Hydrogel consists of a crosslinked polymer matrix imbibed with a solvent such as water at volume fractions that can exceed 90\%. They are important in many scientific and engineering applications due to their tunable physiochemical properties, bio-compatibility, and ultra-low friction. Their multiphase structure leads to a complex interfacial rheology, yet a detailed, microscopic understanding of hydrogel friction is still emerging. Using a custom-built tribometer, here we identify three distinct regimes of frictional behavior for polyacrylic acid (PAA), polyacrylamide (PAAm), and agarose hydrogel spheres on smooth surfaces. We find that at low velocities, friction is controlled by hydrodynamic flow through the porous hydrogel network, and is inversely proportional to the characteristic pore size. At high velocities, a mesoscopic, lubricating liquid film forms between the gel and surface that obeys elastohydrodynamic theory. Between these regimes, the frictional force decreases by an order of magnitude and displays slow relaxation over several minutes. Our results can be interpreted as an interfacial shear thinning of the polymers with an increasing relaxation time due to the confinement of entanglements. This transition can be tuned by varying the solvent salt concentration, solvent viscosity, and sliding geometry at the interface.
To probe the effects of hydrogel particle additives on the water-accessible pore structure of sandy soils, we introduce a custom pressure plate method in which the volume of water expelled from a wet granular packing is measured as a function of applied pressure. Using a capillary bundle model, we show that the differential change in retained water per pressure increment is directly related to the cumulative cross-sectional area distribution $f(r)$ of the water-accessible pores with radii less than $r$. This is validated by measurements of water expelled from a model sandy soil composed of 2 m…
\textbf{Background} Hydrogels are crosslinked polymer networks that can absorb and retain a large fraction of liquid. Near a critical sliding velocity, hydrogels pressed against smooth surfaces exhibit time-dependent frictional behavior occurring over multiple timescales, yet the origin of these dynamics is unresolved. \textbf{Objective} Here, we characterize this time-dependent regime and show that it is consistent with two distinct molecular processes: sliding-induced relaxation and quiescent recovery. \textbf{Methods} Our experiments use a custom pin-on-disk tribometer to examine poly(acryl…
A combined experimental/theoretical method to simultaneously determine diffusivity and free-energy profiles of particles that penetrate into inhomogeneous hydrogel systems is presented. As the only input, arbitrarily normalized concentration profiles from fluorescence intensity data of labeled tracer particles for different penetration times are needed. The method is applied to dextran molecules of varying size which penetrate into hydrogels of polyethylene-glycol (PEG) chains with different lengths that are covalently cross-linked by hyperbranched polyglycerol (hPG) hubs. Extracted dextran bu…
We report on the transient frictional response of contacts between a rigid spherical glass probe and a micrometer-thick poly(dimethylacrylamide) hydrogel film grafted onto a glass substrate when a lateral relative motion is applied to the contact initially at rest. From dedicated experiments with \textit{in situ} contact visualization, both the friction force and the contact size are observed to vary well beyond the occurrence of a full sliding condition at the contact interface. Depending on the imposed velocity and on the static contact time before the motion is initiated, either an overshoo…
We report on the frictional behaviour of thin poly(dimethylacrylamide) (PDMA) hydrogels films grafted on glass substrates in sliding contact with a glass spherical probe. Friction experiments are carried out at various velocities and applied normal loads with the contact fully immersed in water. In addition to friction force measurements, a novel optical set-up is designed to image the shape of the contact under steady-state sliding. The velocity-dependence of both friction force $F_t$ and contact shape is found to be controlled by a Péclet number Pe defined as the ratio of the time $τ$ needed…
Force-driven translocation of a macromolecule through a nanopore is investigated by taking into account the monomer-pore friction as well as the "crowding" of monomers on the {\it trans} - side of the membrane which counterbalance the driving force acting in the pore. The set of governing differential-algebraic equations for the translocation dynamics is derived and solved numerically. The analysis of this solution shows that the crowding of monomers on the trans side hardly affects the dynamics, but the monomer-pore friction can substantially slow down the translocation process. Moreover, the…
We investigated the surface structure of hydrogels of poly(N,N-dimethylacrylamide) (PDMA) hydrogels synthesized and cross-linked simultaneously by redox free radical polymerization. We demonstrate the existence of a less cross-linked layer at the surface of the gel at least at two different length scales characterized by shear rheology and by neutron reflectivity, suggesting the existence of a gradient in cross-linking. The composition of the layer is shown to depend on the degree of hydrophobicity of the mold surface and is weaker for more hydrophobic molds. While the macroscopic tests proved…
Hyaluronic acid is an abundant polyelectrolyte in the human body that forms extracellular hydrogels in connective tissues. It is essential for regulating tissue biomechanics and cell-cell communication, yet hyaluronan overexpression is associated with pathological situations such as cancer and multiple sclerosis. Due to its enormous molecular weight (in the range of millions of Daltons), accumulation of hyaluronan hinders transport of macromolecules including nutrients and growth factors through tissues and also hampers drug delivery. However, the exact contribution of hyaluronan to tissue pen…
Investigating frictional instability due to pressurization in granular media: insights from coupled computational fluid dynamics discrete element method
We review recent progress on the theory of dynamics of polymer translocation through a nanopore based on the iso-flux tension propagation (IFTP) theory. We investigate both pore-driven translocation of flexible and a semi-flexible polymers, and the end-pulled case of flexible chains by means of the IFTP theory and extensive molecular dynamics (MD) simulations. The validity of the IFTP theory can be quantified by the waiting time distributions of the monomers which reveal the details of the dynamics of the translocation process. The IFTP theory allows a parameter-free description of the translo…
