Reversible crosslinkers can enable several desirable mechanical properties, such as improved toughness and self-healing, when incorporated in polymer networks for bioengineering and structural applications. In this work, we performed coarse-grained molecular dynamics to investigate the effect of the energy landscape of reversible crosslinkers on the dynamic mechanical properties of crosslinked polymer network hydrogels. We report that, for an ideal network, the energy potential of the crosslinker interaction drives the viscosity of the network, where a stronger potential results in a higher viscosity. Additional topographical analyses reveal a mechanistic understanding of the structural rearrangement of the network as it deforms and indicate that as the number of defects increases in the network, the viscosity of the network increases. As an important validation for the relationship between the energy landscape of a crosslinker chemistry and the resulting dynamic mechanical properties of a crosslinked ideal network hydrogel, this work enhances our understanding of deformation mechanisms in polymer networks that cannot easily be revealed by experiment and reveals design ideas that can lead to better performance of the polymer network at the macroscale.
Diverse polymer crosslinking techniques allow the synthesis of linear polymer-like structures whose monomers are colloidal particles. In the case where all or part of these colloidal particles are magnetic, one can control the behaviour of these supracolloidal polymers, known as magnetic filaments (MFs), by applied magnetic fields. However, the response of MFs strongly depends on the crosslinking procedure. In the present study, we employ Langevin dynamics simulations to investigate the influence of the type of crosslinking and the distribution of magnetic particles within MFs on their respons…
Transient networks comprised of polymers connected by short-lived bonds are a common design theme for both biological and synthetic materials. Transient bonds can provide mechanical rigidity, while still allowing for visco-elastic flows on timescales longer than the bond lifetime. In many biological polymer networks such as the actin cytoskeleton, the short-lived bonds are formed by accessory proteins that diffuse away after unbinding. By contrast, bonds in synthetic networks, such as the pendant groups of telechelic polymers, can only rebind in the same location. Using a recently developed th…
We describe the large-scale collective behavior of solutions of polar biofilaments and both stationary and mobile crosslinkers. Both mobile and stationary crosslinkers induce filament alignment promoting either polar or nematic order. In addition, mobile crosslinkers, such as clusters of motor proteins, exchange forces and torques among the filaments and render the homogeneous states unstable via filament bundling. We start from a Smoluchowski equation for rigid filaments in solutions, where pairwise crosslink-mediated interactions among the filaments yield translational and rotational current…
The contact of a hydrogel during the rotational shearing on glass surface in concentrated polymer solution was observed in situ. Dynamic contact patterns that rotate in-phase with the rotational shearing of the gel were observed for the first time. The contact patterns with a periodicity in the circumferential direction appeared and developed into fine characters with the shearing time. The patterns appeared more quickly at elevated sliding velocity, polymer concentration, and normal pressure. Furthermore, the softness of the gel also substantially influenced the character of the patterns. The…
Temperature-responsive properties of surface-attached poly(N-isopropylacrylamide) (PNIPAM) network films with well-controlled chemistry are investigated. The synthesis consists of cross-linking and grafting preformed ene-reactive polymer chains through thiol--ene click chemistry. The formation of surface-attached and cross-linked polymer films has the advantage of being wellcontrolled without any caution of no-oxygen atmosphere or addition of initiators. PNIPAM hydrogel films with same cross-link density are synthesized on a wide range of thickness, from nanometers to micrometers. The swelling…
Hydrogels have a distinct combination of mechanical and water-transport behaviors. As hydrogels stiffen, they become less permeable. Here, we combine semi-dilute polymer theory with the Kozeny-Carman equation to develop a simple scaling law describing the relationship between hydraulic permeability and mechanical stiffness. We find that these properties are dictated by the polymer strand spacing, explained via analogy of a bowl of noodle soup. We find a remarkably close agreement between our scaling law and experimental results across four different polymer families with varied crosslinkings.
