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 each pore, similar to observations of an isolated pore. By contrast, when the pore spacing is sufficiently small, the flow exhibits a surprising bistability, stochastically switching between two distinct unstable flow states. We hypothesize that this unusual behavior arises from the interplay between flow-induced polymer elongation and relaxation of polymers as they are advected through the porous medium. Consistent with this idea, we find that the flow state in a given pore persists for long times. Moreover, we find that the flow state is correlated between neighboring pores; however, these correlations do not persist long-range. Our results thus help to elucidate the rich array of flow behaviors that can arise in polymer solution flow through porous media.
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.
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.
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…
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…
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…
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…
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 c…
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…
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…
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…
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…
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…
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 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…
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…
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…
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…
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…
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.
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…
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…
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…
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.
Many key environmental, industrial, and energy processes rely on controlling fluid transport within subsurface porous media. These media are typically structurally heterogeneous, often with vertically-layered strata of distinct permeabilities -- leading to uneven partitioning of flow across strata, which can be undesirable. Here, using direct in situ visualization, we demonstrate that polymer additives can homogenize this flow by inducing a purely-elastic flow instability that generates random spatiotemporal fluctuations and excess flow resistance in individual strata. In particular, we find t…
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…
We study numerically two-dimensional creeping viscoelastic flow past a biperiodic square array of cylinders within the Oldroyd B, FENE-CR and FENE-P constitutive models of dilute polymer solutions. Our results capture the initial mild decrease then dramatic upturn ('thickening') seen experimentally in the drag coefficient as a function of increasing Weissenberg number. By systematically varying the porosity of the flow geometry, we demonstrate two qualitatively different mechanisms underpinning this thickening effect: one that operates in the highly porous case of widely spaced obstacles, and …
The mechanism through which cells determine their fate is intimately related to the spreading of certain biochemical (so-called epigenetic) marks along their genome. The mechanisms behind mark spreading and maintenance are not yet fully understood, and current models often assume a long-range infection-like process for the dynamics of marks, due to the polymeric nature of the chromatin fibre which allows looping between distant sites. While these existing models typically consider antagonising marks, here we propose a qualitatively different scenario which analyses the spreading of a single ma…
Using Monte Carlo simulations, we investigate the self-assembly of model nanoparticles inside a matrix of model equilibrium polymers (or matrix of Wormlike micelles) as a function of the polymeric matrix density and the excluded volume parameter between polymers and nanoparticles. In this paper, we show morphological transitions in the system architecture via synergistic self-assembly of nanoparticles and the equilibrium polymers. In a synergistic self-assembly, the resulting morphology of the system is a result of the interaction between both nanoparticles and the polymers, unlike the polymer…
Liquid flow propelled by capillary forces is one of the most important transport mechanisms in porous environments. It is governed by a fascinating interplay of interfacial, viscous drag as well as gravitational forces which liquids encounter upon invasion into geometries with often complex topologies, such as capillary networks of trees or interconnected fractures in soils and ice. Here, we present fundamentals, concepts and an experimental, gravimetric study on the capillarity-driven invasion dynamics of liquids in networks of pores a few nanometers across in monolithic, nanoporous silica gl…
Porous polymer films of Poly(ethylene oxide)(PEO) are synthesized by solution casting technique using gamma irradiated: (a) PEO powder (S-series) and (b) PEO - methanol solution (L-series). Pore phase forms instantaneously during preparation. Optimization of the pore content and distribution enables tailoring of associated properties for multifaceted applications. This method could be analyzed for mapping of porosity and average pore size. Practicability and repeatability of the developed programme has been established for monophasic system using backscattered imaging mode of SEM. This program…
