氧化石墨烯及其复合材料的制备与表征
摘要
本文通过Hummers法制备氧化石墨,将其分散于有机溶剂中进行超声处理制备氧化石墨烯分散液,选取最具代表性且应用最广的两种塑料——尼龙6(PA6)、聚丙烯(PP)为基体,采用物理溶液混合法制备了聚合物／氧化石墨烯复合材料。采用傅利叶红外光谱扫描仪(FT-IR)、拉曼光谱分析(Raman)、热失重分析仪(TGA/DTG)、差示扫描量热仪(DSC)、X射线衍射仪(XRD)及偏光显微镜(POM)对氧化石墨烯及其复合体系进行了结构表征和性能测试,采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)对其微观分散性进行了观察。
FT-IR, Raman、XRD、SEM和TEM分析表明,采用Hummers法成功制备氧化石墨,经超声处理得到了尺寸为纳米级的氧化石墨烯,能均匀分散于乙二醇中,经异氰酸酯(TDI)改性后能均匀分散于甲酸中。
对于聚合物／氧化石墨烯复合体系,通过SEM表征观察到氧化石墨烯能均匀分散于基体中,POM、XRD和DSC分析表明氧化石墨烯的加入对聚合物基体的晶体尺寸、结晶度、结晶温度、结晶速率等影响比较显著,但不影响其晶型。氧化石墨烯一方面破坏了基体分子链的规整性,另一方面起到成核剂作用使基体的结晶性能增强。TGA/DTG分析表明氧化石墨烯的加入对基体的热稳定性影响不明显。对复合体系作热降解动力学分析的结果表明,氧化石墨烯的加入使聚合物的热降解活化能增大。
In this paper, graphite oxide was prepared by hummers method, and then was subjected to ultrasonic treatment in the organic solvents to prepare graphene oxide. Using typic polymer materials PA and PP as matrix, respectively, grapheme oxide as filler, graphene oxide/ polymer composites were prepared by physical solution blending. Graphene oxide and the composite systems were characterized by means of Fourier IR spectra (FTIR), Raman spectroscopy (Raman), Thermal gravimetric analyzer and Derivative Thermo-gravimetry (TGA/DTG), Differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Polarized optical microscopy (POM). Meanwhile, Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) were used to observe the microstructure of graphene oxide and the composite systems.
The analysis results of FT-IR, Raman, XRD and TEM show that graphene oxide was successfully prepared and graphene oxide was obtained after ultrasonic treatment. The size of graphene oxide has reached the nm level. Graphene oxide can disperse well in ethylene glycol, and also disperse well in formic acid followed by isocyanate treatment.
For the composite systems, SEM photographs show that graphene oxide could disperse well in the matrix, POM、XRD and DSC analysis results indicate that the addition of grahene oxide has a great influence on the crystal performances of the matrix, such as crystal morphology, crystallinity, crystallization temperature, crystallization rate, but has no influence on the crystal form. All of these may because that on the one hand the addition of graphene oxide destroyes the molecular chain regularity, on the other hand it enhances the crystallization of the matrix as nucleating agent. TGA/DTG analysis result shows that the addition of graphene oxide played no obvious role in the thermal stability of the matrix. With the analysis of thermal degradation kinetics, it can be concluded that with the addition of graphene oxide, the thermal degradation activation energy of the polymer increases.
FT-IR, Raman、XRD、SEM和TEM分析表明,采用Hummers法成功制备氧化石墨,经超声处理得到了尺寸为纳米级的氧化石墨烯,能均匀分散于乙二醇中,经异氰酸酯(TDI)改性后能均匀分散于甲酸中。
对于聚合物／氧化石墨烯复合体系,通过SEM表征观察到氧化石墨烯能均匀分散于基体中,POM、XRD和DSC分析表明氧化石墨烯的加入对聚合物基体的晶体尺寸、结晶度、结晶温度、结晶速率等影响比较显著,但不影响其晶型。氧化石墨烯一方面破坏了基体分子链的规整性,另一方面起到成核剂作用使基体的结晶性能增强。TGA/DTG分析表明氧化石墨烯的加入对基体的热稳定性影响不明显。对复合体系作热降解动力学分析的结果表明,氧化石墨烯的加入使聚合物的热降解活化能增大。
In this paper, graphite oxide was prepared by hummers method, and then was subjected to ultrasonic treatment in the organic solvents to prepare graphene oxide. Using typic polymer materials PA and PP as matrix, respectively, grapheme oxide as filler, graphene oxide/ polymer composites were prepared by physical solution blending. Graphene oxide and the composite systems were characterized by means of Fourier IR spectra (FTIR), Raman spectroscopy (Raman), Thermal gravimetric analyzer and Derivative Thermo-gravimetry (TGA/DTG), Differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Polarized optical microscopy (POM). Meanwhile, Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) were used to observe the microstructure of graphene oxide and the composite systems.
The analysis results of FT-IR, Raman, XRD and TEM show that graphene oxide was successfully prepared and graphene oxide was obtained after ultrasonic treatment. The size of graphene oxide has reached the nm level. Graphene oxide can disperse well in ethylene glycol, and also disperse well in formic acid followed by isocyanate treatment.
For the composite systems, SEM photographs show that graphene oxide could disperse well in the matrix, POM、XRD and DSC analysis results indicate that the addition of grahene oxide has a great influence on the crystal performances of the matrix, such as crystal morphology, crystallinity, crystallization temperature, crystallization rate, but has no influence on the crystal form. All of these may because that on the one hand the addition of graphene oxide destroyes the molecular chain regularity, on the other hand it enhances the crystallization of the matrix as nucleating agent. TGA/DTG analysis result shows that the addition of graphene oxide played no obvious role in the thermal stability of the matrix. With the analysis of thermal degradation kinetics, it can be concluded that with the addition of graphene oxide, the thermal degradation activation energy of the polymer increases.
引文
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