Stable covalently photo-cross-linked poly(ionic liquid) membrane with gradient pore size

An imidazolium-based poly(ionic liquid) is covalently cross-linked via UV light-induced thiolene (click) chemistry to yield a stable porous polyelectrolyte membrane with gradients of crosslink density and pore size distribution along its cross-section.Comment: 16 pages, 10 figure

Anisotropic Random Networks of Semiflexible Polymers

Motivated by the organization of crosslinked cytoskeletal biopolymers, we present a semimicroscopic replica field theory for the formation of anisotropic random networks of semiflexible polymers. The networks are formed by introducing random permanent crosslinks which fix the orientations of the corresponding polymer segments to align with one another. Upon increasing the crosslink density, we obtain a continuous gelation transition from a fluid phase to a gel where a finite fraction of the system gets localized at random positions. For sufficiently stiff polymers, this positional localization is accompanied by a {\em continuous} isotropic-to-nematic (IN) transition occuring at the same crosslink density. As the polymer stiffness decreases, the IN transition becomes first order, shifts to a higher crosslink density, and is preceeded by an orientational glass (statistically isotropic amorphous solid) where the average polymer orientations freeze in random directions.Comment: 5 pages, 2 figures; final version with expanded discussion to appear in PR

A model for gelation with explicit solvent effects: Structure and dynamics

We study a two-component model for gelation consisting of $f$-functional monomers (the gel) and inert particles (the solvent). After equilibration as a simple liquid, the gel particles are gradually crosslinked to each other until the desired number of crosslinks has been attained. At a critical crosslink density the largest gel cluster percolates and an amorphous solid forms. This percolation process is different from ordinary lattice or continuum percolation of a single species in the sense that the critical exponents are new. As the crosslink density $p$ approaches its critical value $p_c$, the shear viscosity diverges: $\eta(p)\sim (p_c-p)^{-s}$ with $s$ a nonuniversal concentration-dependent exponent.Comment: 6 pages, 9 figure

Crosslinked biopolymer bundles: crosslink reversibility leads to cooperative binding/unbinding phenomena

We consider a biopolymer bundle consisting of filaments that are crosslinked together. The crosslinks are reversible: they can dynamically bind and unbind adjacent filament pairs as controlled by a binding enthalpy. The bundle is subjected to a bending deformation and the corresponding distribution of crosslinks is measured. For a bundle consisting of two filaments, upon increasing the bending amplitude, a first-order transition is observed. The transition is from a state where the filaments are tightly coupled by many bound crosslinks, to a state of nearly independent filaments with only a few bound crosslinks. For a bundle consisting of more than two filaments, a series of first-order transitions is observed. The transitions are connected with the formation of an interface between regions of low and high crosslink densities. Combining umbrella sampling Monte Carlo simulations with analytical calculations, we present a detailed picture of how the competition between crosslink shearing and filament stretching drives the transitions. We also find that, when the crosslinks become soft, collective behavior is not observed: the crosslinks then unbind one after the other leading to a smooth decrease of the average crosslink density.Comment: 12 pages, 13 figure

A statistical theory of polymer network degradation

A statistical theory was proposed for the degradation (random scission of chains) of a network having f-functional nodes in the case where all chains contain equireactive groups and a chain scission event does not create new groups or suppress more than one group. Closedform relations were established between the conversion ratio of the degradation process and the crosslink density. Emphasis was put on the value of the conversion ratio for which the gel disappears. Some limited cases already considered in the literature were recovered, but a general solution was proposed for networks having any number of reactive groups per chain, be it uniform or not, and for conversion ratios up to the degelation point. The results were applied successfully to recent experiments regarding the hydrolysis of a polyester

Elasto-plastic response of reversibly crosslinked biopolymer bundles

We study the response of F-actin bundles to driving forces through a simple analytical model. We consider two filaments connected by reversibly bound crosslinks and driven by an external force. Two failure modes under load can be defined. \textit{Brittle failure} is observed when crosslinks suddenly and collectively unbind, leading to catastrophic loss of bundle integrity. During \textit{ductile failure}, on the other hand, bundle integrity is maintained, however at the cost of crosslink reorganization and defect formation. We present phase diagrams for the onset of failure, highlighting the importance of the crosslink stiffness for these processes. Crossing the phase boundaries, force-deflection curves display (frequency-dependent) hysteresis loops, reflecting the first-order character of the failure processes. We evidence how the introduction of defects can lead to complex elasto-plastic relaxation processes, once the force is switched off. Depending on, both, the time-scale for defect motion as well as the crosslink stiffness, bundles can remain in a quasi-permanent plastically deformed state for a very long time.Comment: 9 pages, 15 figure