Chitosan (CT) is an antibacterial polysaccharide that has been investigated for drug carriers, haemostats and wound dressings. For these applications, customised CT devices can often be obtained with specific experimental conditions, which can irreversibly alter native biopolymer properties and functions and lead to unreliable material behaviour. In order to investigate the structure-function relationships in CT covalent networks, monosodium 5-sulfoisophthalate (PhS) was selected as heparin-mimicking, growth factor-binding crosslinking segment, whilst 1,4-phenylenediacetic acid (4Ph) and poly(…
A facile route for the fabrication of surface-attached hydrogel thin films with well-controlled chemistry and tailored architecture on wide range of thickness from nanometers to micrometers is reported. The synthesis, which consists in cross-linking and grafting the preformed and ene-reactive polymer chains through thiol--ene click chemistry, has the main advantage of being well-controlled without the addition of initiators. As thiol--ene click reaction can be selectively activated by UV-irradiation (in addition to thermal heating), micropatterned hydrogel films are easily synthesized. The ver…
Tough adhesive hydrogels find broad applications in engineering and medicine. Such hydrogels feature high resistance against both cohesion and adhesion failure. The superior fracture properties may, however, deteriorate when the hydrogels swell upon exposure of water. The underlying correlation between the polymer fraction and fracture properties of tough adhesive hydrogels remains largely unexplored. Here we study how the cohesion and adhesion energies of a tough adhesive hydrogel evolve with the swelling process. The results reveal a similar scaling law of the two quantities on the polymer f…
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…
In this article, we analyze different factors that affect the diffusion behavior of small tracer particles (as they are used e.g.in fluorescence correlation spectroscopy (FCS)) in the polymer network of a hydrogel and perform simulations of various simplified models. We observe, that under certain circumstances the attraction of a tracer particle to the polymer network strands might cause subdiffusive behavior on intermediate time scales. In theory, this behavior could be employed to examine the network structure and swelling behavior of weakly crosslinked hydrogels with the help of FCS.
Biopolymer gels such as fibrin and collagen networks are known to develop tensile axial stress when subject to torsion. This negative normal stress is opposite to the classical Poynting effect observed for most elastic solids including synthetic polymer gels, where torsion provokes a positive normal stress. As recently shown, this anomalous behavior in fibrin gels depends on the open, porous network structure of biopolymer gels, which facilitates interstitial fluid flow during shear and can be described by a phenomenological two-fluid model with viscous coupling between network and solvent. He…
Classical Molecular Dynamics (MD) simulations provide insight on the properties of many soft-matter systems. In some situations it is interesting to model the creation of chemical bonds, a process that is not part of the MD framework. In this context, we propose a parallel algorithm for step- and chain-growth polymerization that is based on a generic reaction scheme, works at a given intrinsic rate and produces continuous trajectories. We present an implementation in the ESPResSo++ simulation software and compare it with the corresponding feature in LAMMPS. For chain growth, our results are co…
Hydrogel coatings absorb water vapor - or other solvents - and, as such, are good candidates for antifog applications. In the present study, the transfer of vapor from the atmosphere to hydrogel thin films is measured in a situation where water vapor flows alongside the coating which is set to a temperature lower that the ambient temperature. The effect of the physico-chemistry of the hydrogel film on the swelling kinetics is particularly investigated. By using model thin films of surface-grafted polymer networks with controlled thickness, varied crosslinks density, and varied affinity for wat…
In this paper, a micro-mechanical model is introduce to characterize the stress softening phenomenon in double network hydrogels. Damage in polymer matrices under deformation, which appears as the rupture of cross-linking, is assumed to result in stress softening. The evolution of a polymer matrix is described with the network evolution method by Dargazany and Itskov [Dargazany and Itskov, International Journal of Solids and Structures, 2009, 46, 2967]. The model includes a number of physically-motivated material parameters and obtains good agreement against different sets of experimental data…
While most chemical bonds weaken under the action of mechanical force (called slip bond behavior), nature has developed bonds that do the opposite: their lifetime increases as force is applied. While such catch bonds have been studied quite extensively at the single molecule level and in adhesive contacts, recent work has shown that they are also abundantly present as crosslinkers in the actin cytoskeleton. However, their role and the mechanism by which they operate in these networks have remained unclear. Here, we present computer simulations that show how polymer networks crosslinked with ei…
Temperature-sensitive hydrogels based on polymers such as poly(N-isopropylacrylamide) (PNIPAM) undergo a volume phase transition in response to changes in temperature. During this transition, distinct changes in both thermal and mechanical properties are observed. Here, we illustrate and exploit the inherent thermodynamic link between thermal and mechanical properties by showing that the compressive elastic modulus of PNIPAM hydrogels can be probed using differential scanning calorimetry. We validate our approach by using conventional osmotic compression tests. Our method could be particularly…
We demonstrated recently that polyelectrolytes with cationic moieties along the chain and a single anionic head are able to form physical hydrogels due to the reversible nature of the head-to-body ionic bond. Here we generate a variety of such polyelectrolytes with various cationic moieties and counterion combinations starting from a common polymeric platform. We show that the rheological properties (shear modulus, critical strain) of the final hydrogels can be modulated over three orders of magnitude depending on the cation/anion pair. Our data fit remarkably well within a scaling model invol…
