核壳结构磁性高分子微球的制备与性能研究
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摘要
纳米材料是当前最热门的学科之一，特别是自碳纳米管被发现以后，对纳米材料结构的设计与调控一直是纳米材料科学领域研究的重点。核壳结构纳米材料通常能通过协同效应，将两种或者多种材料的性能结合，从而打破材料之间的界限，并有可能获得新的独特的性质。作为新型的功能材料，核壳结构磁性高分子微球因其巨大的应用潜力已引起了各国研究者的高度重视，在药物载体、磁性橡胶、导电橡胶等领域有重要应用。本论文主要研究了核壳结构Ni_(0.5)Zn_(0.5)Fe_2O_4/ PANI、核壳结构Ni/PANI以及中孔MnFe_2O_4/PANI核壳结构磁性高分子微球的制备及性能。主要研究内容如下：
(1)以铁、镍、锌硝酸盐为金属盐，NaOH为沉淀剂，吐温80为表面活性剂，正戊醇为助表面活性剂组成的微乳液，通过微乳液法制备得到单分散性磁性Ni_(0.5)Zn_(0.5)Fe_2O_4纳米颗粒；再以苯胺盐酸盐为单体，通过微乳液聚合法，最终制得了Ni_(0.5)Zn_(0.5)Fe_2O_4/PANI核壳结构磁性高分子微球。SEM、TEM、FTIR以及TGA结果均表明，磁性Ni_(0.5_Zn_(0.5)Fe_2O_4纳米颗粒以及与PANI结合，并形成了一定厚度的包覆层，为典型的核壳结构。VSM结果显示，磁性Ni_(0.5)Zn_(0.5)Fe_2O_4纳米颗粒的的矫顽力、剩余磁化强度和饱和磁化强度分别为3.16Oe，2.48 emu/g，34.10emu/g，表现出良好的磁响应性。
(2)通过水热法制备了单分散Ni微球，并且通过原位分散聚合技术制得了Ni/PANI磁性高分子微球。通过SEM和TEM表征，观察到Ni微球以及Ni/PANI复合微球均具有很好的单分散性，粒径分布较窄；此外，还观察到Ni/PANI微球具有明显的核壳结构；FTIR和TGA结果进一步表明，PANI在Ni微球上有很好的结合，附着的PANI质量比率约为22%。VSM结果表明，最终得到的Ni/PANI核壳结构磁性高分子微球具有很好的磁响应性，其矫顽力和饱和磁化强度分别为0Oe，20.04emu/g。最后，对Ni微球和Ni/PANI核壳结构的形成机理进行了较为细致深入的探讨。
(3)通过溶胶-凝胶结合C微球模板法，制备了中孔结构MnFe_2O_4微球；并采用原位分散聚合技术，成功制得了中孔MnFe_2O_4/PANI核壳结构磁性高分子微球。FTIR和TGA结果表明，PANI与MnFe_2O_4有很好的结合，PANI的附着质量比率约为16%；SEM与TEM结果显示，MnFe_2O_4微球与MnFe_2O_4/PANI微球均具有很好的分散性，并且具有非常典型的中孔结构。VSM结果表明，最终得到的中孔MnFe_2O_4/PANI核壳结构磁性高分子微球具有很好的磁响应性，其矫顽力、剩余磁化强度和饱和磁化强度分别为0Oe，81.10emu/g，因而在药物载体领域可能有重要的潜在应用价值。
Nanomaterials have always been one of the hottest topics and the design and controlsynthesis of nanomaterials has always been of great importance since the discovery of carbonnanotubes in recent years. Core-shell structural nanomaterials, which combine the propertiesof two kinds or even more materials due to special effects, may show distinct properties andapplications, and over through the wall among different materials. As a novel and importantfunctional materials, core-shell structural magnetite polymetric composite microspheres haveshown apparent applications in the field of drug delivery, magnetic rubber and electronicrubber and have attracted significant attention all over the world. In this work, the fabricationand properties of core-shell structural magnetic polymetric composite microspheres, includingNi_(0.5)Zn_(0.5)Fe_2O_4/PANI, Ni/PANI and mesoporous MnFe_2O_4/PANI, have been carried out. Themain contest for the study can be described as follows:
(1) Mono-dispersed Ni_(0.5)Zn_(0.5)Fe_2O_4magnetic nano-particles were obtained throughmicro-emulsion, which was made up of the water phase, oil phase, surfactant andco-surfactant, by using Fe, Ni, and Zn nitrogen salt as metal source and employing NaOH asprecipitant. Further, Ni_(0.5)Zn_(0.5)Fe_2O_4/PANI core-shell structural magnetic polymetriccomposite microspheres were also fabricated in a similar micro-emulsion. The SEM, TEM,FTIR and TGA result might show that PANI has been coated on the outer surface layer ofNi_(0.5)Zn_(0.5)Fe_2O_4particles and typical core-shell structures have been obtained. The VSMresults revealed that the Ni_(0.5)Zn_(0.5)Fe_2O_4particles are magnetic and the value of Hc, Mr, andMs was 3.16Oe, 2.48 emu/g and 34.10emu/g, respectively.
