PI/Al_2O_3纳米杂化膜聚集态结构研究及成分分析
摘要
聚酰亚胺(Polyimide,简称PI)作为一种高性能工程材料,在宽广的温度范围内具有优异的物理、化学和电性能,应用领域已经相当广泛。SiO_2、Al_2O_3和TiO_2等无机纳米粒子具有非常优异的物理化学性能,将其引入到聚酰亚胺基体中,能使材料表现出优异的综合性能。目前国内外关于不同掺杂方法对PI/Al_2O_3杂化薄膜聚集态结构的影响、杂化薄膜聚集态结构与热性能之间的关系及对杂化膜准确的成分分析方法还鲜有较为系统的报道。
本论文以均苯四甲酸二酐和4,4′-二胺基二苯醚为有机单体,在N, N-二甲基乙酰胺中的逐步缩聚反应制备聚酰胺酸,分别通过纳米粒子直接掺杂法和溶胶改性法引入无机组分,再热亚胺化成膜。以纳米粒子直接掺杂法引入无机组分,称为纳米粒子杂化薄膜,以溶胶改性法引入无机组分,称为铝溶胶杂化薄膜。采用傅立叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、原子力显微镜(AFM)、热重分析仪(TG)、X射线荧光光谱仪波长色散型(WDXRF)分别表征和分析杂化薄膜的化学结构、聚集态结构、热性能和无机组分含量。
研究结果表明:在聚集态结构上,与纳米粒子杂化膜相比,铝溶胶杂化膜的无机粒子粒径较小且分布均匀。随Al_2O_3含量的增加,铝溶胶杂化膜中,无机相由孤立球形粒子逐渐形成网络结构,而在纳米粒子杂化膜中,无机相由较大尺寸团聚粒子趋于连续分布;从热性能上看,氧化铝的加入,改善了两种杂化薄膜的热稳定性,但铝溶胶杂化膜的热稳定性优于纳米粒子杂化膜。杜邦膜击穿后,击穿孔边缘破坏严重,有机相被破坏,同时无机相发生迁移,而在击穿孔附近被有机相残留物包裹的无机相结构变化较小。在成分分析上,与电子能谱仪(EDX)相比,应用X射线荧光光谱波长色散型(WDXRF)分析杂化膜,其结果精度更高、偏差分布更窄。用其分析杂质金属元素的含量,对分析矿化度值、改进制备工艺及原料处理工艺有较大参考价值。
As a high-performance engineering material, polyimide (PI) had excellent physical, chemical and electrical properties in a broad temperature range, and had a wide application area. SiO_2, Al_2O_3 and TiO_2 nano-particles with super good physical and chemical properties were introduced into the PI matrix, and the composite materials showed excellent combined property. Presently at home and overseas, the coherent articles on the affects about different doped methods to the aggregation structure, the relationship between the thermal performance and state gathered, and the accurate component analysis were very rare.
In this paper, the polyamide acid (PAA) were prepared with the Pyromellitic dianhydride (PMDA), 4, 4′oxydianilline (ODA) in the solution of the N, N′-dimethylacetamide (DMAc) by the poly-condensation. The PAA were doped with the way of sol-gel and mixed with the nano-particles directly. At last the films which contained nano-particles (named as nano-particles film) and the Al sol (named as Al Sol film) individually were obtained by the imidization. The chemical structure, aggregation structure, thermal properties and inorganic component content of two films were characterized and analyzed by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and X-ray fluorescence spectrometer - dispersion wavelength (WDXRF), respectively.
The results showed that, compared with nano-particles film, the nano-particles in the Al Sol film were smaller, and were dispersed very homogeneously from the aspect on aggregation structure. Increased with the content of Al_2O_3, the inorganic phase had evolved into network structure from the isolated spherical phase in the Al Sol film, but that of nano-particles film changed into the continuous distribution from the larger particle size. The thermal stability of two films had been improved with the addition of alumina from the aspect on thermal property. The thermal stability of the Al Sol film was better than that of nano-particles film. After the breakdown of DuPont membrane, the films had been damaged seriously on the edge of role. The organic matrix was completely decomposed and the inorganic particles were removed. However, the structure of inorganic phase embedded by organic leftovers had been changed a little near the breakdown hole. From the application of component analysis, the results with the method WDXRF was better than that with the way of electronic spectroscopy (EDX). The accuracy was higher and the deviation dispersed more narrowly. The results used with the method WDXRF about the content of heavy metal, the analysis of mineralization value, the improvement of preparation technology and treatment of the raw materials had great reference value.
