【作者】 靳玉伟；

【导师】 王策；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2006， 博士

【摘要】 随着纳米技术的发展,纳米自组装技术也得到了不断的发展和完善,近几年来,在高压电场下来实现高分子和相关材料的有序组装是构筑微尺度图案化结构的最新方法。本论文以电纺丝技术为基础,通过高压电场的诱导进行电组装。首先通过在高分子中不添加金属卟啉有机络合物电组装过程获得的复合纤维形貌进行研究,得到了具有规则螺旋及折叠结构的微米纤维。其次在高分子中掺杂第二组分金属有机络合物,如锌卟啉、锰卟啉;不同配体的金属锰卟啉;以及不带中心离子的非金属卟啉有机络合物如四苯基卟啉,利用不同卟啉结构性质的差异,电组装出不同形貌的微米/纳米复合纤维图案化,详细研究了纳米纤维制备的影响因素,并探讨其形成机理,研究结果确证了卟啉中心金属离子的极化是一维纤维材料连续组装形成的主要因素和主要驱动形式,建立了在高压电场诱导下图案化结构连续形成的新方法,为进一步相关有序结构的构筑与器件打下良好的基础。更多还原

【Abstract】 Ever since 1980, when the nano-technology was initiated, thenano self-assembly technical has been developed and improved,intriguing the preparation of various material and study ofperformance.Nano self-assembly technology develops to interspace restricteddirection using some composition spontaneity, formation schism orcontinous entity in molecule、covalent bond 、 super-molecule andnon-covalent bond. It includes “top-down” and “bottom-top”self-assembly. However, the ultimate challenge that both face is thecontinuous self-assembly of nano structure and patterning. In thisdissertation, we used high voltage and electrospinning technology,adding metal organic polymers, formation nanofibers and continuousstructure of Porphyrin/Polymer composite under high voltage electricfield. We called it electric self-assembly, which origins fromelectrospinning.In this dissertation, we obtain the continuous self-assemblynanofibers of Porphyrin/PVP by using the special structure andcharacearistics of Porphyrin via electric self-assembly, study thevarious parameters that have influence on the patterning and discussthe formation mechanism.In Chapter two introduces the formation of micro fibers ofregulation helix ring and collapse structure. We chose the raw materialof PVP, not adding metal organic polymer. From the research wefound that the shapes of PVP microfibril can change by improving theconcentration of solution, the variational disciplinarians of the shapesvary from beeline to helix to fold to out-of-order. We also found thatwhen the concentrations increase, separately, if we enlarged thevoltage the morphologies could change from out-of-order to fold tohelix to out-of-order, and the main factor is bending instability of thecharges of nanofibers.In Chapter three, we choose PVP, adding TFBOPPZn, water andethanol separately as solvent. Study the influence that the quantity ofmetal organic polymer and voltage have on the patterning of fibers.We found that as the quantity increases. The size of particles decrease,and the regulation of nanofibers and patterning increases. We thinkthat the cause is the weak force such as hyollogen bond.In Chapter four, we choose PVP, adding the center mental of Mn,one is the Manganese (Ⅲ) tetrakis (1-methyl-4-pyridyl) porphyrinpentachloride,MnTMPyP.the other is Manganese ( Ⅲ ) tetrakis(4-benzoic acid) Porphyrin, MnTBAP. This study described thepreparation of discontinuous helical fibers of poly (N-vinylpyrrolidone)(PVP) containing metalloporphyrin molecules using electrospinningmethod. SEM images showed that before adding the metalloporphyrinmolecules, the electrospun nanofibers are straight and smooth, whileafter adding a little metalloporphyrin molecules into the PVP solutions,SEM images clearly showed that there were two different types ofmaterialS: the thinner fibrous phase and the thicker discontinuoushelical fibers. The structure of the resulting PVP/metalloporphyrincomposite fibers was characterized by Fourier-transform infrared(FTIR) and energy dispersive X-ray (EDX) analysis. And thePhotoluminescence spectra of PVP/metalloporphyrin composite fiberswere also investigated. We have described the preparation ofdiscontinuous helical fibers of poly (N-vinylpyrrolidone) containingmetalloporphyrin molecules using electrospinning method in ethanolsolution. SEM images clearly showed that there were two differenttypes of material to be visible: the thinner fibrous phase and thethicker discontinuous helical fibers. When electrospun in DMSO/H2Osolutions, it was found that the thinner fibers could not be found, whilethe discontinuous helical fibers could still be obtained. We think thatthe formation of the discontinuous helical fibers may probably beascribed to the polarization of metalloporphyrin molecules in the PVPmatrices under high voltage.In Chapter five, we choose PVP, adding the TPP, non-metal ion.The result is that no continuous patterning was found. It shows thatcause of the formation of continuous patterning is the polarization ofcenter of metal ion.In conclusion, we have obtained the continuous self-assembly ofnano structure and patterning, established a new method to prepare.continuous nano materials under high voltage. We believed by furtherstudying of the course of electric self-assembly, exploiting equipment,we can produce new material, new electronic apparatus.更多还原