We perform Brownian dynamics simulations of active stiff polymers undergoing run-reverse dynamics, and so mimic bacterial swimming, in porous media. In accord with recent experiments of \emph{Escherichia coli}, the polymer dynamics are characterized by trapping phases interrupted by directed hopping motion through the pores. We find that the effective translational diffusivities of run-reverse agents can be enhanced up to two orders in magnitude, compared to their non-reversing counterparts, and exhibit a non-monotonic behavior as a function of the reversal rate, which we rationalize using a coarse-grained model. Furthermore, we discover a geometric criterion for the optimal spreading, which emerges when their run lengths are comparable to the longest straight path available in the porous medium. More significantly, our criterion unifies results for porous media with disparate pore sizes and shapes and thus provides a fundamental principle for optimal transport of microorganisms and cargo-carriers in densely-packed biological and environmental settings.
We study a single flexible chain molecule grafted to a membrane which has pores of size slightly larger than the monomer size. On both sides of the membrane there is the same solvent. When this solvent is good, i.e. when the polymer is described by a self avoiding walk, it can fairly easily penetrate the membrane, so that the average number of membrane crossings tends, for chain length $N\to\infty$, to a positive constant. The average numbers of monomers on either side of the membrane diverges in this limit, although their ratio becomes infinite. For a poor solvent, in contrast, the entire pol…
We show that the critical behavior of a colloid-polymer mixture inside a random porous matrix of quenched hard spheres belongs to the universality class of the random-field Ising model. We also demonstrate that random-field effects in colloid-polymer mixtures are surprisingly strong. This makes these systems attractive candidates to study random-field behavior experimentally.
The spreading of polymer droplets is studied using molecular dynamics simulations. To study the dynamics of both the precursor foot and the bulk droplet, large drops of ~200,000 monomers are simulated using a bead-spring model for polymers of chain length 10, 20, and 40 monomers per chain. We compare spreading on flat and atomistic surfaces, chain length effects, and different applications of the Langevin and dissipative particle dynamics thermostats. We find diffusive behavior for the precursor foot and good agreement with the molecular kinetic model of droplet spreading using both flat and a…
We study the conformational properties of charged polymers in a solvent in the presence of structural obstacles correlated according to a power law $\sim x^{-a}$. We work within the continuous representation of a model of linear chain considered as a random sequence of charges $q_i=\pm q_0$. Such a model captures the properties of polyampholytes -- heteropolymers comprising both positively and negatively charged monomers. We apply the direct polymer renormalization scheme and analyze the scaling behavior of charged polymers up to the first order of an $ε=6-d$, $δ=4-a$-expansion.
We present a quantitative picture of the separation of star polymers in a solution where part of the volume is influenced by a porous medium. To this end, we study the impact of long-range-correlated quenched disorder on the entropy and scaling properties of $f$-arm star polymers in a good solvent. We assume that the disorder is correlated on the polymer length scale with a power-law decay of the pair correlation function $g(r) \sim r^{-a}$. Applying the field-theoretical renormalization group approach we show in a double expansion in $ε=4-d$ and $δ=4-a$ that there is a range of correlation st…
Spontaneous spreading of a polymer drop on a solid substrate can be forced by a low pressure gaseous discharge applied between the cathode that supports the drop and a remote electrode. We prone to think that the driving force for this plasma driven spreading is the spatial distribution of the electric field at the cathode. Two distinct effects caused by the gas plasma are observed: spreading of a thin film and shrinking of the rest liquid into a spherical drop upon its own film. The last effect, never reported before, can be addressed to the effect of the electric stresses developed in the io…
An assumption in micromechanical analysis of polymers is that the constitutive polymeric media is non-porous. Non-porosity of media, however, is merely a simplifying assumption. In this paper, we neglect this assumption and studied polymer networks with a different porosity volume fraction. A random morphology description function is used to model the porosity of the network and nonlinear finite element analyses are conducted to perform structural analysis of porous polymer networks. The results show that the porosity effect is significant in mechanical behavior of polymer networks and may inc…
