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Register a new userWhy polymer chains in a melt are not random walks
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A cornerstone of modern polymer physics is the `Flory ideality hypothesis which states that a chain in a polymer melt adopts `ideal random-walk-like conformations. Here we revisit theoretically and numerically this pivotal assumption and demonstrate that there are noticeable deviations from ideality. The deviations come from the interplay of chain connectivity and the incompressibility of the melt, leading to an effective repulsion between chain segments of all sizes $s$. The amplitude of this repulsion increases with decreasing $s$ where chain segments become more and more swollen. We illustrate this swelling by an analysis of the form factor $F(q)$, i.e. the scattered intensity at wavevector $q$ resulting from intramolecular interferences of a chain. A `Kratky plot of $q^2F(q)$ {em vs.} $q$ does not exhibit the plateau for intermediate wavevectors characteristic of ideal chains. One rather finds a conspicuous depression of the plateau, $delta(F^{-1}(q)) = |q|^3/32rho$, which increases with $q$ and only depends on the monomer density $rho$.
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A small fraction of intermediate-mass main sequence (A and B type) stars have strong, organised magnetic fields. The large majority of such stars, however, show no evidence for magnetic fields, even when observed with very high precision. In this paper we describe a simple model, motivated by qualitatively new observational results, that provides a natural physical explanation for the small fraction of observed magnetic stars.
Continuous time random walks (CTRW) on finite arbitrarily inhomogeneous chains are studied. By introducing a technique of counting all possible trajectories, we derive closed-form solutions in Laplace space for the Greens function and for the first passage time probability density function (PDF) for nearest neighbor CTRWs in terms of the input waiting time PDFs. These solutions are also the Laplace space solutions of the generalized master equation (GME). Moreover, based on our counting technique, we introduce the adaptor function for expressing higher order propagators (joint PDFs of time-position variables) for CTRWs in terms of Greens functions. Using the derived formulae, an escape problem from a biased chain is considered.
It is commonly accepted that in concentrated solutions or melts high-molecular weight polymers display random-walk conformational properties without long-range correlations between subsequent bonds. This absence of memory means, for instance, that the bond-bond correlation function, $P(s)$, of two bonds separated by $s$ monomers along the chain should exponentially decay with $s$. Presenting numerical results and theoretical arguments for both monodisperse chains and self-assembled (essentially Flory size-distributed) equilibrium polymers we demonstrate that some long-range correlations remain due to self-interactions of the chains caused by the chain connectivity and the incompressibility of the melt. Suggesting a profound analogy with the well-known long-range velocity correlations in liquids we find, for instance, $P(s)$ to decay algebraically as $s^{-3/2}$. Our study suggests a precise method for obtaining the statistical segment length bstar in a computer experiment.
In this paper we study a system of entangled chains that bear reversible cross-links in a melt state. The cross-links are tethered uniformly on the backbone of each chain. A slip-link type model for the system is presented and solved for the relaxation modulus. The effects of entanglements and reversible cross-linkers are modelled as discrete form of constraints that influence the motion of the primitive path. In contrast to a non-associating entangled system the model calculations demonstrate that the elastic modulus has a much higher first plateau and a delayed terminal relaxation. These effects are attributed to the evolution of the entangled chains as influenced by tethered reversible linkers. The model is solved for the case when linker survival time $tau_s$ is greater than the entanglement time $tau_e$ but less than the Rouse time $tau_R$.
Conformation-dependent design of polymer sequences can be considered as a tool to control macromolecular self-assembly. We consider the monomer unit sequences created via the modification of polymers in a homogeneous melt in accordance with the spatial positions of the monomer units. The geometrical patterns of lamellae, hexagonally packed cylinders, and balls arranged in a body-centered cubic lattice are considered as typical microphase-separated morphologies of block copolymers. Random trajectories of polymer chains are described by the diffusion-type equations and, in parallel, simulated in the computer modeling. The probability distributions of block length $k$, which are analogous to the first-passage probabilities, are calculated analytically and determined from the computer simulations. In any domain, the probability distribution can be described by the asymptote $~k^{-3/2}$ at moderate values of $k$ if the spatial size of the block is less than the smallest characteristic size of the domain. For large blocks, the exponential asymptote $exp(-const , k a^2/d_{as}^2)$ is valid, $d_{as}$ being the asymptotic domain length (a is the monomer unit size). The number average block lengths and their dispersities change linearly with the block length for lamellae, cylinders, and balls, when the domain is characterized by a single characteristic size. If the domain is described by more than one size, the number average block length can grow nonlinearly with the domain sizes and the length das can depend on all of them.
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