Brownian dynamics (BD) simulations are used to study the translocation dynamics of a coarse-grained polymer through a cylindrical nanopore. We consider the case of short polymers, with a polymer length, N, in the range N=21-61. The rate of translocation is controlled by a tunable friction coefficient, gamma_{0p}, for monomers inside the nanopore. In the case of unforced translocation, the mean translocation time scales with polymer length N as <tau_1>~ (N-N_p)^alpha, where N_p is the average number of monomers in the nanopore. The exponent approaches the value alpha=2 when the pore friction is…
We present a modified model based on shear rate and aging time dependent static friction between a soft solid such as gelatin hydrogel and a hard surface for instance glass surface. Earlier the model for static friction (Juvekar and Singh, 2016) considered only the bond rupture process as a result, the friction model over predicts the static friction in the experiment. The friction model now takes into account both formation and rupture of molecular chains at the sliding interface. It is also assumed that age of the newly formed bonds during the rupture process is the same as the aging time. A…
On the interaction of dilatancy and friction in the behavior of fluid-saturated sheared granular materials: a coupled Computational Fluid Dynamics--Discrete Element Method study
We investigate the dynamics of polymer translocation through a nanopore using two-dimensional Langevin dynamics simulations. In the absence of external driving force, we consider a polymer which is initially placed in the middle of the pore and study the escape time $τ_e$ required for the polymer to completely exit the pore on either side. The distribution of the escape times is wide and has a long tail. We find that $τ_e$ scales with the chain length $N$ as $τ_e \sim N^{1+2ν}$, where $ν$ is the Flory exponent. For driven translocation, we concentrate on the influence of the friction coefficie…
Recent work on suspension flows has shown that contact mechanics plays a role in suspension flow dynamics. The contact mechanics between particulate matter in dispersions should depend sensitively on the composition of the dispersed phase: evidently emulsion droplets interact differently with each other than angular sand particles. We therefore ask: what is the role of contact mechanics in dispersed media flow? We focus on slow flows, where contacts are long-lasting and hence contact mechanics effects should be most visible. To answer our question, we synthesize soft hydrogel particles with di…
Soft living tissues like cartilage can be considered as biphasic materials comprised of a fibrous complex biopolymer network and a viscous background liquid. Here, we show by a combination of experiment and theoretical analysis that both the hydraulic permeability and the elastic properties of (bio)polymer networks can be determined with simple ramp compression experiments in a commercial rheometer. In our approximate closed-form solution of the poroelastic equations of motion, we find the normal force response during compression as a combination of network stress and fluid pressure. Choosing …
During polymer translocation driven by e.g. voltage drop across a nanopore, the segments in the cis-side is incessantly pulled into the pore, which are then pushed out of it into the trans-side. This pulling and pushing polymer segments are described in the continuum level by nonlinear transport processes known, respectively, as fast and slow diffusions. By matching solutions of both sides through the mass conservation across the pore, we provide a physical basis for the cis and trans dynamical asymmetry, a feature repeatedly reported in recent numerical simulations. We then predict how the to…
We develop a theory for polymer translocation driven by a time-dependent force through an oscillating nanopore. To this end, we extend the iso-flux tension propagation theory (IFTP) [Sarabadani \textit{et al., J. Chem. Phys.}, 2014, \textbf{141}, 214907] for such a setup. We assume that the external driving force in the pore has a component oscillating in time, and the flickering pore is similarly described by an oscillating term in the pore friction. In addition to numerically solving the model, we derive analytical approximations that are in good agreement with the numerical simulations. Our…
We study translocation of semiflexible polymers driven by force $f_d$ inside a nanometer-scale pore using our three-dimensional Langevin dynamics model. We show that the translocation time $τ$ increases with increasing bending rigidity $κ$. Similarly, the exponent $β$ for the scaling of $τ$ with polymer length $N$, $τ\sim N^β$, increases with increasing $κ$ as well as with increasing $f_d$. By comparing waiting times between semiflexible and fully flexible polymers we show that for realistic $f_d$ translocation dynamics is to a large extent, but not completely, determined by the polymer's elas…
We investigate the dynamics of pore-driven polymer translocation by theoretical analysis and molecular dynamics (MD) simulations. Using the tension propagation theory within the constant flux approximation we derive an explicit equation of motion for the tension front. From this we derive a scaling relation for the average translocation time $τ$, which captures the asymptotic result $τ\propto N_0^{1+ν}$, where $N_0$ is the chain length and $ν$ is the Flory exponent. In addition, we derive the leading correction-to-scaling term to $τ$ and show that all terms of order $N_0^{2ν}$ exactly cancel o…
The deformation kinetics for glassy polymers confined in microscopic domain at very low temperature regime was investigated using a transition-rate-state dependent model considering the shear thinning behavior which means, once material being subjected to high shear rates, the viscosity diminishes with increasing shear rate. The preliminary results show that there might be nearly frictionless fields for rate of deformation due to the almost vanishing shear stress in micropores at very low temperature regime subjected to some surface conditions : The relatively larger roughness (compared to the…
We investigate the driven polymer translocation through a nanometer-scale pore in the presence and absence of hydrodynamics both in good and bad solvent. We present our results on tension propagating along the polymer segment on the cis-side that is measured for the first time using our method that works also in the presence of hydrodynamics. For simulations we use stochastic rotation dynamics, also called multi-particle collision dynamics. We find that in the good solvent the tension propagates very similarly whether hydrodynamics is included or not. Only the tensed segment is by a constant f…