The spreading of one- and two-component polymer nanodroplets is studied using molecular dynamics simulation in a cylindrical geometry. The droplets consist of polymer chains of length 10, 40, and 100 monomers per chain described by the bead-spring model spreading on a flat surface with a surface-coupled Langevin thermostat. Each droplet contains ~350,000 monomers. The dynamics of the individual components of each droplet are analyzed and compared to the dynamics of single component droplets for the spreading rates of the precursor foot and bulk croplet, the time evolution of the contact angle,…
We study the dependence of the fracture surface energy on the pulling velocity for nano-porous polypropylene (PP) sheets to find two components: the static and dynamic ones. We show that these terms can be interpreted respectively as plastoelastic and viscoelastic components, as has been shown for soft polyethylene (PE) foams in a previous work. Considering significant differences in the pore size, volume fraction and Young's modulus of the present PP and previous PE sheets, the present results suggest a universal physical mechanism for fracture of porous polymer sheets. The simple physical in…
The conformational behavior of a polymer in a critical binary solvent confined in a porous medium is studied. The size of the polymer in bulk, which is mainly governed by the correlation length of the solvent density fluctuations, depends on the proximity to the critical point of the binary mixture. We find that in contrast to the bulk behavior, the conformational properties of the polymer in a porous medium depends strongly on the pore size. The latter controls the correlation length of the solvent density fluctuations and thus determines the polymer size.
We theoretically analyze the waveguide regime of light propagation in a cylindrical pore of a polymer matrix filled with liquid crystals assuming that the effective radial optical anisotropy is biaxial. From numerical analysis of the dispersion relations, the waveguide modes are found to be sensitive to the field-induced changes of the anisotropy. The electro-optic properties of the polymer porous polyethylene terephthalate (PET) films filled with the nematic liquid crystal 5CB are studied experimentally and the experimental results are compared with the results of the theoretical investigatio…
As a generic model for liquid-vapour type transitions in random porous media, the Asakura-Oosawa model for colloid-polymer mixtures is studied in a matrix of quenched spheres using extensive Monte Carlo (MC) simulations. Since such systems at criticality, as well as in the two-phase region, exhibit lack of self-averaging, the analysis of MC data via finite size scaling requires special care. After presenting the necessary theoretical background and the resulting subtleties of finite size scaling in random-field Ising-type systems, we present data on the order parameter distribution (and its mo…
Spreading on the free surface of a complex fluid is ubiquitous in nature and industry, owing to the wide existence of complex fluids. Here we report on a fingering instability that develops during Marangoni spreading on a deep layer of polymer solution. In particular, the wavelength depends on molecular weight and concentration of the polymer solution. We use the Transmission Lattice Method to characterize the finger height at the micron scale. We model the evolution of spreading radius, involving viscoelastic and shear thinning effects, to suggest a more generalized law than the spreading of …
Imidazolium based porous cationic polymers were synthesized using an innovative and facile approach, which takes advantage of the Debus Radziszewski reaction to obtain meso- and microporous polymers following click chemistry principles. In the obtained set of materials, click based porous cationic polymers have the same cationic backbone, whereas they bear the commonly used anions of imidazolium poly(ionic liquid)s. These materials show hierarchical porosity and a good specific surface area. Furthermore, their chemical structure was extensively characterized using ATR FTIR and SS NMR spectrosc…
Spreading and solidification of liquid droplets are elementary processes of relevance for additive manufacturing. Here we investigate the effect of heat transfer on spreading of a thermoresponsive solution (Pluronic F127) that undergoes a sol-gel transition above a critical temperature $T_m$. By controlling the concentration of Pluronic F127 we systematically vary $T_m$, while also imposing a broad range of temperatures of the solid and the liquid. We subsequently monitor the spreading dynamics over several orders of magnitude in time and determine when solidification stops the spreading. It i…
Inspired by how the shape deformations in active organisms help them to migrate through disordered porous environments, we simulate active ring polymers in two-dimensional random porous media. Flexible and inextensible active ring polymers navigate smoothly through the disordered media. In contrast, semiflexible rings undergo transient trapping inside the pore space; the degree of trapping is inversely correlated with the increase in activity. We discover that flexible rings swell while inextensible and semiflexible rings monotonically shrink upon increasing the activity. Together, our finding…