Elasticity in strongly interacting soft solids: polyelectrolyte network

This paper discusses the elastic behavior of a very long crosslinked polyelectrolyte chain (Debye-H\"uckel chain), which is weakly charged. Therefore the response of the crosslinked chain (network) on an external constant force $f$ acting on the ends of the chain is considered. A selfconsistent variational computation of an effective field theory is employed. It is shown, that the modulus of the polyelectrolyte network has two parts: the first term represents the usual entropy elasticity of connected flexible chains and the second term takes into account the electrostatic interaction of the monomers. It is proportional to the squared crosslink density and the Debye - screening parameter.Comment: submitted for publication to PR

Normal stresses at the gelation transition

A simple Rouse-type model, generalised to incorporate the effects of chemical crosslinks, is used to obtain a theoretical prediction for the critical behaviour of the normal-stress coefficients $\Psi_{1}$ and $\Psi_{2}$ at the gelation transition. While the exact calculation shows $\Psi_{2}\equiv 0$, a typical result for these types of models, an additional scaling ansatz is used to demonstrate that $\Psi_{1}$ diverges with a critical exponent $\ell = k+z$. Here, $k$ denotes the critical exponent of the shear viscosity and $z$ the exponent governing the divergence of the time scale in the Kohlrausch decay of the shear-stress relaxation function. For crosslinks distributed according to mean-field percolation, this scaling relation yields $\ell =3$, in a accordance with an exact expression for the first normal-stress coefficient based on a replica calculation. Alternatively, using three-dimensional percolation for the crosslink ensemble we find the value $\ell \approx 4.9$. Results on time-dependent normal-stress response are also presented.Comment: RevTeX4, 6 pages, 2 figures; changes: explanatory comments expande

Elastic response of filamentous networks with compliant crosslinks

Experiments have shown that elasticity of disordered filamentous networks with compliant crosslinks is very different from networks with rigid crosslinks. Here, we model and analyze filamentous networks as a collection of randomly oriented rigid filaments connected to each other by flexible crosslinks that are modeled as worm-like chains. For relatively large extensions we allow for enthalpic stretching of crosslinks' backbones. We show that for sufficiently high crosslink density, the network linear elastic response is affine on the scale of the filaments' length. The nonlinear regime can become highly nonaffine and is characterized by a divergence of the elastic modulus at finite strain. In contrast to the prior predictions, we do not find an asymptotic regime in which the differential elastic modulus scales linearly with the stress, although an approximate linear dependence can be seen in a transition from entropic to enthalpic regimes. We discuss our results in light of the recent experiments.Comment: 10 pages, 11 figure

Structure, morphology, and mechanical properties of polysiloxane elastomer composites prepared by in situ polymerization of zinc dimethacrylate

Methyl vinyl silicone rubber/zinc dimethacrylate (VMQ/ZDMA) composites were prepared through in situ polymerization of ZDMA monomers during the peroxide curing. The polymerization conversion of ZDMA and morphology of the VMQ/ZDMA composites were studied. The results showed that most of the ZDMA monomers participated in the in situ polymerization during the cross-linking of the VMQ matrix and uniform nanophases were formed in the composites. The ‘dissolving-diffusion’ model was used to explain the micro-nano transformation of ZDMA. According to the model, a uniform nano-dispersed structure could be obtained through the in situ reaction even though the initial dispersion of ZDMA in the blends was poor. In addition, tensile tests of VMQ/ZDMA composites showed that ZDMA had a significant reinforcement on the mechanical properties of VMQ, and the best mechanical properties were obtained when the amounts of peroxide and ZDMA were 5 and 40 phr, respectively. The gross crosslink density and ionic crosslink density increased as the amount of ZDMA increased, but the covalent crosslink density decreased slightly. These results indicated that the ionic crosslink structure had a significant effect on the mechanical properties of VMQ/ZDMA composites