本论文以均苯四甲酸二酐和4,4′-二胺基二苯醚为有机单体,在N, N-二甲基乙酰胺中的逐步缩聚反应制备聚酰胺酸,分别通过纳米粒子直接掺杂法和溶胶改性法引入无机组分,再热亚胺化成膜。以纳米粒子直接掺杂法引入无机组分,称为纳米粒子杂化薄膜,以溶胶改性法引入无机组分,称为铝溶胶杂化薄膜。采用傅立叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、原子力显微镜(AFM)、热重分析仪(TG)、X射线荧光光谱仪波长色散型(WDXRF)分别表征和分析杂化薄膜的化学结构、聚集态结构、热性能和无机组分含量。
研究结果表明:在聚集态结构上,与纳米粒子杂化膜相比,铝溶胶杂化膜的无机粒子粒径较小且分布均匀。随Al_2O_3含量的增加,铝溶胶杂化膜中,无机相由孤立球形粒子逐渐形成网络结构,而在纳米粒子杂化膜中,无机相由较大尺寸团聚粒子趋于连续分布;从热性能上看,氧化铝的加入,改善了两种杂化薄膜的热稳定性,但铝溶胶杂化膜的热稳定性优于纳米粒子杂化膜。杜邦膜击穿后,击穿孔边缘破坏严重,有机相被破坏,同时无机相发生迁移,而在击穿孔附近被有机相残留物包裹的无机相结构变化较小。在成分分析上,与电子能谱仪(EDX)相比,应用X射线荧光光谱波长色散型(WDXRF)分析杂化膜,其结果精度更高、偏差分布更窄。用其分析杂质金属元素的含量,对分析矿化度值、改进制备工艺及原料处理工艺有较大参考价值。
As a high-performance engineering material, polyimide (PI) had excellent physical, chemical and electrical properties in a broad temperature range, and had a wide application area. SiO_2, Al_2O_3 and TiO_2 nano-particles with super good physical and chemical properties were introduced into the PI matrix, and the composite materials showed excellent combined property. Presently at home and overseas, the coherent articles on the affects about different doped methods to the aggregation structure, the relationship between the thermal performance and state gathered, and the accurate component analysis were very rare.
In this paper, the polyamide acid (PAA) were prepared with the Pyromellitic dianhydride (PMDA), 4, 4′oxydianilline (ODA) in the solution of the N, N′-dimethylacetamide (DMAc) by the poly-condensation. The PAA were doped with the way of sol-gel and mixed with the nano-particles directly. At last the films which contained nano-particles (named as nano-particles film) and the Al sol (named as Al Sol film) individually were obtained by the imidization. The chemical structure, aggregation structure, thermal properties and inorganic component content of two films were characterized and analyzed by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), atomic force microscopy (AFM), thermogravimetric analysis (TGA) and X-ray fluorescence spectrometer - dispersion wavelength (WDXRF), respectively.
The results showed that, compared with nano-particles film, the nano-particles in the Al Sol film were smaller, and were dispersed very homogeneously from the aspect on aggregation structure. Increased with the content of Al_2O_3, the inorganic phase had evolved into network structure from the isolated spherical phase in the Al Sol film, but that of nano-particles film changed into the continuous distribution from the larger particle size. The thermal stability of two films had been improved with the addition of alumina from the aspect on thermal property. The thermal stability of the Al Sol film was better than that of nano-particles film. After the breakdown of DuPont membrane, the films had been damaged seriously on the edge of role. The organic matrix was completely decomposed and the inorganic particles were removed. However, the structure of inorganic phase embedded by organic leftovers had been changed a little near the breakdown hole. From the application of component analysis, the results with the method WDXRF was better than that with the way of electronic spectroscopy (EDX). The accuracy was higher and the deviation dispersed more narrowly. The results used with the method WDXRF about the content of heavy metal, the analysis of mineralization value, the improvement of preparation technology and treatment of the raw materials had great reference value.
引文
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