Polymer solutions are often injected in porous media for applications such as oil recovery and groundwater remediation. As the fluid navigates the tortuous pore space, elastic stresses build up, causing the flow to become unstable at sufficiently large injection rates. However, it is poorly understood how the spatial and temporal characteristics of this unstable flow depend on pore space geometry. We elucidate this dependence by systematically varying the spacing between pore constrictions in a model porous medium. We find that when the pore spacing is large, unstable eddies form upstream of e…
When a liquid drop spreads on an adaptive substrate the latter changes its properties what may result in an intricate coupled dynamics of drop and substrate. Here we present a generic mesoscale hydrodynamic model for such processes that is written as a gradient dynamics on an underlying energy functional. We specify the model details for the example of a drop spreading on a dry polymer brush. There, liquid absorption into the brush results in swelling of the brush causing changes in the brush topography and wettability. The liquid may also advance within the brush via diffusion (or wicking) re…
A composite porous polymer membrane with aligned CNTs in its matrix is developed which exhibits programmable, anisotropic actuation towards organic vapors. The alignment of CNTs in multiple directions and the gradient porous structure of the membrane are critical for the actuation, and the actuating direction can be well controlled at a direction perpendicular to the longitudinal orientation of CNTs. The reversible actuation may be repeated for 300 cycles without obvious fatigue. These polymer composites are promising building blocks for a wide variety of applications such as sensors and actua…
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…
We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compare…
We will utilise the self-avoiding walk (SAW) mapping of the vortex line conformations in turbulence to get the Kolmogorov scale dependence of energy dispersion from SAW statistics, and the knowledge of the disordered fractal geometries on the SAW statistics. These will give us the Kolmogorov energy dispersion exponent value for turbulence in porous media in terms of the size exponent for polymers in the same. We argue that the exponent value will be somewhat less than 5/3 for turbulence in porous media.
We investigate the rapid spreading dynamics of a viscoelastic drop on a solid. Upon contact, surface tension drives a fast motion of the contact line along the substrate. Here, we resolve this motion for viscoelastic liquids by experiments on aqueous polymer solutions of varying concentration. It is found that while the contact line motion is only mildly affected by the polymers, the interface profile becomes much sharper owing to singular polymer stress. This behaviour is reminiscent of that observed for viscoelastic drop coalescence; in this light we revisit the analogy between spreading and…
The motion of active polymers in a porous medium is shown to depend critically on flexibilty, activity and degree of polymerization. For given Peclet number, we observe a transition from localisation to diffusion as the stiffness of the chains is increased. Whereas stiff chains move almost unhindered through the porous medium, flexible ones spiral and get stuck. Their motion can be accounted for by the model of a continuous time random walk with a renewal process corresponding to unspiraling. The waiting time distribution is shown to develop heavy tails for decreasing stiffness, resulting in s…
From biological tissues to layers of paint, macroscopic non-porous materials with the capacity to swell when brought in contact with an appropriate solvent are ubiquitous. Here, we study experimentally and theoretically one of the conceptually simplest of such systems, the swelling of a thin hydrogel layer by a single water drop. Using a bespoke experimental setup, we observe fast absorption leading to a radially spreading axisymmetric blister. Employing a linear poroelastic framework and thin-layer scalings, we develop a non-linear one-dimensional diffusion equation for the evolution of the b…
Molecular dynamics simulations are used to study the spreading of binary polymer nanodroplets in a cylindrical geometry. The polymers, described by the bead-spring model, spread on a flat surface with a surface-coupled Langevin thermostat to mimic the effects of a corrugated surface. Each droplet consists of chains of length 10 or 100 monomers with ~350,000 monomers total. The qualitative features of the spreading dynamics are presented for differences in chain length, surface interaction strength, and composition. When the components of the droplet differ only in surface interaction strength,…
