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1.
D. Langevin 《The European physical journal. E, Soft matter》2001,5(1):81-85
Studies of thin liquid films, made from semidilute polyelectrolyte solutions, are presented. The disjoining pressure variation
with film thickness exhibits oscillations, corresponding to film stratification. The oscillations become sharper as the polymer
concentration c increases, and disappear when salt is added. The period of the oscillations scales as c
-1/2. The observed stratification is related to the polymer network and the size of the steps to the mesh size ξ.
Received 25 April 2000 and Received in final form 3 October 2000 相似文献
2.
3.
Semenov AN 《The European physical journal. E, Soft matter》2002,9(4):353-363
Adsorption of ideal polymers with stiff backbone onto a flat surface is considered theoretically. Both scaling approach and
quantitative theory are developed. We predict a self-similar monomer concentration profile c(x) ∼ x
-4/3 near the surface (when the distance to the surface x is much smaller than the chain persistence length l /2). The typical conformation of a weakly adsorbed chain can be viewed as a sequence of alternating flat (2-dimensional)
trains of wormlike short loops (flat blobs) and coil-like (3-dimensional) loops forming a triple-layer structure: contact
layer (x < Δ) of adsorbed fragments virtually laid on the surface, proximal layer (Δ < x < l) of flat blobs, and more dilute distal corona layer (x > l). Here Δ defines the range of monomer/surface attraction, Δ ≪ l. The adsorption transition is continuous. However, its relative width is small (T
* is the adsorption temperature, ΔT is the relevant temperature interval): ∼
, i.e. a discontinuous transition in the limit Δ/l↦ 0.
Received 10 October 2002 and Received in final form 22 November 2002
RID="a"
ID="a"Permanent address: Physics Department, Moscow State University, Moscow 119992, Russia. e-mail: semenov@polly.phys.msu.ru 相似文献
4.
S. Villain-Guillot D. Andelman 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,4(1):95-101
We study interfacial behavior of a lamellar (stripe) phase coexisting with a disordered phase. Systematic analytical expansions
are obtained for the interfacial profile in the vicinity of a tricritical point. They are characterized by a wide interfacial
region involving a large number of lamellae. Our analytical results apply to systems with one dimensional symmetry in true
thermodynamical equilibrium and are of relevance to metastable interfaces between lamellar and disordered phases in two and
three dimensions. In addition, good agreement is found with numerical minimization schemes of the full free energy functional
having the same one dimensional symmetry. The interfacial energy for the lamellar to disordered transition is obtained in
accord with mean field scaling laws of tricritical points.
Received: 28 March 1997 / Revised: 6 February 1998 / Accepted: 16 February 1998 相似文献
5.
We discuss theoretically the relaxation of charge fluctuations in polyampholyte solutions. It has been shown previously by
some of us (J. Wittmer et al. Europhys. Lett. 24, 263 (1993)) that the charge distribution along the polyampholyte backbone has a dramatic influence on the polarization energy
and hence on the solubility. Here it is demonstrated that a similar effect exists for the charge relaxation. The charge relaxation
mechanism qualitatively depends on the statistics: for alternating polyampholytes the relaxation is mainly due to local dipole
inversion and is not primarily driven by electrostatic interactions, whereas for random polyampholytes it is driven by electrostatic
interactions. Intermediate statistics (with short-ranged (exponential) correlations) appear as a combination of these two
limiting cases: short-wavelength modes are insensitive to the loss of correlations along the backbone, whereas long-wavelength
modes correspond to a random statistics with renormalized charges. The relaxation of the dielectric constant is also calculated.
Received: 20 December 2002 / Accepted: 13 March 2003 / Published online: 24 April 2003
RID="a"
ID="a"e-mail: johner@ics.u-strasbg.fr 相似文献
6.
The interaction between two parallel plates due to non-adsorbing polymer chains with excluded volume is calculated using the
adsorption method. The adsorption is calculated from the profile of the polymer segment concentration between the plates,
which is obtained from the product function of the concentration profile near a single wall, involving the correlation length.