The emerging applications of hydrogels in devices and machines require these soft materials to maintain robustness under cyclic mechanical loads. Whereas hydrogels have been made tough to resist fracture under a single cycle of mechanical load, these toughened gels still suffer from fatigue fracture under multiple cycles of loads. The reported fatigue threshold (i.e., the minimal fracture energy at which crack propagation occurs under cyclic loads) for synthetic hydrogels is on the order of 1-100 J/m2, which is primarily associated with the energy required to fracture a single layer of polymer…
Ice-templating, also referred to as freeze-casting, is a process exploiting unidirectional crystallization of ice to structure macroporous materials from colloidal solutions. Commonly applied to inorganic and polymeric materials, we employ it here to cast soft self-assembled matter into spongy solid foams. Use of ice-templating to cast soft matter is generally confined to polymers. In the case of polymeric hydrogels, cross-linking ensures a good stability towards the harsh conditions (fast cooling at temperatures as low as-80{\textdegree}C) employed during ice-templating. However, freeze-casti…
Microtubules are an essential physical building block of cellular systems. They are organized using specific crosslinkers, motors, and influencers of nucleation and growth. With the addition of anti-parallel crosslinkers, microtubule pattern goes through transition from fan-like structures to homogeneous tactoid condensates in vitro. Tactoids are reminiscent of biological mitotic spindles, the cell division machinery. To accomplish these organizations, we use polymer crowding agents. Here we study how altering the properties of the crowders, such as size, concentration, and molecular weight, a…
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 hydr…
In this paper we study the elastic response of synthetic hydrogels to an applied shear stress. The hydrogels studied here have previously been shown to mimic the behaviour of biopolymer networks when they are sufficiently far above the gel point. We show that near the gel point they exhibit an elastic response that is consistent with the predicted critical behaviour of networks near or below the isostatic point of marginal stability. This point separates rigid and floppy states, distinguished by the presence or absence of finite linear elastic moduli. Recent theoretical work has also focused o…
We study self-assembly in suspensions of supracolloidal polymer-like structures made of crosslinked magnetic particles. Inspired by self-assembly motifs observed for dipolar hard spheres, we focus on four different topologies of the polymer-like structures: linear chains, rings, Y-shaped and X-shaped polymers. We show how the presence of the crosslinkers, the number of beads in the polymer and the magnetic interparticle interaction affect the structure of the suspension. It turns out that for the same set of parameters, the rings are the least active in assembling larger structures, whereas th…
We propose and study a simplified model for the surface and bulk structures of crosslinked polymer gels, into which voids are introduced through templating by surfactant micelles. Such systems were recently studied by Atomic Force Microscopy [M. Chakrapani et al., e-print cond-mat/0112255]. The gel is represented by a frustrated, triangular network of nodes connected by springs of random equilibrium lengths. The nodes represent crosslinkers, and the springs correspond to polymer chains. The boundaries are fixed at the bottom, free at the top, and periodic in the lateral direction. Voids are in…
Non-uniform swelling of polyelectrolyte hydrogels: effects of charge regulation
Wenzhou University（温州大学）；Zhejiang Key Laboratory of Soft Matter Biomedical Materials, Wenzhou Institute, University of Chinese Academy of Sciences（中国科学院大学温州研究院软物质生物医用材料浙江省重点实验室）；School of Physical Sciences, University of Chinese Academy of Sciences（中国科学院大学物理科学学院）；School of Physics and Astronomy, & Center for Physics and Chemistry of Living Systems, Tel Aviv University（特拉维夫大学物理与天文学学院及生命系统物理化学中心）；School of Sino-German Engineering, Shanghai Technical Institute of Electronics and Information（上海电子与信息工程技术学院中德工程学院）
When an electric field is applied to an electrolyte-saturated polymer gel embedded with charged colloidal particles, the force that must be exerted by the hydrogel on each particle reflects a delicate balance of electrical, hydrodynamic and elastic stresses. This paper examines the displacement of a single charged spherical inclusion embedded in an uncharged hydrogel. We present numerically exact solutions of coupled electrokinetic transport and elastic-deformation equations, where the gel is treated as an incompressible, elastic Brinkman medium. This model problem demonstrates how the displac…
We show that smoothing of multiaffine surfaces that are generated by simulating a crosslinked polymer gel by a frustrated, triangular network of springs of random equilibrium lengths [G.M. Buend{\'ı}a, S.J. Mitchell, P.A. Rikvold, Phys. Rev. E 66 (2002) 046119] changes the scaling behavior of the surfaces such that they become self-affine. The self-affine behavior is consistent with recent atomic force microscopy (AFM) studies of the surface structure of crosslinked polymer gels into which voids are introduced through templating by surfactant micelles [M. Chakrapani, S.J. Mitchell, D.H. Van Wi…
In the scientific literature little attention has been given to the use of dynamic light scattering (DLS) as a tool for extracting the thermodynamic information contained in the absolute intensity of light scattered by gels. In this article we show that DLS yields reliable measurements of the intensity of light scattered by the thermodynamic fluctuations, not only in aqueous polymer solutions, but also in hydrogels. In hydrogels, light scattered by osmotic fluctuations is heterodyned by that from static or slowly varying inhomogeneities. The two components are separable owing to their differen…
