351 research outputs found
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
Compression of finite size polymer brushes
We consider edge effects in grafted polymer layers under compression. For a
semi-infinite brush, the penetration depth of edge effects is larger than the natural height and the actual height
. For a brush of finite lateral size (width of a stripe or radius of a
disk), the lateral extension of the border chains follows the scaling law
. The scaling function is estimated within
the framework of a local Flory theory for stripe-shaped grafting surfaces. For
small , decays as a power law in agreement with simple arguments.
The effective line tension and the variation with compression height of the
force applied on the brush are also calculated.Comment: 6 pages, 7 figures, submitted to PCC
A finite excluded volume bond-fluctuation model: Static properties of dense polymer melts revisited
The classical bond-fluctuation model (BFM) is an efficient lattice Monte
Carlo algorithm for coarse-grained polymer chains where each monomer occupies
exclusively a certain number of lattice sites. In this paper we propose a
generalization of the BFM where we relax this constraint and allow the overlap
of monomers subject to a finite energy penalty \overlap. This is done to vary
systematically the dimensionless compressibility of the solution in order
to investigate the influence of density fluctuations in dense polymer melts on
various s tatic properties at constant overall monomer density. The
compressibility is obtained directly from the low-wavevector limit of the
static structure fa ctor. We consider, e.g., the intrachain bond-bond
correlation function, , of two bonds separated by monomers along the
chain. It is shown that the excluded volume interactions are never fully
screened for very long chains. If distances smaller than the thermal blob size
are probed () the chains are swollen acc ording to the classical
Fixman expansion where, e.g., . More importantly, the
polymers behave on larger distances () like swollen chains of
incompressible blobs with P(s) \si m g^0s^{-3/2}.Comment: 46 pages, 12 figure
Non-extensivity of the chemical potential of polymer melts
Following Flory's ideality hypothesis the chemical potential of a test chain
of length immersed into a dense solution of chemically identical polymers
of length distribution P(N) is extensive in . We argue that an additional
contribution arises ( being the
monomer density) for all if which can be traced back to the
overall incompressibility of the solution leading to a long-range repulsion
between monomers. Focusing on Flory distributed melts we obtain for , hence,
if is similar to the typical
length of the bath . Similar results are obtained for monodisperse
solutions. Our perturbation calculations are checked numerically by analyzing
the annealed length distribution P(N) of linear equilibrium polymers generated
by Monte Carlo simulation of the bond-fluctuation model. As predicted we find,
e.g., the non-exponentiality parameter to decay
as for all moments of the distribution.Comment: 14 pages, 6 figures, submitted to EPJ
Slow plasmon modes in polymeric salt solutions
The dynamics of polymeric salt solutions are presented. The salt consists of
chains and , which are chemically different and interact with a
Flory-interaction parameter , the chain ends carry a positive
charge whereas the chain ends are modified by negative charges. The
static structure factor shows a peak corresponding to a micro phase separation.
At low momentum transfer, the interdiffusion mode is driven by electrostatics
and is of the plasmon-type, but with an unusually low frequency, easily
accessible by experiments. This is due to the polymer connectivity that
introduces high friction and amplifies the charge scattering thus allowing for
low charge densities. The interdiffusion mode shows a minimum (critical slowing
down) at finite when the interaction parameter increases we find then a low
frequency quasi-plateau.Comment: accepted in Europhys. Let
Long Range Bond-Bond Correlations in Dense Polymer Solutions
The scaling of the bond-bond correlation function along linear polymer
chains is investigated with respect to the curvilinear distance, , along the
flexible chain and the monomer density, , via Monte Carlo and molecular
dynamics simulations. % Surprisingly, the correlations in dense three
dimensional solutions are found to decay with a power law with and the exponential behavior commonly assumed is
clearly ruled out for long chains. % In semidilute solutions, the density
dependent scaling of with
( being Flory's exponent) is set by the
number of monomers contained in an excluded volume blob of size
. % Our computational findings compare well with simple scaling arguments
and perturbation calculation. The power-law behavior is due to
self-interactions of chains on distances caused by the connectivity
of chains and the incompressibility of the melt. %Comment: 4 pages, 4 figure
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