(2) Mono-dispersed Ni microspheres and Ni/PANI magnetic composite microsphereswere also fabricated through a hydrothermal route and in-situ polymerization technique,respectively. The SEM and TEM results illustrated that both the obtained Ni microspheres andNi/PANI microspheres shown a narrow size distribution and mono-dispersion. Moreover, theTEM results directly confirmed the core-shell structure of Ni/PANI composite microspheres.In addition, it could be inferred from the FTIR and TGA results that the weight rate of coated PANI is ca. 22%. The VSM results suggested that the final products of Ni/PANI compositemicrospheres show good magnetic properties, and the value of Hc, and Ms of sample was 0Oe,and 20.04emu/g, respectively.
(3) Mesoporous MnFe_2O_4magnetic microspheres and mesoporous MnFe_2O_4/PANIcore-shell structured composite microspheres were prepared through a sol-gel assisted carbonspheres template method and in-situ polymerization process, respectively. The FTIR and TGAresults confirmed the combination of PANI and MnFe_2O_4, which may reveal the core-shellstructure. The weight rate of absorbed PANI was ca. 16%. Further, the SEM and TEM resultsillustrated that the obtained MnFe_2O_4microspheres and MnFe_2O_4/PANI compositemicrospheres have a typical mesoporous structure and a well-dispersion. At last, the VSMresults confirmed the enhanced magnetic properties of MnFe_2O_4/PANI compositemicrospheres, whose Hc, and Ms value was 0Oe, and 81.10emu/g, respectively. The obtainedproducts might show significant potential applications in the field of drug delivery and so on.
(1)以铁、镍、锌硝酸盐为金属盐，NaOH为沉淀剂，吐温80为表面活性剂，正戊醇为助表面活性剂组成的微乳液，通过微乳液法制备得到单分散性磁性Ni_(0.5)Zn_(0.5)Fe_2O_4纳米颗粒；再以苯胺盐酸盐为单体，通过微乳液聚合法，最终制得了Ni_(0.5)Zn_(0.5)Fe_2O_4/PANI核壳结构磁性高分子微球。SEM、TEM、FTIR以及TGA结果均表明，磁性Ni_(0.5_Zn_(0.5)Fe_2O_4纳米颗粒以及与PANI结合，并形成了一定厚度的包覆层，为典型的核壳结构。VSM结果显示，磁性Ni_(0.5)Zn_(0.5)Fe_2O_4纳米颗粒的的矫顽力、剩余磁化强度和饱和磁化强度分别为3.16Oe，2.48 emu/g，34.10emu/g，表现出良好的磁响应性。
(2)通过水热法制备了单分散Ni微球，并且通过原位分散聚合技术制得了Ni/PANI磁性高分子微球。通过SEM和TEM表征，观察到Ni微球以及Ni/PANI复合微球均具有很好的单分散性，粒径分布较窄；此外，还观察到Ni/PANI微球具有明显的核壳结构；FTIR和TGA结果进一步表明，PANI在Ni微球上有很好的结合，附着的PANI质量比率约为22%。VSM结果表明，最终得到的Ni/PANI核壳结构磁性高分子微球具有很好的磁响应性，其矫顽力和饱和磁化强度分别为0Oe，20.04emu/g。最后，对Ni微球和Ni/PANI核壳结构的形成机理进行了较为细致深入的探讨。
(3)通过溶胶-凝胶结合C微球模板法，制备了中孔结构MnFe_2O_4微球；并采用原位分散聚合技术，成功制得了中孔MnFe_2O_4/PANI核壳结构磁性高分子微球。FTIR和TGA结果表明，PANI与MnFe_2O_4有很好的结合，PANI的附着质量比率约为16%；SEM与TEM结果显示，MnFe_2O_4微球与MnFe_2O_4/PANI微球均具有很好的分散性，并且具有非常典型的中孔结构。VSM结果表明，最终得到的中孔MnFe_2O_4/PANI核壳结构磁性高分子微球具有很好的磁响应性，其矫顽力、剩余磁化强度和饱和磁化强度分别为0Oe，81.10emu/g，因而在药物载体领域可能有重要的潜在应用价值。
