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arXiv 1102.4694cond-mat.softcond-mat.mes-hall
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表面吸附胶体的状态方程

Equation of state of surface-adsorbing colloids

Robert D. Groot, Simeon D. Stoyanov

摘要:

我们已经开发了一个模拟模型来描述颗粒从液体界面的吸附和解吸。利用这个模型,我们制定了一个封闭的界面状态方程的排斥弹性球。通过微扰理论引入了长程吸引作用的影响,并利用直接模拟研究了短程吸引作用的影响。基于我们的模型预测,我们得出结论,聚合物颗粒的表面压力不能直接模拟惰性粒子,通过一些有效的潜力相互作用。凝胶颗粒内的内部自由度非常重要。因此,完全填充层的表面压力与kT/d^2不成比例,其中d是颗粒直径;但与kT/dm ^2成比例,其中dm是组成颗粒的分子单元的大小。这使表面压力和模量增加了大约四个数量级。对于短程相互作用,我们研究的动态行为,并发现在低浓度下的分形结构。在中等覆盖度下,形成类似于亚稳系统的不规则结构。这个系统冻结,这阻止了spinodal结构。在高表面覆盖率的模拟显示多晶域。对于稀体系,表面层的强度由模拟的压缩和膨胀确定。我们发现表面压力的幂律(Pi ~ γ ^10 +/-0.5)与吸附网络的(分形)结构有关。幂律与表面渗流一致。

英文摘要:

We have developed a simulation model to describe particle adsorption to and desorption from liquid interfaces. Using this model we formulate a closed interfacial equation of state for repulsive elastic spheres. The effect of a long-range attractive interaction is introduced by perturbation theory, and the effect a short-range attraction is studied using direct simulation. Based on our model predictions we conclude that for polymeric particles the surface pressure cannot be modelled directly by inert particles that interact via some effective potential. Internal degrees of freedom within gel particles are all-important. Consequently, the surface pressure of a fully packed layer is not proportional to kT/d^2, where d is the particle diameter; but proportional to kT/dm^2, where dm is the size of the molecular units that make up the particle. This increases the surface pressure and modulus by some four orders of magnitude. For short range interaction we study the dynamic behaviour, and find fractal-like structures at low concentrations. At intermediate coverage an irregular structure is formed that resembles a spinodal system. This system freezes, which arrests the spinodal structure. At high surface coverage the simulations show poly-crystalline domains. For dilute systems, the strength of the surface layers is determined by simulated compression and expansion. We find a power law for the surface pressure (Pi ~ Gamma^10+/-0.5), which is related to the (fractal) structure of the adsorbed network. The power law is consistent with surface percolation.

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