Crosslinked polymer chains with excluded volume: A new class of branched polymers?

In this note microgels with and without excluded volume interactions are considered. Based on earlier exact computations on Gaussian mircogels, which are formed by self-crosslinking (with $M$ crosslinks) of polymer chains with chain length $N$ Flory type approximations are used to get first insight to their behavior in solution. It is shown that two different types of microgels exist: A special type of branched polymer whose size scales as $R \propto N^{2/5} M^{-1/5}$, instead of $R \propto N^{1/2}$. The second type are $c^*$ - microgels whose average mesh sizes $r$ are swollen and form self avoiding walks with a scaling law of the form $r = a (N/M)^{3/5}$.Comment: 5 pages, 2 figures, accepted in Macromol. Theory Simu

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

Polyelectrolyte Networks: Elasticity, Swelling, and the Violation of the Flory - Rehner Hypothesis

This paper discusses the elastic behavior of polyelectrolyte networks. The deformation behavior of single polyelectrolyte chains is discussed. It is shown that a strong coupling between interactions and chain elasticity exists. The theory of the complete crosslinked networks shows that the Flory - Rehner - Hypothesis (FRH) does not hold. The modulus contains contributions from the classical rubber elasticity and from the electrostatic interactions. The equilibrium degree of swelling is estimated by the assumption of a $c^{*}$-network.Comment: submitted to Computational and Theoretical Polymer Scienc

How to break the replica symmetry in structural glasses

The variational principle (VP) has been used to capture the metastable states of a glass-forming molecular system without quenched disorder. It has been shown that VP naturally leads to a self-consistent random field Ginzburg-Landau model (RFGLM). In the framework of one-step replica symmetry breaking (1-RSB) the general solution of RFGLM is discussed in the vicinity of the spinodal temperature T_{A} in terms of ``hidden'' formfactors $\tilde g(k)$, g_{0}(k) and $\Delta(k)$. The self-generated disorder spontaneously arises. It is argued that at T < T_{A} the activated dynamics is dominant.Comment: 11 pages, no figures, accepted by Europhys. Let

Langevin Dynamics of a Polymer with Internal Distance Constraints

We present a novel and rigorous approach to the Langevin dynamics of ideal polymer chains subject to internal distance constraints. The permanent constraints are modelled by harmonic potentials in the limit when the strength of the potential approaches infinity (hard crosslinks). The crosslinks are assumed to exist between arbitrary pairs of monomers. Formally exact expressions for the resolvent and spectral density matrix of the system are derived. To illustrate the method we study the diffusional behavior of monomers in the vicinity of a single crosslink within the framework of the Rouse model. The same problem has been studied previously by Warner (J. Phys. C: Solid State Phys. {\bf 14}, 4985, (1981)) on the basis of Lagrangian multipliers. Here we derive the full, hence exact, solution to the problem.Comment: To appear in PRE, Figures on reques

Size and scaling in ideal polymer networks

The scattering function and radius of gyration of an ideal polymer network are calculated depending on the strength of the bonds that form the crosslinks. Our calculations are based on an {\it exact} theorem for the characteristic function of a polydisperse phantom network that allows for treating the crosslinks between pairs of randomly selected monomers as quenched variables without resorting to replica methods. From this new approach it is found that the scattering function of an ideal network obeys a master curve which depends on one single parameter $x= (ak)^2 N/M$, where $ak$ is the product of the persistence length times the scattering wavevector, $N$ the total number of monomers and $M$ the crosslinks in the system. By varying the crosslinking potential from infinity (hard $\delta$-constraints) to zero (free chain), we have also studied the crossover of the radius of gyration from the collapsed regime where R_{\mbox{\tiny g}}\simeq {\cal O}(1) to the extended regime R_{\mbox{\tiny g}}\simeq {\cal O}(\sqrt{N}). In the crossover regime the network size R_{\mbox{\tiny g}} is found to be proportional to $(N/M)^{1/4}$.Comment: latex, figures available on request, to be published: J. Phys I Franc

Collective Dynamics of Random Polyampholytes

We consider the Langevin dynamics of a semi-dilute system of chains which are random polyampholytes of average monomer charge $q$ and with a fluctuations in this charge of the size $Q^{-1}$ and with freely floating counter-ions in the surrounding. We cast the dynamics into the functional integral formalism and average over the quenched charge distribution in order to compute the dynamic structure factor and the effective collective potential matrix. The results are given for small charge fluctuations. In the limit of finite $q$ we then find that the scattering approaches the limit of polyelectrolyte solutions.Comment: 13 pages including 6 figures, submitted J. Chem. Phy

Stretching necklaces

Polyelectrolytes in poor solvents show a necklace structure where collapsed polymer pearls are linked to stretched strings. In the present paper the elasticity of such chains is studied in detail. Different deformation regimes are addressed. The first is the continuous regime, where many pearls are present. A continuous force extension relation ship is calculated. The main contribution comes from the tension balance and the electrostatic repulsion of consecutive pearls. The main correction term stems from the finite size of the pearls, which monitors their surface energy. For a finite amount of pearls discontinuous stretching is predicted. Finally counterion effects are discussed qualitatively.Comment: to appear in European Phys. Journal E (soft matter