Nanomaterials have always been one of the hottest topics and the design and controlsynthesis of nanomaterials has always been of great importance since the discovery of carbonnanotubes in recent years. Core-shell structural nanomaterials, which combine the propertiesof two kinds or even more materials due to special effects, may show distinct properties andapplications, and over through the wall among different materials. As a novel and importantfunctional materials, core-shell structural magnetite polymetric composite microspheres haveshown apparent applications in the field of drug delivery, magnetic rubber and electronicrubber and have attracted significant attention all over the world. In this work, the fabricationand properties of core-shell structural magnetic polymetric composite microspheres, includingNi_(0.5)Zn_(0.5)Fe_2O_4/PANI, Ni/PANI and mesoporous MnFe_2O_4/PANI, have been carried out. Themain contest for the study can be described as follows:
(1) Mono-dispersed Ni_(0.5)Zn_(0.5)Fe_2O_4magnetic nano-particles were obtained throughmicro-emulsion, which was made up of the water phase, oil phase, surfactant andco-surfactant, by using Fe, Ni, and Zn nitrogen salt as metal source and employing NaOH asprecipitant. Further, Ni_(0.5)Zn_(0.5)Fe_2O_4/PANI core-shell structural magnetic polymetriccomposite microspheres were also fabricated in a similar micro-emulsion. The SEM, TEM,FTIR and TGA result might show that PANI has been coated on the outer surface layer ofNi_(0.5)Zn_(0.5)Fe_2O_4particles and typical core-shell structures have been obtained. The VSMresults revealed that the Ni_(0.5)Zn_(0.5)Fe_2O_4particles are magnetic and the value of Hc, Mr, andMs was 3.16Oe, 2.48 emu/g and 34.10emu/g, respectively.
(2) Mono-dispersed Ni microspheres and Ni/PANI magnetic composite microsphereswere also fabricated through a hydrothermal route and in-situ polymerization technique,respectively. The SEM and TEM results illustrated that both the obtained Ni microspheres andNi/PANI microspheres shown a narrow size distribution and mono-dispersion. Moreover, theTEM results directly confirmed the core-shell structure of Ni/PANI composite microspheres.In addition, it could be inferred from the FTIR and TGA results that the weight rate of coated PANI is ca. 22%. The VSM results suggested that the final products of Ni/PANI compositemicrospheres show good magnetic properties, and the value of Hc, and Ms of sample was 0Oe,and 20.04emu/g, respectively.
(3) Mesoporous MnFe_2O_4magnetic microspheres and mesoporous MnFe_2O_4/PANIcore-shell structured composite microspheres were prepared through a sol-gel assisted carbonspheres template method and in-situ polymerization process, respectively. The FTIR and TGAresults confirmed the combination of PANI and MnFe_2O_4, which may reveal the core-shellstructure. The weight rate of absorbed PANI was ca. 16%. Further, the SEM and TEM resultsillustrated that the obtained MnFe_2O_4microspheres and MnFe_2O_4/PANI compositemicrospheres have a typical mesoporous structure and a well-dispersion. At last, the VSMresults confirmed the enhanced magnetic properties of MnFe_2O_4/PANI compositemicrospheres, whose Hc, and Ms value was 0Oe, and 81.10emu/g, respectively. The obtainedproducts might show significant potential applications in the field of drug delivery and so on.
引文
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