Ditsch Andre, Laibinis Paul E, Wang Daniel I C, Hatton T Alan
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
Langmuir. 2005 Jun 21;21(13):6006-18. doi: 10.1021/la047057+.
The clustering and stability of magnetic nanoparticles coated with random copolymers of acrylic acid, styrenesulfonic acid, and vinylsulfonic acid has been studied. Clusters larger than 50 nm are formed when the coatings are made using too low or too high molecular weight polymers or using insufficient amounts of polymer. Low-molecular-weight polymers result in thin coatings that do not sufficiently screen van der Waals attractive forces, while high-molecular-weight polymers bridge between particles, and insufficient polymer results in bare patches on the magnetite surface. The stability of the resulting clusters is poor, but when an insufficient polymer is used as primary coating, and a secondary polymer is added to coat remaining bare magnetite, the clusters are stable in high salt concentrations (>5 M NaCl), while retaining the necessary cluster size for efficient magnetic recovery. The magnetite cores were characterized by TEM and vibrating sample magnetometry, while the clusters were characterized by dynamic light scattering. The clustering and stability are interpreted in terms of the particle-particle interaction forces, and the optimal polymer size can be predicted well on the basis of these forces and the solution structure and hydrophobicity of the polymer. The size of aggregates formed by limited polymer can be predicted with a diffusion-limited colloidal aggregation model modified with a sticking probability based on fractional coating of the magnetite cores.
已对涂覆有丙烯酸、苯乙烯磺酸和乙烯基磺酸无规共聚物的磁性纳米颗粒的聚集和稳定性进行了研究。当使用分子量过低或过高的聚合物或聚合物用量不足进行包覆时,会形成大于50 nm的聚集体。低分子量聚合物会导致涂层过薄,无法充分屏蔽范德华吸引力,而高分子量聚合物会在颗粒之间形成桥连,聚合物用量不足会导致磁铁矿表面出现裸露斑块。所得聚集体的稳定性较差,但当使用不足量的聚合物作为 primary coating,并添加 secondary polymer 来包覆剩余的裸露磁铁矿时,聚集体在高盐浓度(>5 M NaCl)下是稳定的,同时保留了有效磁回收所需的聚集体尺寸。通过透射电子显微镜(TEM)和振动样品磁强计对磁铁矿核心进行了表征,而通过动态光散射对聚集体进行了表征。根据颗粒间相互作用力对聚集和稳定性进行了解释,并且基于这些力以及聚合物的溶液结构和疏水性,可以很好地预测最佳聚合物尺寸。由有限聚合物形成的聚集体的尺寸可以用基于磁铁矿核心部分包覆的粘附概率修正的扩散限制胶体聚集模型来预测。