Capillary electrophoresis has long been been recognized as a powerful analytic tool. Here it is demonstrated that the same capillary electrophoretic experiments also reveal dynamic properties of the polymer solutions being used as the support medium. The dependence of the electrophoretic mobility on the size of the probe and the properties of the matrix polymers shows a unity of behavior between electrophoresis and other methods of studying polymer properties.
We present a computational parameter estimation tool aimed at assisting molecule characterization applying nonlinear least-squares optimization to a specific closed-form solution of a capillary electrophoretic transport problem. Numerical estimates for the respective physicochemical parameters are generated. Among other features, the tool facilitates automated and user-controllable hypothesis testing and model selection. It can also be used to perform fully automated batch-processing in true concurrent mode.
Elucidating the physics of a concentrated suspension of ring polymers, or of an ensemble of ring polymers in a complex environment, is an important outstanding question in polymer physics. Many of the characteristic features of these systems arise due to topological interactions between polymers, or between the polymers and the environment, and it is often challenging to describe this quantitatively. Here we review recent research which suggests that a key role is played by inter-ring threadings (or penetrations), which become more abundant as the ring size increases. As we discuss, the physic…
Chain conformations in adsorbed layer during polymer capillary imbibition
South China Advanced Institute for Soft Matter Science and Technology, School of Emergent Soft Matter, South China University of Technology（华南先进软物质研究院， emergent soft matter 学院，华南理工大学）；Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology（广东省功能与智能杂化材料器件重点实验室，华南理工大学）；National-Certified Enterprise Technology Center, Kingfa Science and Technology Co., LTD.（国家认定企业技术中心，金发科技股份有限公司）
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…
Enhancement of coil--stretch hysteresis by self-concentration in extensional flows, and its implications for capillary thinning of liquid bridges of dilute polymer solutions
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）
We present the first experimental study on the simultaneous capillary instability amongst viscous concentric rings suspended atop an immiscible medium. The rings ruptured upon annealing, with three types of phase correlation between neighboring rings. In the case of weak substrate confinement, the rings ruptured independently when they were sparsely distanced, but via an out-of-phase mode when packed closer. If the substrate confinement was strong, the rings would rupture via an in-phase mode, resulting in radially aligned droplets. The concentric ring geometry caused a competition between the…
Surface tension-driven flow techniques have recently emerged as an efficient means of shedding light into the rheology of thin polymer films. Motivated by experimental and theoretical approaches in films bearing a varying surface topography, we present results on the capillary relaxation of a square pattern at the free surface of a viscoelastic polymer film, using molecular dynamics simulations of a coarse-grained polymer model. Height profiles are monitored as a function of time after heating the system above its glass-transition temperature and their time dependence is fitted to the theory o…
A highly sensitive optical capillary electrophoresis measurement method based on a nanofluidic optical fiber platform is presented. By using scaling arguments and considering realistic instrument limitations, I underline the feasibility of measuring the electrophoretic mobility of a single freely-diffusing nanoparticle or macromolecule in vitro, continuously and indefinitely, with microsecond time resolution. The high speed of this technique opens up new possibilities for studying reaction kinetics at the single molecule level.
We analyze the capillarity-driven thinning dynamics of entangled polymer solutions described by the Doi-Edwards-Marrucci-Grizzuti (DEMG) model and the Rolie-Poly (RP) model. Both models capture polymer reptation, finite rates of chain retraction and finite extensibility of single polymer molecules, while differing slightly in their final form regarding to the convective constraint release. We calculate numerically the filament thinning profiles predicted by the two models with realistic entanglement densities, assuming cylindrical filament shapes and no fluid inertia. Both results reveal an ea…
We investigate the dynamics of spreading in a regime where the shape of the drop is close to a spherical cap. The latter simplification is applicable in the late (viscous) stage of spreading for highly viscous drops with a diameter below the capillary length. Moreover, it applies to the spreading of a drop on a swellable polymer brush, where the complex interaction with the substrate leads to a very slow spreading dynamics. The spherical cap geometry allows to derive a closed ordinary differential equation (ODE) for the spreading if the capillary number is a function of the contact angle as it…
In capillary-driven fluid dynamics, simple departures from equilibrium offer the chance to quantitatively model the resulting relaxations. These dynamics in turn provide insight on both practical and fundamental aspects of thin-film hydrodynamics. In this work, we describe a model trilayer dewetting experiment elucidating the effect of solid, no-slip confining boundaries on the bursting of a liquid film in a viscous environment. This experiment was inspired by an industrial polymer processing technique, multilayer coextrusion, in which thousands of alternating layers are stacked atop one anoth…
An experimental investigation is reported on the effect of shear on the bursting of molten ultra-thin polymer films embedded in an immiscible matrix. By using an optical microscope coupled with a shearing hotstage, the dewetting dynamics, i.e. the growth of dewetting holes is monitored over time at various shear rates. It is observed that their circularity is modified by shear and that for all temperatures and thicknesses studied, the growth speed of the formed holes rapidly increases with increasing shear rate. A model balancing capillary forces and viscous dissipation while taking into accou…
Motivated by recent experimental studies probing i) the existence of a mobile layer at the free surface of glasses, and ii) the capillary leveling of polymer nanofilms, we study the evolution of square-wave patterns at the free surface of a generic glass-forming binary Lennard-Jones mixture over a wide temperature range, by means of molecular dynamics simulations. The pattern's amplitude is monitored and the associated decay rate is extracted. The evolution of the latter as a function of temperature exhibits a crossover between two distinct behaviours, over a temperature range typically bounde…
Physically confining polymers into nanoscale pores induces significant changes in their dynamics. Although different results on the effect of confinement on the dynamics of polymers have been reported, changes in the segmental mobility of polymers typically are correlated with changes in their chain mobility due to increased monomeric relaxation times. In this study, we show that translational and segmental dynamics of polymers confined in disordered packings of nanoparticles can exhibit completely opposite behavior. We monitor the capillary rise dynamics of entangled polystyrene (PS) in disor…
We present gravimetrical, optical, and neutron imaging measurements of the capillarity-driven infiltration of mesoporous silica glass by hydrocarbons. Square-root-of-time Lucas-Washburn invasion kinetics are found for linear alkanes from n-decane (C10) to n-hexacontane (C60) and for squalane, a branched alkane, in porous Vycor with 6.5 nm or 10 nm pore diameter, respectively. Humidity-dependent experiments allow us to study the influence on the imbibition kinetics of water layers adsorbed on the pore walls. Except for the longest molecule studied, C60, the invasion kinetics can be described by…