The renormalization group theory provides expressions for the osmotic pressure and consequently for the osmotic compressibility,
chemical potential and correlation length of a polymer solution. Both the local polymer concentration profiles as well as
the minimum of the interaction potential between the plates agree with recently published self-avoiding random walk computer
simulations.
Received 9 August 2001 相似文献
7.
Khokhlov AR Semenov AN Subbotin AV 《The European physical journal. E, Soft matter》2005,17(3):283-306
Shapes of globules formed by amphiphilic multi-block-copolymers in a selective solvent are considered theoretically. We focus on copolymers consisting mostly of insoluble H-units forming large core surrounded by a shell of soluble P-blocks. It is shown that the globule becomes non-spherical when the effective shell tension is low enough. The resultant shape depends on the shell bending energy: it is prolate if this energy is larger than the elastic energy of the core, and oblate in the opposite case. The central result is the prediction of the formation of a surface pattern of fingers accompanying or even preempting the shape transition mentioned above. We elucidate and discuss the following finger morphologies: 1) nearly spherical knob; 2) a necklace of spherical beads extending away from the surface; 3) mostly cylindrical fingers; 4) large thorn-like fingers. The first 3 morphologies develop at equilibrium as the shell area increases (or, equivalently, the shell tension decreases). Considering the relevant kinetical aspects we show that formation of fingers is a nucleation and growth process, and that the energy of their equilibrium nucleation is likely to be high. Therefore, the finger formation may be delayed, and may actually occur in the regime where the plain spherical surface is metastable. It is the last morphology (thorn-like fingers) that characterizes the metastable regimes when the finger formation is controlled by a high activation energy. The universal features of the above predictions inviting experimental tests are discussed. 相似文献
8.
Y.O. Popov A.N. Semenov 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,6(2):245-256
Nematic ordering in anisotropic non-Gaussian elastomers is considered theoretically using mean field approximation. We focus on the effect of anisotropy during network
cross-linking on the system elasticity and, in particular, on the so-called soft deformation mode. As the main result, we
calculate the dependence of the elastomer free energy on the angle between the axis of “frozen” anisotropy and the nematic
director. The dependence of the isotropic-nematic transition point on the orientational field acting on the monomers during
the cross-linking process is also calculated.
Received: 5 November 1997 / Revised and Accepted: 29 June 1998 相似文献
9.
Jarkova E Johner A Maresov EA Semenov AN 《The European physical journal. E, Soft matter》2006,21(4):371-386
A mean-field theory of globules of random amphiphilic copolymers in selective solvents is developed for the case of an annealed
copolymer sequence: each unit can be in one of two states, H (insoluble) or P (soluble or less insoluble). The study is focussed
on the regime when H and P units tend to form long blocks, and when P units dominate in the dilute phase, but are rare in
the globule core. A first-order coil-to-globule transition is predicted at some T = T
cg. The globule core density at the transition point increases as the affinity of P units to the solvent, ˜, is increased. Two
collapse transitions, coil → “loose” globule and “loose” globule → “dense” globule, are predicted if ˜ is high enough and
P units are marginally soluble or weakly insoluble. H and P concentration profiles near the globule surface are obtained and
analyzed in detail. It is shown that the surface excess of P units rises as ˜ is increased. The surface tension decreases
in parallel. Considering the interaction between close enough surfaces of two globules, we show that they always attract each
other at a complete equilibrium. It is pointed out, however, that such equilibrium may be difficult to reach, so that partially equilibrium structures (defined by the condition that a chain forming one globule does not penetrate into the core of the other globule)
are relevant. It is shown that at such partial equilibrium the interaction is repulsive, so the globules may be stabilized
from aggregation. The strongest repulsion is predicted at the coil-to-globule transition point T
cg: the repulsion force decreases with the distance between the surfaces according to a power law. In the general case (apart
from T
cg) the force vs. distance decay becomes exponential; the decay length ξ diverges as T → T
cg. The developed theory explains certain anomalous properties observed for globules of amphiphilic homopolymers. 相似文献
10.
