元素,内层为纯PI,整体属于无机—有机—无机复合结构。其电晕老化击穿过程由潜伏期、树枝化的扩展和崩溃性击穿三个阶段组成。其电晕老化属于电、热、化学老化作用的结果。
利用不同条件测得TG曲线,首次采用Coats-Redfern方法计算PI/Al2O3纳米杂化薄膜的热降解动力学参数,求得活化能(E)、碰撞因子(A)及反应级数(n)；按照材料热分解动力学与热老化之间的关系,拟合出杂化薄膜的热老化寿命曲线,进一步估算杂化薄膜长期使用的温度。实验结果表明,Coats-Redfern方法可用于PI/Al2O3纳米杂化薄膜热老化寿命的预测。
As a high-performance engineering material, polyimide (PI) having excellent physical, chemical and electrical properties in a broad temperature range, have been applied on the electric insulatation, microelectronics, and aerospace industry. With the developing power electronics technology, variable frequency speed control technology is widely applied in the electrical machine, power saving 20 to 30%. The effect on the power saving is quite remarkable. Traditional polyimide partial discharge resistant properties have been unable to meet the requirements of frequency modulation, thus limiting the polyimide applications. So study on corona-resistant PI hybrid films is of importance. Now the research on preparation conditions, the dispersion of nano-materials, thermal stability, insulating properties of corona resistant PI hybrid films are mainly foucsed on. The corona resistant of PI have been greatly improved, but its breakdown mechanism of aging, prediction of thermal aging, and inorganic hybrid membrane components such as component analysis problem for inorganic hybrid film has not yet been resolved.
Qualitative analysis and quantitative analysis on the Al content of PI/Al2O3 hybrid films were investigated using Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES), X-ray Fluorescence Spectrometry (XRF), Fourier Transform Infrared Spectrometry (FT-IR), X-ray Energy Dispersive Spectrometry (EDS), Gravimetric Method, Thermo-gravimetric Analysis (TG, in air atmosphere). The result showed that FT-IR and EDS were good qualitative analysis methods. FT-IR was used to confirm the structure and component via analyzing the group of hybrid films. EDS was mainly used to monitor elements contained in the surface of hybrid films. The relative standard deviations (RSD) of EDS and TG were too great to use quantitative analysis, then they only could be used as semi-quantitative analysis methods. On the contrary, ICP-AES and Gravimetric Method were excellent quantitative analysis methods. The RSD of Gravimetric Method is below 0.8%.The RSD of ICP-AES is below 0.6%. And the recovery of standard sample for ICP-AES is 103.24%. At last, the fast and accurate analysis method for the A1 content in the hybrid films was set up eventually by ICP-AES.
The aggregation structure of series hybrid films were measured via Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM).The result show that, compared with the PI/Al2O3 hybrid film, particle size and distribution of Al2O3 in PI/Al2O3 nano hybrid films were smaller. And increased with the content of Al2O3, the inorganic phase had evolved into network structure from the isolated spherical phase in the hybrid film.
The DuPont corona-resistant PI film (Kapton 100-CR) was treated with the device of corona aging test made by ourselves for 10 hours, and characterized via SEM, AFM, and EDS. The mechanism of corona aging and breakdown of Kapton 100-CR was studied depend on the variation trend of the microstructure and the element content. The results indicated that Kapton 100-CR film was made up of three layers. The outer layers contained a lot of Al element and the middle layer was pure PI. All of the films belonged to inorganic-organic-inorganic composite structure. The process of aging and breakdown had been composed of incubation course, expansion of branch and collapse breakdown. The corona aging of Kapton 100-CR derived from the electricity, heat and chemical reaction.
The thermal stabilization of PI/Al2O3 hybrid films made by ourselves was studied by TGA. First the thermal decomposition kinetics parameters (activation energy of thermal decomposition, collision coefficient and action progression) of PI hybride films containing 4wt% and 8wt% nano-alumina particles were calculated with the Coats-Redfern method at different heating rate in N2 and air, respectively.Then based on the relationship between thermal aging and the thermal decomposition kinetics, the thermal aging curve of PI hybrid films in air atmosphere and nitrogen atmosphere were draw out, getting the temperature for long term service. The results show that the Coats-Redfern method is reliable methods for prediction thermal aging life of PI/Al2O3 hybrid materials.
