We performed molecular dynamics simulations with a coarse-grained model to investigate the capillary filling dynamics of polymer chains in nanopores. Short chains fill slower than predicted by the Lucas-Washburn equation but long chains fill faster. The analysis shows that the combination of the confinement effect on the free energy of chains and the reduction of the effective radius due to the "dead zone" slow down the imbibition. Reduction of the entanglements is the main factor behind the reversing dynamics because of the lower effective viscosity, which leads to a faster filling. This effect is enhanced in the smaller capillary and more profound for longer chains. The observed increase in the mean square radius of gyration during capillary filling provides a clear evidence of chain orientation, which leads to the decrease in the number of entanglements. For the scaling relation between the effective viscosity and the degree of polymerization, we find the exponent will increase in the larger nanopore.
We study the effect of physical confinement on the capillary infiltration of polymers into cylindrical nanopores using molecular dynamics simulations. In particular, we probe whether the critical contact angle above which capillary rise infiltration ceases to occur changes for long chain polymers, possibly due to loss of conformation entropy induced by chain confinement. Surprisingly, the critical contact angle does not strongly depend on the length of polymer chains and stays constant for large N. A free energy model is developed to show that the critical angle for infiltration depends strong…
Using molecular simulation, we analyze the capillary condensation and evaporation processes for Argon confined in a cylindrical nanopore. For this purpose, we define the entropy of the adsorbed fluid as a reaction coordinate and determine the free energy associated with both processes along entropic pathways. For capillary condensation, we identify a complex free energy profile resulting from the multi-stage nature of this phenomenon. We find capillary condensation to proceed through the nucleation of a liquid bridge across the nanopore, followed by its expansion throughout the pore to give ri…
Capillary filling of star polymer melts in nanopores
South China University of Technology（华南理工大学）；Max Planck Institute for Polymer Research（马克斯·普朗克聚合物研究所）；University of Ioannina（约阿尼纳大学）；Institute of Materials Science and Computing, University Research Center of Ioannina (URCI)（约阿尼纳大学研究中心材料科学与计算研究所）
Capillary filling in small length scale is an important process in nanotechnology and microfabrication. When one end of the tube or channel is sealed, it is important to consider the escape of the trapped gas. We develop a dynamic model on capillary filling in closed-end tubes, based on the diffusion-convection equation and Henry's law of gas dissolution. We systematically investigate the filling dynamics for various sets of parameters, and compare the results with a previous model which assumes a linear density profile of dissolved gas and neglect the convective term.
We revisit the classical problem of flow of electrolyte solutions through charged capillary nanopores or nanotubes as described by the capillary pore model (also called "space charge" theory). This theory assumes very long and thin pores and uses a one-dimensional flux-force formalism which relates fluxes (electrical current, salt flux, fluid velocity) and driving forces (difference in electric potential, salt concentration, pressure). We analyze the general case with overlapping electric double layers in the pore and a nonzero axial salt concentration gradient. The 3$\times$3 matrix relating …
The merging of immiscible drops differs significantly from the merging of miscible drops due to the formation of a liquid-liquid interface between drops. The immiscibility requires the formation of a four-phase contact point, where the drops, the gas and the substrate meet. We show that this point has its own unique dynamics, never studied beforehand. For very different scenarios, the propagation distance of this point follows scales with time like t^{0.5}. A model balancing the driving and dissipative forces agrees with our experiments.
Surface Block Identity Controls Transport of Symmetric Diblock Copolymer Through Nanopores
University of Pennsylvania（宾夕法尼亚大学）；Université de Lyon, CNRS, Université Claude Bernard Lyon 1, INSA Lyon, Université Jean Monnet（里昂大学、法国国家科学研究中心、里昂第一大学、里昂国立应用科学学院、让·莫内大学）；KU-KIST Graduate School of Converging Science and Technology, Korea University（高丽大学-韩国科学技术院融合科学与技术研究生院）
We present gravimetrical and optical imaging experiments on the capillarity-driven imbibition of silicone oils in monolithic silica glasses traversed by 3D networks of pores (mesoporous Vycor glass with 6.5 nm or 10 nm pore diameters). As evidenced by a robust square-root-of-time Lucas-Washburn (L-W) filling kinetics, the capillary rise is governed by a balance of capillarity and viscous drag forces in the absence of inertia and gravitational effects over the entire experimental times studied, ranging from a few seconds up to 10 days. A video on the infiltration process corroborates a collecti…
We analyze the dynamics of liquid filling in a thin, slightly inflated rectangular channel driven by capillary forces. We show that although the amount of liquid $m$ in the channel increases in time following the classical Lucas-Washburn law, $m \propto t^{1/2}$, the prefactor is very sensitive to the deformation of the channel because the filling takes place by the growth of two parts, the bulk part (where the cross-section is completely filled by the liquid), and the finger part (where the cross-section is partially filled). We calculate the time dependence of $m$ accounting for the coupling…
