Flores A, Corvera-Poiré E, Garza C, Castillo R
Instituto de Física, UNAM, P. O. Box 20-364, DF 01000, México.
J Phys Chem B. 2006 Mar 16;110(10):4824-35. doi: 10.1021/jp0537308.
We present a study of how patterns formed by Langmuir monolayer domains of a stable phase, usually solid or liquid condensed, propagate into a metastable one, usually liquid expanded. During this propagation, the interface between the two phases moves as the metastable phase is transformed into the more stable one. The interface becomes unstable and forms patterns as a result of the competition between a chemical potential gradient that destabilizes the interface on one hand and line tension that stabilizes the interface on the other. During domain growth, we found a morphology transition from tip splitting to side branching; doublons were also found. These morphological features were observed with Brewster angle microscopy in three different monolayers at the water/air interface: dioctadecylamine, ethyl palmitate, and ethyl stearate. In addition, we observed the onset of the instability in round domains when an abrupt lateral pressure jump is made on the monolayer. Frequency histograms of unstable wavelengths are consistent with the linear-instability dispersion relation of classical free-boundary models. For the case of dendritic morphologies, we measured the radius of the dendrite tip as a function of the dendrite length as well as the spacing of the side branches along a dendrite. Finally, a possible explanation of why Langmuir monolayers present this kind of nonequilibrium growth patterns is presented. In the steady state, the growth behavior is determined by Laplace's equation in the particle density with specific boundary conditions. These equations are equivalent to those used in the theory of morphology diagrams for two-dimensional diffusional growth, where morphological transitions of the kind observed here have been predicted.
我们展示了一项关于稳定相(通常为固体或液体凝聚相)的朗缪尔单分子层域所形成的图案如何传播到亚稳相(通常为液体膨胀相)的研究。在这种传播过程中,随着亚稳相转变为更稳定的相,两相之间的界面会移动。由于一方面使界面不稳定的化学势梯度与另一方面使界面稳定的线张力之间的竞争,界面变得不稳定并形成图案。在域生长过程中,我们发现了从尖端分裂到侧向分支的形态转变;还发现了双聚体。利用布鲁斯特角显微镜在水/空气界面的三种不同单分子层中观察到了这些形态特征:二十八烷基胺、棕榈酸乙酯和硬脂酸乙酯。此外,当在单分子层上施加突然的横向压力跃变时,我们观察到圆形域中不稳定性的开始。不稳定波长的频率直方图与经典自由边界模型的线性不稳定性色散关系一致。对于树枝状形态的情况,我们测量了树枝状尖端的半径作为树枝状长度以及沿树枝状的侧分支间距的函数。最后,给出了关于为什么朗缪尔单分子层呈现这种非平衡生长模式的一种可能解释。在稳态下,生长行为由具有特定边界条件的粒子密度中的拉普拉斯方程决定。这些方程等同于二维扩散生长形态图理论中所使用的方程,在该理论中已经预测到了此处观察到的那种形态转变。