Gotter Martin, Strey Reinhard, Olsson Ulf, Wennerström Håkan
Institut für Physikalische Chemie, Universität zu Köln, Köln D-50939, Germany.
Faraday Discuss. 2005;129:327-38; discussion 353-66. doi: 10.1039/b405363j.
The system water-oil (n-decane)-nonionic surfactant (C12E5) forms bilayer phases in a large concentration region, but, for a given oil-to-surfactant ratio, only in a narrow temperature range. In addition to the anisotropic lamellar phase (Lalpha) there is also, at slightly higher temperature, a sponge or L3-phase where the bilayers build up an isotropic structure extending macroscopically in three dimensions. In this phase the bilayer mid-surface has a mean curvature close to zero and a negative Euler characteristic. In this paper we study how the bilayers in the lamellar and the sponge phase respond dynamically to sudden temperature changes. The monolayer spontaneous curvature depends sensitively on temperature and a change of temperature thus provides a driving force for a change in bilayer topology. The equilibration therefore involves kinetic steps of fusion/fission of bilayers. Such dynamic processes have previously been monitored by temperature jump experiments using light scattering in the sponge phase. These experiments revealed an extraordinarily strong dependence of the relaxation time on the bilayer volume fraction phi. At phi < 0.1 the relaxation times are so slow that experiments using deuterium nuclear magnetic resonance (2H-NMR) appear feasible. We here report on the first experiments concerned with the dynamics of the macroscopic phase transition sponge-lamellae by 2H-NMR. We find that the sponge-to-lamellae transition occurs through a nucleation process followed by domain growth involving bilayer fission at domain boundaries. In contrast, the lamellae-to-sponge transformation apparently occurs through a succession of uncorrelated bilayer fusion events.
水 - 油(正癸烷) - 非离子表面活性剂(C12E5)体系在较大浓度区域形成双层相,但对于给定的油与表面活性剂比例,仅在狭窄的温度范围内如此。除了各向异性的层状相(Lα)外,在略高的温度下还有一种海绵相或L3相,其中双层形成宏观上在三维方向延伸的各向同性结构。在这个相中,双层中间表面的平均曲率接近零且欧拉特征为负。在本文中,我们研究层状相和海绵相中的双层如何动态响应温度的突然变化。单分子层的自发曲率对温度敏感,因此温度变化为双层拓扑结构的改变提供了驱动力。平衡因此涉及双层融合/裂变的动力学步骤。此前,此类动态过程已通过在海绵相中使用光散射的温度跳跃实验进行监测。这些实验揭示了弛豫时间对双层体积分数φ的极强依赖性。在φ < 0.1时,弛豫时间非常慢,以至于使用氘核磁共振(2H - NMR)的实验似乎可行。我们在此报告首次通过2H - NMR研究宏观相变海绵 - 层状相动力学的实验。我们发现海绵相向层状相的转变通过成核过程发生,随后是畴生长,涉及畴边界处的双层裂变。相比之下,层状相向海绵相的转变显然通过一系列不相关的双层融合事件发生。