Chemistry Laboratory Center, Department of Chemistry, Harbin Institute of Technology, Harbin 150001, China.
J Phys Chem B. 2012 Aug 9;116(31):9523-31. doi: 10.1021/jp3024099. Epub 2012 Jul 27.
Composites consisting of Fe(3)O(4) microspheres (FMS) and polyaniline (PANI), FMS/PANI, have been successfully prepared through a two-step oxidative polymerization of aniline monomers in the presence of Fe(3)O(4) microspheres. In our two-step polymerization technique, Fe(3+) and ammonium persulfate (APS) are used as the oxidants in each step. It is discovered that the two-step oxidative process plays a dominant role in the morphology of these composites: aniline oligomers oxidized by Fe(3+) are mainly produced in the first stage, and "egg-like" PANI aggregates are obtained in the second stage. It can be found that embedding Fe(3)O(4) microspheres in the polymer matrixes will not only modulate the complex permittivity but also produce magnetic resonance and loss in the composites. Therefore, the characteristic impedance and reflection loss of these composites are greatly improved. Especially, the composite with equal amount of FMS and PANI, FMS/PANI(50), displays very strong reflection loss over a wide frequency range that can be manipulated by the absorber thickness. More importantly, the composites prepared from the two-step chemical oxidative polymerization using hierarchical magnetic materials have better microwave absorption and environmental stability as compared with those composites from Fe(3)O(4) nanoparticles, one-step oxidative polymerization, and physical mixture. We believe the two-step oxidative polymerization technique can be a novel route for the design and preparation of lightweight and highly effective microwave absorbers in the future.
由 Fe(3)O(4) 微球 (FMS) 和聚苯胺 (PANI) 组成的复合材料 FMS/PANI 通过在 Fe(3)O(4) 微球存在下苯胺单体的两步氧化聚合成功制备。在我们的两步聚合技术中,Fe(3+)和过硫酸铵 (APS) 分别用作每一步的氧化剂。研究发现,两步氧化过程对这些复合材料的形态起着主导作用:在第一阶段,Fe(3+)氧化的苯胺低聚物主要生成,而在第二阶段则得到“蛋形”PANI 聚集体。可以发现,将 Fe(3)O(4)微球嵌入聚合物基质中不仅会调节复介电常数,而且会在复合材料中产生磁共振和损耗。因此,这些复合材料的特征阻抗和反射损耗得到了极大的提高。特别是,具有等量 FMS 和 PANI 的复合材料 FMS/PANI(50) 在很宽的频率范围内表现出非常强的反射损耗,可以通过吸收剂厚度来控制。更重要的是,与使用纳米 Fe(3)O(4)粒子、一步氧化聚合和物理混合物制备的复合材料相比,使用分级磁性材料的两步化学氧化聚合制备的复合材料具有更好的微波吸收和环境稳定性。我们相信,两步氧化聚合技术可以为设计和制备轻量化、高效的微波吸收剂提供一种新途径。