Gangopadhyay Rupali
Centre for Advanced Materials, Indian Association for the Cultivation of Science, Kolkata 700 032, India.
J Colloid Interface Sci. 2009 Oct 15;338(2):435-43. doi: 10.1016/j.jcis.2009.06.050. Epub 2009 Jun 30.
The paper describes steady and dynamic rheological characterization of a system in which polyaniline (PAn) is dispersed in aqueous medium by the effect of a surfactant sodium dodecyl sulphate (SDS). During polymerization of aniline in SDS medium, large and agglomerated micelle-polymer structures are formed (supported by TEM and DLS) resulting in high viscosity of the medium. On application of steady shear micellar entanglements are ruptured and the system exhibits yield properties followed by shear thinning. From the frequency dependence of storage and loss modulii (G' and G'') it seems that the system behaves more like a viscous fluid rather than an elastic liquid. Carrying out the same experiments on another dispersion in which PAn is stabilized by dodecyl benzenesulphonic acid (DBSA), very different viscoelastic response was received. DBSA molecules become counter-ions to PAn chains and this way large and interconnected PAn-DBSA structures are formed by mutual sharing of DBSA anions and PAn chains. This system therefore, exhibits gel like properties and encounters a gel to sol transition at larger deformation. Detailed studies have established that PAn-SDS is a stabilized dispersion that resembles entangled polymeric solutions to some extent while PAn-DBSA is a partially flocculated system. Therefore, rheological response of the system is mainly governed by the mutual orientation of PAn with respect to the micelles rather than the individual properties of the components. None of these systems, however, follow the established Maxwell's model and a single relaxation time is not obtained. Rather, Rouse model of multiple relaxation times is partially applicable to PAn-SDS dispersion.
本文描述了一种体系的稳态和动态流变学特性,在该体系中,聚苯胺(PAn)通过表面活性剂十二烷基硫酸钠(SDS)的作用分散于水介质中。在SDS介质中苯胺聚合期间,形成了大的且团聚的胶束 - 聚合物结构(由透射电子显微镜和动态光散射证实),导致介质具有高粘度。施加稳态剪切时,胶束缠结被破坏,体系呈现屈服特性,随后是剪切变稀。从储能模量和损耗模量(G'和G'')的频率依赖性来看,该体系表现得更像粘性流体而非弹性液体。对另一种用十二烷基苯磺酸(DBSA)稳定PAn的分散体进行相同实验时,得到了非常不同的粘弹性响应。DBSA分子成为PAn链的抗衡离子,通过这种方式,DBSA阴离子和PAn链相互共享形成了大的且相互连接的PAn - DBSA结构。因此,该体系表现出凝胶状特性,并且在较大变形时会发生凝胶 - 溶胶转变。详细研究表明,PAn - SDS是一种稳定的分散体,在一定程度上类似于缠结的聚合物溶液,而PAn - DBSA是一种部分絮凝的体系。因此,该体系的流变响应主要由PAn相对于胶束的相互取向决定,而非各组分的个体性质。然而,这些体系均不遵循已有的麦克斯韦模型,也未获得单一的弛豫时间。相反,具有多个弛豫时间的劳斯模型部分适用于PAn - SDS分散体。