11.
The fluctuations of interfaces between fluid phases are governed by an effective nonlocal interface Hamiltonian whose gradient expansion leads to the Helfrich Hamiltonian. Based on density functional theory we discuss the validity of this expansion and study the expansion coefficients multiplying the corresponding curvature terms. 相似文献
12.
The European Physical Journal E - The structure of aqueous dispersion of charged anisotropic nano-composites (synthetic Laponite clays) have been studied by NMR and numerical simulations based on a... 相似文献
13.
14.
Single- and double-stranded DNA and many biological and synthetic polyelectrolytes undergo two structural transitions upon
increasing the concentration of multivalent salt or molecules. First, the expanded-stretched chains in low monovalent salt
solutions collapse into nearly neutral compact structures when the density of multivalent salt approaches that of the monomers.
With further addition of multivalent salt the chains redissolve acquiring expanded-coiled conformations. We study the redissolution
transition using a two-state model (F.J. Solis, M. Olvera de la Cruz, J. Chem. Phys. 112, 2030 (2000)). The redissolution occurs when there is a high degree of screening of the electrostatic interactions between
monomers, thus reducing the energy of the expanded state. The transition is determined by the chemical potential of the multivalent
ions in the solution, μ and the inverse screening length, κ. The transition point also depends on the charge distribution
along the chain but is nearly independent of the molecular weight and degree of flexibility of the polyelectrolytes. We generate
a diagram of μversusκ2 where we find two regions of expanded conformations, one with charged chains and the other with overcharged (inverted charge)
chains, separated by a collapsed nearly neutral conformation region. The collapse and redissolution transitions occur when
the trajectory of the properties of the salt crosses the boundaries between these regions. We find that in most cases the
redissolution occurs within the same expanded branch from which the chain precipitates.
Received 15 May 2000 and Received in final form 28 June 2000 相似文献
15.
E. Zhulina A.V. Dobrynin M. Rubinstein 《The European physical journal. E, Soft matter》2001,5(1):41-49
We develop a scaling theory for a single polyampholyte chain adsorbed on a charged spherical particle in a theta-solvent.
Adsorption of a polyampholyte molecule is due to its polarization in the electrostatic field of the particle. For large particles
with sizes exceeding the thickness of the adsorbed layer, the conformations of the chain are similar to the one found for
polyampholyte adsorption on charged planar surface. However, an adsorbed polyampholyte chain forms a self-similar flower-like
structure near the particles with sizes smaller than its Gaussian size. These self-similar structures result from the balance
of the polarization energy of loops and the excluded volume interactions between monomers. The structure of an adsorbed polyampholyte
in the flower-like conformation is similar to that of a neutral star polymer.
Received 3 March 2000 and Received in final form 5 July 2000 相似文献
16.
Higgins AM Sferrazza M Jones RA Jukes PC Sharp JS Dryden LE Webster J 《The European physical journal. E, Soft matter》2002,8(2):137-143
We investigate the dynamics of spinodal dewetting in liquid-liquid polymer systems. Dewetting of poly(methyl-methacrylate)
(PMMA) thin films on polystyrene (PS) “substrates” is followed in situ using neutron reflectivity. By following the development of roughness at the PS/PMMA interface and the PMMA surface we extract
characteristic growth times for the dewetting process. These characteristic growth times are measured as a function of the
molecular weight of the two polymers. By also carrying out experiments in the regime where the dynamics are independent of
the PS molecular weight, we are able to use dewetting to probe the scaling of the PMMA thin film viscosity with temperature
and molecular weight. We find that this scaling reflects bulk behaviour. However, absolute values are low compared to bulk
viscosities, which we suggest may be due in part to slippage at the polymer/polymer interface.
Received 25 June 2001 and Received in final form 5 December 2001 相似文献
17.
