Ueno Kazuhide, Imaizumi Satoru, Hata Kenji, Watanabe Masayoshi
Department of Chemistry and Biotechnology, Yokohama National University 79-5 Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan.
Langmuir. 2009 Jan 20;25(2):825-31. doi: 10.1021/la803124m.
To understand the important factors that dominate colloidal stability in ionic liquids (ILs), rheology of the dispersions of hydrophilic and hydrophobic silica nanoparticles were investigated in ILs with different ionic structures. The dispersion of hydrophilic silica nanoparticles in [BF(4)] anion-based ILs and in an IL containing a hydroxyl group, 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethane sulfonyl)amide ([C(2)OHmim][NTf(2)]), showed an intriguing shear thickening response. Nonflocculation of the hydrophilic silica nanoparticles in the [BF(4)] anion-based ILs and in [C(2)OHmim][NTf(2)], where the interparticle electrostatic repulsion appears to be depressed, suggests that an IL-based steric hindrance or solvation force provides an effective repulsive barrier for the colloidal aggregation. On the other hand, the other dispersions presented shear thinning behavior with an increase in shear rates and gelled at relatively low particle concentrations. The elastic modulus (G') of the gels formed by the hydrophilic silica was correlated with the polarity scale, lambda(Cu), of the ILs, indicating that the silica-IL interactions, especially the silica-anion interactions, appear to affect the rheological behavior, even in flocculated systems. All the ILs used in this study can be solidified by the addition of hydrophobic silica particles. The rheological behavior of the silica colloidal dispersions was strongly affected by the ionic structure of the ILs and the surface structure of the silica particles.
为了解主导离子液体(ILs)中胶体稳定性的重要因素,研究了亲水性和疏水性二氧化硅纳米颗粒在具有不同离子结构的离子液体中的分散体流变学。亲水性二氧化硅纳米颗粒在基于[BF(4)]阴离子的离子液体以及含有羟基的离子液体1-(2-羟乙基)-3-甲基咪唑双(三氟甲烷磺酰)酰胺([C(2)OHmim][NTf(2)])中的分散体表现出有趣的剪切增稠响应。在基于[BF(4)]阴离子的离子液体和[C(2)OHmim][NTf(2)]中,亲水性二氧化硅纳米颗粒未发生絮凝,而在这些体系中颗粒间的静电排斥似乎受到抑制,这表明基于离子液体的空间位阻或溶剂化力为胶体聚集提供了有效的排斥屏障。另一方面,其他分散体随着剪切速率的增加呈现出剪切变稀行为,并在相对较低的颗粒浓度下形成凝胶。由亲水性二氧化硅形成的凝胶的弹性模量(G')与离子液体的极性标度lambda(Cu)相关,这表明二氧化硅 - 离子液体相互作用,特别是二氧化硅 - 阴离子相互作用,似乎会影响流变行为,即使在絮凝体系中也是如此。本研究中使用的所有离子液体通过添加疏水性二氧化硅颗粒均可固化。二氧化硅胶体分散体的流变行为受到离子液体的离子结构和二氧化硅颗粒的表面结构的强烈影响。