The force-assisted desorption kinetics of a macromolecule from adhesive surface is studied theoretically, using the notion of tensile (Pincus) blobs, as well as by means of Monte-Carlo (MC) and Molecular Dynamics (MD) simulations. We show that the change of detached monomers with time is governed by a differential equation which is equivalent to the nonlinear porous medium equation (PME), employed widely in transport modeling of hydrogeological systems. Depending on the pulling force and the strength of adsorption, three kinetic regimes can be distinguished: (i) "trumpet" (weak adsorption and …
We consider star polymers, consisting of two different polymer species, in a solvent subject to quenched correlated structural obstacles. We assume that the disorder is correlated with a power-law decay of the pair correlation function g(x)\sim x^{-a}. Applying the field-theoretical renormalization group approach in d dimensions, we analyze different scenarios of scaling behavior working to first order of a double ε=4-d, δ=4-a expansion. We discuss the influence of the correlated disorder on the resulting scaling laws and possible manifestations such as diffusion controlled reactions in the vi…
Using experiments and numerical simulations, we investigate the spontaneous spreading of droplets of aqueous glycerol (Newtonian) and aqueous polymer (shear-thinning) solutions on smooth surfaces. We find that in the first millisecond the spreading of the shear-thinning solutions is identical to the spreading of water, regardless of the polymer concentration. In contrast, aqueous glycerol solutions show a different behavior, namely, significantly slower spreading rate than water. In the initial rapid spreading phase, the dominating forces that can resist the wetting are inertial forces and con…
Membranes derived from ultrathin polymeric films are promising to meet fast separations, but currently available approaches to produce polymer films with greatly reduced thicknesses on porous supports still faces challenges. Here, defect-free ultrathin polymer covering films (UPCFs) are realized by a facile general approach of rapid solvent evaporation. By fast evaporating dilute polymer solutions, we realize ultrathin coating (~30 nm) of porous substrates exclusively on the top surface, forming UPCFs with a block copolymer of polystyrene-block-poly(2-vinyl pyridine) at room temperature or a h…
Diverse processes rely on the viscous flow of polymer solutions through porous media. In many cases, the macroscopic flow resistance abruptly increases above a threshold flow rate in a porous medium---but not in bulk solution. The reason why has been a puzzle for over half a century. Here, by directly visualizing the flow in a transparent 3D porous medium, we demonstrate that this anomalous increase is due to the onset of an elastic instability. We establish that the energy dissipated by the unstable flow fluctuations, which vary across pores, generates the anomalous increase in flow resistanc…
Slippery liquid-infused porous surfaces (SLIPS) are porous nanostructures impregnated with a low surface tension lubricant. They have recently shown great promise in various applications that require non-wettable superhydrophobic surfaces. In this paper, we investigate experimentally the influence of the oil thickness on the wetting properties and drop impact dynamics of new SLIPS. By tuning the thickness of the oil layer deposited through spin-coating, we show that a sufficiently thick layer of oil is necessary to avoid dewetting spots on the porous nanostructure and thus increasing the homog…
We introduced a new concept for fabricating solvent stimulus polymer actuators with unprecedented sensitivity and accuracy. This was accomplished by integrating porous architectures and electrostatic complexation gradients in a poly(ionic liquid) membrane that bears ionic liquid species for solvent sorption. In contact with 1.5 mol% of acetone molecules in water, the actuator membrane (1 mm x 20 mm x 30 um) bent into a closed loop. While the interaction between solvents and the polymer drives the actuation, the continuous gradient in complexation degree combined with the porous architecture op…
Fundamental understanding of the effect of microscopic parameters on the dynamics of probe particles in different complex environments has wide implications. Examples include diffusion of proteins in the biological hydrogels, porous media, polymer matrix, etc. Here, we use extensive molecular dynamics simulations to investigate the dynamics of the probe particle in a polymer network on a diamond lattice which provides substantial crowding to mimic the cellular environment. Our simulations show that the dynamics of the probe increasingly becomes restricted, non-Gaussian and subdiffusive on incr…
The migration of liquids in porous media, such as sand, has been commonly considered at high saturation levels with liquid pathways at pore dimensions. In this letter we reveal a low saturation regime observed in our experiments with droplets of extremely low volatility liquids deposited on sand. In this regime the liquid is mostly found within the grain surface roughness and in the capillary bridges formed at the contacts between the grains. The bridges act as variable-volume reservoirs and the flow is driven by the capillary pressure arising at the wetting front according to the roughness le…
