Shrestha Rekha Goswami, Shrestha Lok Kumar, Aramaki Kenji
Graduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai 79-7, Hodogaya-ku, Yokohama 240-8501, Japan.
J Colloid Interface Sci. 2007 Jul 1;311(1):276-84. doi: 10.1016/j.jcis.2007.02.050. Epub 2007 Feb 23.
Formation of wormlike micelles in mixed anionic/cationic system without the addition of any salt has been studied. Amino-acid based anionic surfactant N-dodecylglutamic acid (LAD), which is practically immiscible with water at 25 degrees C upon neutralization by 2,2',2''-nitrilotriethanol (TEA) forms small micellar aggregates and the solution behaves like a Newtonian fluid. The rheological behavior of LAD/water/hexadecyltrimethylammonium bromide (CTAB) and LAD/water/dodecyltrimethylammonium bromide (DTAB) systems were investigated at different degrees of neutralization of the LAD depending on the concentration of the cationic surfactants and on temperature. Addition of CTAB to the dilute aqueous solution of the LAD-TEA-x (the neutralized product, where x represents the mole ratio of TEA) causes one dimensional micellar growth. After certain concentration the elongated micelles entangle forming a rigid network of viscoelastic wormlike micelles. Thus formed viscoelastic solutions follow Maxwellian behavior over a wide range of frequency and thus are considered to consist of transient network of wormlike micelles. By varying the degree of neutralization from 1:1 via 1:1.5 to 1:2 (molar ratio) phase and rheological behavior were modified in that the highly viscous region of viscoelastic wormlike micelles shifted to higher CTAB concentrations and no maxima in the zero-shear viscosity could be observed for the higher degree of neutralization of the LAD (1:1.5 and 1:2). However, the obtained rheological parameters showed scaling relationships that were consistent with the living polymer model. The zero-shear viscosity decays exponentially with temperature following Arrhenius behavior. The flow activation energy calculated from the Arrhenius plot is very close to the value reported for the typical wormlike micellar solution. In contrast to CTAB no formation of viscoelastic wormlike micelles could be observed with DTAB, although, the solution viscosity increases. The elongated micelles could not entangle to form a rigid network of wormlike micelles in this system. For the first time viscoelastic wormlike micelles could be obtained in salt-free mixed anionic/cationic surfactant systems.
对在不添加任何盐的情况下混合阴离子/阳离子体系中蠕虫状胶束的形成进行了研究。基于氨基酸的阴离子表面活性剂N - 十二烷基谷氨酸(LAD),在25℃下用2,2',2'' - 次氮基三乙醇(TEA)中和后实际上与水不混溶,形成小的胶束聚集体,溶液表现得像牛顿流体。根据阳离子表面活性剂的浓度和温度,研究了LAD/水/十六烷基三甲基溴化铵(CTAB)和LAD/水/十二烷基三甲基溴化铵(DTAB)体系在不同LAD中和程度下的流变行为。向LAD - TEA - x(中和产物,其中x代表TEA的摩尔比)的稀水溶液中添加CTAB会导致一维胶束生长。在一定浓度后,伸长的胶束缠结形成粘弹性蠕虫状胶束的刚性网络。如此形成的粘弹性溶液在很宽的频率范围内遵循麦克斯韦行为,因此被认为由蠕虫状胶束的瞬态网络组成。通过将中和度从1:1变化到1:1.5再到1:2(摩尔比),相行为和流变行为发生了改变,即粘弹性蠕虫状胶束的高粘性区域向更高的CTAB浓度移动,并且对于LAD的更高中和度(1:1.5和1:2),在零剪切粘度中未观察到最大值。然而,获得的流变参数显示出与活性聚合物模型一致的标度关系。零剪切粘度随温度呈指数衰减,遵循阿仑尼乌斯行为。从阿仑尼乌斯图计算出的流动活化能非常接近典型蠕虫状胶束溶液报道的值。与CTAB相反,使用DTAB未观察到粘弹性蠕虫状胶束的形成,尽管溶液粘度增加。在该体系中,伸长的胶束无法缠结形成蠕虫状胶束的刚性网络。首次在无盐的混合阴离子/阳离子表面活性剂体系中获得了粘弹性蠕虫状胶束。