以自制PI/Al2O3杂化薄膜(纳米氧化铝直接掺杂法制备)、本课题组提供的系列PI/Al2O3纳米杂化薄膜(异丙醇铝溶胶-凝胶法制备)为研究对象,首次使用电感耦合等离子体原子发射光谱(ICP-AES)、X射线荧光光谱(XRF),结合傅立叶变换红外光谱(FT-IR)、X射线能量色散谱(EDS)、重量法、热失重(TG)等测试方法,对系列杂化亚胺薄膜的无机组分进行了定性、定量分析。结果表明：FT-IR和EDS技术可用于杂化薄膜的定性分析,FT-IR通过对材料的官能团进行分析,进而推断材料的结构和组成；而EDS则主要分析材料表面所含元素的含量。TG和EDS方法对杂化薄膜成分进行分析,其实测值和理论值相差较大,相对标准偏差(RSD)较大,TG和EDS方法只能进行半定量分析；而ICP-AES和重量法的实测值和理论值相差较小,重量法的RSD小于0.8%；ICP-AES的RSD小于0.6%,加标回收率为103.24%。最终建立了ICP-AES分析PI/Al2O3杂化薄膜中Al含量的分析方法。
利用扫描电子显微镜(SEM)、原子力显微镜(AFM)测定了系列杂化薄膜的微观结构。研究结果表明：在聚集态结构上,与PI/Al2O3杂化薄膜相比,PI/Al2O3纳米杂化薄膜中Al2O3粒径较小且分布均匀；随A1203含量的增加,杂化薄膜中Al2O3无机相由孤立球形粒子逐渐形成网络结构。
本文利用自制的电晕老化装置对DuPont耐电晕聚酰亚胺薄膜(Kapton100-CR)进行了10小时电晕老化处理。采用扫描电镜(SEM)、原子力显微镜(AFM)和能谱(EDS)等测试方法对电晕前后薄膜结构、成分进行分析,依据薄膜微观结构和元素含量的变化趋势,对耐电晕薄膜的电晕老化击穿机理进行了探讨。分析认为：薄膜为三层结构,外面两层含有大量的铝元素,内层为纯PI,整体属于无机—有机—无机复合结构。其电晕老化击穿过程由潜伏期、树枝化的扩展和崩溃性击穿三个阶段组成。其电晕老化属于电、热、化学老化作用的结果。
利用不同条件测得TG曲线,首次采用Coats-Redfern方法计算PI/Al2O3纳米杂化薄膜的热降解动力学参数,求得活化能(E)、碰撞因子(A)及反应级数(n)；按照材料热分解动力学与热老化之间的关系,拟合出杂化薄膜的热老化寿命曲线,进一步估算杂化薄膜长期使用的温度。实验结果表明,Coats-Redfern方法可用于PI/Al2O3纳米杂化薄膜热老化寿命的预测。
As a high-performance engineering material, polyimide (PI) having excellent physical, chemical and electrical properties in a broad temperature range, have been applied on the electric insulatation, microelectronics, and aerospace industry. With the developing power electronics technology, variable frequency speed control technology is widely applied in the electrical machine, power saving 20 to 30%. The effect on the power saving is quite remarkable. Traditional polyimide partial discharge resistant properties have been unable to meet the requirements of frequency modulation, thus limiting the polyimide applications. So study on corona-resistant PI hybrid films is of importance. Now the research on preparation conditions, the dispersion of nano-materials, thermal stability, insulating properties of corona resistant PI hybrid films are mainly foucsed on. The corona resistant of PI have been greatly improved, but its breakdown mechanism of aging, prediction of thermal aging, and inorganic hybrid membrane components such as component analysis problem for inorganic hybrid film has not yet been resolved.
Qualitative analysis and quantitative analysis on the Al content of PI/Al2O3 hybrid films were investigated using Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES), X-ray Fluorescence Spectrometry (XRF), Fourier Transform Infrared Spectrometry (FT-IR), X-ray Energy Dispersive Spectrometry (EDS), Gravimetric Method, Thermo-gravimetric Analysis (TG, in air atmosphere). The result showed that FT-IR and EDS were good qualitative analysis methods. FT-IR was used to confirm the structure and component via analyzing the group of hybrid films. EDS was mainly used to monitor elements contained in the surface of hybrid films. The relative standard deviations (RSD) of EDS and TG were too great to use quantitative analysis, then they only could be used as semi-quantitative analysis methods. On the contrary, ICP-AES and Gravimetric Method were excellent quantitative analysis methods. The RSD of Gravimetric Method is below 0.8%.The RSD of ICP-AES is below 0.6%. And the recovery of standard sample for ICP-AES is 103.24%. At last, the fast and accurate analysis method for the A1 content in the hybrid films was set up eventually by ICP-AES.
The aggregation structure of series hybrid films were measured via Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM).The result show that, compared with the PI/Al2O3 hybrid film, particle size and distribution of Al2O3 in PI/Al2O3 nano hybrid films were smaller. And increased with the content of Al2O3, the inorganic phase had evolved into network structure from the isolated spherical phase in the hybrid film.
The DuPont corona-resistant PI film (Kapton 100-CR) was treated with the device of corona aging test made by ourselves for 10 hours, and characterized via SEM, AFM, and EDS. The mechanism of corona aging and breakdown of Kapton 100-CR was studied depend on the variation trend of the microstructure and the element content. The results indicated that Kapton 100-CR film was made up of three layers. The outer layers contained a lot of Al element and the middle layer was pure PI. All of the films belonged to inorganic-organic-inorganic composite structure. The process of aging and breakdown had been composed of incubation course, expansion of branch and collapse breakdown. The corona aging of Kapton 100-CR derived from the electricity, heat and chemical reaction.
The thermal stabilization of PI/Al2O3 hybrid films made by ourselves was studied by TGA. First the thermal decomposition kinetics parameters (activation energy of thermal decomposition, collision coefficient and action progression) of PI hybride films containing 4wt% and 8wt% nano-alumina particles were calculated with the Coats-Redfern method at different heating rate in N2 and air, respectively.Then based on the relationship between thermal aging and the thermal decomposition kinetics, the thermal aging curve of PI hybrid films in air atmosphere and nitrogen atmosphere were draw out, getting the temperature for long term service. The results show that the Coats-Redfern method is reliable methods for prediction thermal aging life of PI/Al2O3 hybrid materials.
引文
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