Velocity relaxation of a spherically symmetric polymer, immersed in a viscous incompressible fluid, and after a sudden small impulse or a sudden twist from a state of rest, is studied on the basis of the linearized Navier-Stokes equations with an added Darcy type drag term. Explicit expressions for the translational and rotational velocity relaxation functions of the polymer and for the flow pattern of the fluid are derived for a uniform permeable sphere. Surprisingly, it is found that the added mass vanishes. For fairly large values of the ratio of sphere radius to the screening length charac…
The transport of deformable particles through porous media underlies a wealth of applications ranging from filtration to oil recovery to the transport and spreading of biological agents. Using direct numerical simulations, we analyze the dynamics of semiflexible polymers under the influence of an imposed flow in a structured two-dimensional lattice serving as an idealization of a porous medium. This problem has received much attention in the limit of reptation and for long-chain polymer molecules such as DNA that are transported through micropost arrays for electrophoretic chromatographic sepa…
Porous polymer membranes via electrostatic complexation triggered by neutralization are fabricated for the first time from a water-soluble poly(ionic liquid) (PIL). The porous structure is formed as a consequence of simultaneous phase separation of the PIL and ionic complexation, which occurred in a basic solution of a non-solvent for the PIL. These membranes have a stimuli-responsive porosity, with open and closed pores in isopropanol and in water, respectively. This property is quantitatively demonstrated in filtration experiments, where water is passing much slower through the membranes tha…
The flow of viscoelastic wormlike micellar solutions (WLMs) in porous media is encountered in many practical applications like enhanced oil recovery or groundwater remediation. To understand the flow dynamics of these complex fluids in porous media, a model porous media consisting of a straight microchannel with micropore throats present in it, is very often used. In this study, we perform an extensive numerical investigation to understand the flow dynamics of wormlike micellar solutions based on the two-species Vasquez-Cook-McKinley (VCM) model for micelles through such model porous media. We…
The role of activity on the hydrodynamic dispersion of bacteria in a model porous medium is studied by tracking thousands of bacteria in a microfluidic chip containing randomly placed pillars. We first evaluate the spreading dynamics of two populations of motile and non-motile bacteria injected at different flow rates. In both cases, we observe that the mean and the variance of the distances covered by the bacteria vary linearly with time and flow velocity, a result qualitatively consistent with the standard geometric dispersion picture. However, quantitatively, the motiles bacteria display a …
The spreading of liquid nanodroplets of different initial radii $R_{0}$ is studied using molecular dynamics simulation. Results for two distinct systems, Pb on Cu(111), which is non-wetting, and a coarse grained polymer model, which wets the surface, are presented for Pb droplets ranging in size from $\sim55 000$ to $220 000$ atoms and polymer droplets ranging in size from $\sim200 000$ to $780 000$ monomers. In both cases, a precursor foot precedes the spreading of the main droplet. This precursor foot spreads as $r_{f}^{2}(t)=2D_{eff}t$ with an effective diffusion constant that exhibits a dr…
A small amount of polymer dissolved in a droplet suppresses droplet rebound when it impinges on a supersolvophobic surface. This work investigates impacting dynamics of a droplet of dilute polymer solution depending on the molecular weight and the concentration of the polymer by using multi-body dissipative particle dynamics simulations. Either the longer polymer or the high polymer concentration suppresses rebound of a droplet although its shear viscosity and the liquid-vapor surface tension are not different from those of a pure solvent droplet. We found a new mechanism of the anti-rebound i…
We discuss the temporal distribution of dynamic processes in driven polymer transport inherent to flexible chains due to stochastic tension propagation. The stochasticity originates from the disordered initial configuration of an equilibrium polymer coil, which results in random paths for tension propagation. We consider the process time for when translocation occurs across a fixed pore and when stretching occurs by pulling the chain end. A scaling argument for the mean and standard deviation of the process time is provided using the two-phase picture for stochastic propagation. The two cases …
