Do you want to publish a course? Click here

Intramolecular Form Factor in Dense Polymer Systems: Systematic Deviations from the Debye formula

55   0   0.0 ( 0 )
 Added by J. P. Wittmer
 Publication date 2007
  fields Physics
and research's language is English




Ask ChatGPT about the research

We discuss theoretically and numerically the intramolecular form factor $F(q)$ in dense polymer systems. Following Florys ideality hypothesis, chains in the melt adopt Gaussian configurations and their form factor is supposed to be given by Debyes formula. At striking variance to this, we obtain noticeable (up to 20%) non-monotonic deviations which can be traced back to the incompressibility of dense polymer solutions beyond a local scale. The Kratky plot ($q^2F(q)$ {it vs.} wavevector $q$) does not exhibit the plateau expected for Gaussian chains in the intermediate $q$-range. One rather finds a significant decrease according to the correction $delta(F^{-1}(q)) = q^3/32rho$ that only depends on the concentration $rho$ of the solution, but neither on the persistence length or the interaction strength.



rate research

Read More

60 - M. Watzlawek 1998
The core-core structure factor of dense star polymer solutions in a good solvent is shown theoretically to exhibit an unusual behaviour above the overlap concentration. Unlike usual liquids, these solutions display a structure factor whose first peak decreases by increasing density while the second peak grows. The scenario repeats itself with the subsequent peaks as the density is further enhanced. For low enough arm numbers $f$ ($f leq 32$), various different considerations lead to the conclusion that the system remains fluid at all concentrations.
163 - H. Meyer , T. Kreer , M. Aichele 2009
Self-avoiding polymers in two-dimensional ($d=2$) melts are known to adopt compact configurations of typical size $R(N) sim N^{1/d}$ with $N$ being the chain length. Using molecular dynamics simulations we show that the irregular shapes of these chains are characterized by a perimeter length $L(N) sim R(N)^{dpm}$ of fractal dimension $dpm = d-Theta_2 =5/4$ with $Theta_2=3/4$ being a well-known contact exponent. Due to the self-similar structure of the chains, compactness and perimeter fractality repeat for subchains of all arc-lengths $s$ down to a few monomers. The Kratky representation of the intramolecular form factor $F(q)$ reveals a strong non-monotonous behavior with $q^2F(q) sim 1/(qN^{1/d})^{Theta_2}$ in the intermediate regime of the wavevector $q$. Measuring the scattering of labeled subchains %($s F(q) sim L(s)$) the form factor may allow to test our predictions in real experiments.
The way tension propagates along a chain is a key to govern many of anomalous dynamics in macromolecular systems. After introducing the weak and the strong force regimes of the tension propagation, we focus on the latter, in which the dynamical fluctuations of a segment in a long polymer during its stretching process is investigated. We show that the response, i.e., average drift, is anomalous, which is characterized by the nonlinear memory kernel, and its relation to the fluctuation is nontrivial. These features are discussed on the basis of the generalized Langevin equation, in which the role of the temporal change in spring constant due to the stress hardening is pinpointed. We carried out the molecular dynamics simulation, which supports our theory.
Presenting theoretical arguments and numerical results we demonstrate long-range intrachain correlations in concentrated solutions and melts of long flexible polymers which cause a systematic swelling of short chain segments. They can be traced back to the incompressibility of the melt leading to an effective repulsion $u(s) approx s/rho R^3(s) approx ce/sqrt{s}$ when connecting two segments together where $s$ denotes the curvilinear length of a segment, $R(s)$ its typical size, $ce approx 1/rho be^3$ the ``swelling coefficient, $be$ the effective bond length and $rho$ the monomer density. The relative deviation of the segmental size distribution from the ideal Gaussian chain behavior is found to be proportional to $u(s)$. The analysis of different moments of this distribution allows for a precise determination of the effective bond length $be$ and the swelling coefficient $ce$ of asymptotically long chains. At striking variance to the short-range decay suggested by Florys ideality hypothesis the bond-bond correlation function of two bonds separated by $s$ monomers along the chain is found to decay algebraically as $1/s^{3/2}$. Effects of finite chain length are considered briefly.
We study dry, dense active nematics at both particle and continuous levels. Specifically, extending the Boltzmann-Ginzburg-Landau approach, we derive well-behaved hydrodynamic equations from a Vicsek-style model with nematic alignment and pairwise repulsion. An extensive study of the phase diagram shows qualitative agreement between the two levels of description. We find in particular that the dynamics of topological defects strongly depends on parameters and can lead to ``arch solutions forming a globally polar, smectic arrangement of Neel walls. We show how these configurations are at the origin of the defect ordered states reported previously. This work offers a detailed understanding of the theoretical description of dense active nematics directly rooted in their microscopic dynamics.
comments
Fetching comments Fetching comments
Sign in to be able to follow your search criteria
mircosoft-partner

هل ترغب بارسال اشعارات عن اخر التحديثات في شمرا-اكاديميا