Department of Chemical Engineering, Centre for Self-Assembled Chemical Structures, McGill University, Montreal, Quebec H3A 2B2, Canada.
Langmuir. 2011 Sep 20;27(18):11416-29. doi: 10.1021/la203033s. Epub 2011 Aug 23.
Despite considerable efforts to synthesize nanotubes using porous alumina or polycarbonate membrane templates, few studies have addressed the resulting nanotube dispersion. We prepared dispersions of multilayered polyethylenimine/maleic anhydride alternating copolymer (PEI/MAAC) nanotubes synthesized with porous alumina templates. After mechanical polishing to remove the residual polymer surface layer from templates and subsequent template dissolution, the multilayered PEI/MAAC nanotubes were easily dispersed in water at neutral pH by polyelectrolyte adsorption, producing nanotube dispersions that were stable for at least 3 months. We characterized the dispersions using phase-contrast optical microscopy, electro-optics, electrophoresis, and viscometry to help understand their colloidal properties in the dilute and semidilute regimes. The dispersions were resistant to salt-induced aggregation up to at least 1 mM NaCl and were optically anisotropic when subjected to an electric field or flow. Interestingly, the electrophoretic mobility of polystyrene sulfonate (PSS)-stabilized nanotubes increases with increasing ionic strength, because of the high surface charge and softness of the adsorbed polyelectrolyte. Furthermore, unlike many rod-like colloid systems, the polymer nanotube dispersion has low viscosity because of weak rotary Brownian motions and strong tendency to shear thinning. At the high shear rates achieved in capillary viscometry experiments, however, we observed a slight shear thickening, which can be attributed to transient hydrocluster formation.
尽管人们已经付出了相当大的努力,利用多孔氧化铝或聚碳酸酯膜模板来合成纳米管,但很少有研究涉及到由此产生的纳米管分散体。我们制备了用多孔氧化铝模板合成的多层聚乙撑亚胺/马来酸酐交替共聚物(PEI/MAAC)纳米管的分散体。经过机械抛光以去除模板上残留的聚合物表面层,然后再溶解模板,多层PEI/MAAC 纳米管很容易在中性 pH 值下通过聚电解质吸附分散在水中,产生至少稳定 3 个月的纳米管分散体。我们使用相差光学显微镜、电光、电泳和粘度计来对分散体进行了表征,以帮助理解其在稀和半稀区的胶体性质。该分散体具有抗盐诱导聚集的能力,在至少 1mM 的 NaCl 下仍保持稳定,并且在施加电场或流动时具有各向异性光学性质。有趣的是,由于吸附的聚电解质具有高表面电荷和柔软性,聚苯乙烯磺酸盐(PSS)稳定的纳米管的电泳迁移率随离子强度的增加而增加。此外,与许多棒状胶体系统不同,聚合物纳米管分散体的粘度较低,这是由于旋转布朗运动较弱和强烈的剪切变稀趋势所致。然而,在毛细管粘度计实验中达到的高剪切速率下,我们观察到了轻微的剪切增稠现象,这可以归因于瞬态水簇的形成。