Binder K 《The European physical journal. E, Soft matter》2002,9(3):293-298
After a brief review of the scaling concepts for static and dynamic properties of polymer brushes in good solvents and Theta
solvents, the Monte Carlo evidence is discussed. It is shown that under typical conditions the diameter of the last blob is
of the order of 10-20% of the brush height, and therefore pronounced deviations from the self-consistent field predictions
occur. In bad solvents, lateral microphase separation occurs leading to an irregular pattern of “dimples”. Particularly interesting
is the response of brushes to shear deformation, and the interaction between two interpenetrating brushes. Recent attempts
to understand the resulting shear forces via molecular-dynamics simulations are briefly described, and an outlook on related experiments is given.
Dedicated to Prof. H.E. Stanley on the occasion of his 60th birthday
Received 11 March 2002 and Received in final form 3 June 2002 相似文献
18.
Dielectric measurement in the range 0.1 Hz to 1 MHz were used to study the motions of polymers and ions in an ion-conducting
polymer, polypropylene oxide containing small quantities (on the order of 1%) of lithium ions (LiClO4), confined as a sandwich of uniform thickness between parallel insulating mica surfaces. In the dielectric loss spectrum,
we observed three peaks; they originated from the normal mode of the polymer, segmental mode of the polymer, and ion motions.
With decreasing film thickness, the peak frequencies corresponding to the normal mode and ion motion shifted to lower frequencies,
indicating retardation due to confinement above 30 nm. This was accompanied by diminished intensity of the dielectric normal-mode
relaxation, suggesting that confinement diminished the fluctuations of the end-to-end vector of the chain dipole in the direction
between the confining surfaces. On the contrary, the segmental mode was not affected at that thickness. Finally, significant
retardation of the segmental mode was observed only for the thinnest film (14 nm). The different dynamical modes of the polymer
(segmental and slowest normal modes) respond with different thickness and temperature dependence to confinement.
Received 31 August 2001 and Received in final form 30 October 2001 相似文献
19.
In a SANS experiment, we have directly determined for the first time the conformation of hyaluronan, a model semirigid polyelectrolyte. At high ionic strength, this is completely possible, where the scattered intensity crosses over (when decreasing q) from a q(-1) rod variation to a q(-2) and, where fitting to the "wormlike" chain model gives the backbone, intrinsic, persistence length: L0 = 86.5 A. At low ionic strength, we can safely check that the measured persistence length appears increased by at least the amount predicted by Odijk for the electrostatic contribution, L(e) (approximately kappa(-2), square of the Debye screening length). However, the intensity at the lowest q is not only due to the single chain, since it crosses over from a q(-1) to a q(-4) variation, characteristic of polymer associations. 相似文献
20.
We consider a low-density assembly of spherical colloids, such that each is clothed by L end-grafted chemically incompatible polymer chains either of types A or B. These are assumed to be dissolved in a good common solvent. We assume that colloids are of small size to be considered as
star-polymers. Two adjacent star-polymers A and B interact through a force F originating from both excluded-volume effects and chemical mismatch between unlike monomers. Using a method developed by
Witten and Pincus (Macromolecules 19, 2509 (1986)) in the context of star-polymers of the same chemical nature, we determine exactly the force F as a function of the center-to-center distance h. We find that this force is the sum of two contributions F
e and F
s. The former, that results from the excluded volume, decays as F
e∼A
L
h
-1, with the L -dependent universal amplitude A
L∼L
3/2. While the second, which comes from the chemical mismatch, decays more slowly as F
s∼χB
L
h
-1 - τ, where τ is a critical exponent whose value is found to be τ 0.40, and χ is the standard Flory interaction parameter. We find that the corresponding L-dependent universal amplitude is B
L∼L
3 + τ
/2. Theses forces are comparable near the cores of two adjacent star-polymers, i.e. for h∼h
c∼a
(a is the monomer size). Finally, for two star-polymers of the same chemical nature (A or B), the force F that simply results from excluded-volume effects coincides exactly with F
e, and then the known result is recovered.
Received 2 October 2000 and Received in final form 24 January 2001 相似文献