Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht 3584 CC, The Netherlands.
Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw 01-224, Poland.
Proc Natl Acad Sci U S A. 2023 Feb 28;120(9):e2213044120. doi: 10.1073/pnas.2213044120. Epub 2023 Feb 24.
Sedimentation is a ubiquitous phenomenon across many fields of science, such as geology, astrophysics, and soft matter. Sometimes, sedimentation leads to unusual phenomena, such as the Brazil-nut effect, where heavier (granular) particles reside on top of lighter particles after shaking. We show experimentally that a Brazil-nut effect can be realized in a binary colloidal system of long-range repulsive charged particles driven purely by Brownian motion and electrostatics without the need for activity. Using theory, we argue that not only the mass-per-charge for the heavier particles needs to be smaller than the mass-per-charge for the lighter particles but also that at high overall density, the system can be trapped in a long-lived metastable state, which prevents the occurrence of the equilibrium Brazil-nut effect. Therefore, we envision that our work provides valuable insights into the physics of strongly interacting systems, such as partially glassy and crystalline structures. Finally, our theory, which quantitatively agrees with the experimental data, predicts that the shapes of sedimentation density profiles of multicomponent charged colloids are greatly altered when the particles are charge-regulating with more than one ion species involved. Hence, we hypothesize that sedimentation experiments can aid in revealing the type of ion adsorption processes that determine the particle charge and possibly the value of the corresponding equilibrium constants.
沉降是许多科学领域(如地质学、天体物理学和软物质)中普遍存在的现象。有时,沉降会导致异常现象,例如巴西坚果效应,即在摇晃后较重(颗粒状)的颗粒会位于较轻的颗粒之上。我们通过实验表明,在由布朗运动和静电力驱动的长程排斥带电粒子的二元胶体系统中,可以实现巴西坚果效应,而无需活性。通过理论,我们认为不仅较重颗粒的质量-电荷比需要小于较轻颗粒的质量-电荷比,而且在高总体密度下,系统可以被困在长寿命的亚稳状态,从而防止出现平衡巴西坚果效应。因此,我们设想我们的工作为强相互作用系统的物理提供了有价值的见解,例如部分玻璃态和结晶态结构。最后,我们的理论与实验数据定量吻合,预测当涉及到多于一种离子物种的电荷调节时,多组分带电胶体的沉降密度分布的形状会发生很大的改变。因此,我们假设沉降实验可以帮助揭示决定颗粒电荷的离子吸附过程的类型,并可能揭示相应的平衡常数的值。