Miyahara Minoru, Watanabe Satoshi, Gotoh Yoshiaki, Higashitani Ko
Department of Chemical Engineering, Kyoto University-Katsura, Nishikyo-ku, Kyoto, 615-8510 Japan.
J Chem Phys. 2004 Jan 15;120(3):1524-34. doi: 10.1063/1.1632896.
Adsorption process and order formation of electrostatically stabilized colloidal particles with a radius of 50 nm onto a planar surface with countercharge are examined. We perform Brownian dynamics simulations with a new three-dimensional cell model, in which the particle-particle and particle-substrate interactions are modeled based on the DLVO theory. The simulations yield the following results: (1) a larger bulk concentration would be required for larger kappaa to reach order formation to compensate for the decrease in the bulk potential; (2) the phase transition from a disordered to an ordered structure of the adsorbed particles on the substrate is considered to be of the Kirkwood-Alder type of transition through the examination of the two-dimensional pressure of the adsorbed particles; (3) the adsorbed particles are found to form a hexagonally ordered array, only if what we call "one-directional average force" acting on an adsorbed particle exceeds a critical value, which is independent of the ionic strength, or the interaction potentials. The critical value of the one-directional average force is interpreted as the force needed to keep an ordered structure by localizing adsorbed particles at fixed positions. In addition, the critical force is used to develop a new model to estimate the surface coverage at the order-disorder transition and it is demonstrated that the new model gives better estimation than other models previously reported.
研究了半径为50纳米的静电稳定胶体颗粒在带有反电荷的平面上的吸附过程和有序形成。我们使用一种新的三维细胞模型进行布朗动力学模拟,其中基于DLVO理论对颗粒 - 颗粒和颗粒 - 底物相互作用进行建模。模拟得出以下结果:(1)对于较大的κ,为了达到有序形成,需要更大的本体浓度来补偿本体电势的降低;(2)通过检查吸附颗粒的二维压力,认为吸附在底物上的颗粒从无序结构到有序结构的相变属于柯克伍德 - 阿尔德类型的转变;(3)只有当作用在吸附颗粒上的我们所谓的“单向平均力”超过一个临界值时,吸附颗粒才会形成六边形有序阵列,该临界值与离子强度或相互作用势无关。单向平均力的临界值被解释为通过将吸附颗粒定位在固定位置来保持有序结构所需的力。此外,利用该临界力开发了一个新模型来估计有序 - 无序转变时的表面覆盖率,结果表明该新模型比先前报道的其他模型具有更好的估计效果。