253 research outputs found
Huge Seebeck coefficients in non-aqueous electrolytes
The Seeebeck coefficients of the non-aqueous electrolytes tetrabutylammonium
nitrate, tetraoctylphosphonium bromide and tetradodecylammonium nitrate in
1-octanol, 1-dodecanol and ethylene-glycol are measured in a temperature range
from T=30 to T=45 C. The Seebeck coefficient is generally of the order of a few
hundreds of microvolts per Kelvin for aqueous solution of inorganic ions. Here
we report huge values of 7 mV/K at 0.1M concentration for tetrabutylammonium
nitrate in 1-dodecanol. These striking results open the question of
unexpectedly large kosmotrope or "structure making" effects of
tetraalkylammonium ions on the structure of alcohols.Comment: Submitted to J. Chem. Phy
Monte-Carlo simulations of star-branched polyelectrolyte micelles
The concentration profiles of monomers and counterions in star-branched
polyelectrolyte micelles are calculated through Monte-Carlo simulations, using
the simplest freely-jointed chain model. We have investigated the onset of
different regimes corresponding to the spherical and Manning condensation of
counterions as a function of the strength of the Coulomb coupling. The
Monte-Carlo results are in fair agreement with the predictions of
Self-Consistent-Field analytical models. We have simulated a real system of
diblock copolymer micelles of (sodium-polystyrene-sulfonate)(NaPSS)--
(polyethylene-- propylene)(PEP) with f=54 hydrophilic branches of N=251
monomers at room temperature in salt-free solution and compared the calculated
form factor with our neutron-scattering data.Comment: 14 pages, 20 figure
Breaking of the Bancroft rule for multiple emulsions stabilized by a single stimulable polymer
International audienceWe investigated emulsions of water and toluene stabilized by (co)polymers consisting of styrene (S) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) monomer units with different compositions and structures such as a PDMAEMA homopolymer, a P(S-co-DMAEMA) random copolymer and various PS-b-PDMAEMA and PS-b-(S-co-DMAEMA) block copolymers. The model system is used to study the fundamental conditions under which the different kinds of polymer-stabilized emulsions (direct oil in water, inverse water in oil and multiple emulsions) are stabilized or destabilized by pH change (at constant temperature). Polymer properties like chain conformation at the toluene-water interface as probed by SANS and neutron reflectivity at the liquid-liquid interface, the oil-water partitioning of the polymer chains (Bancroft's rule of thumb) as determined by UV spectroscopy and interfacial tensions measured by the rising and spinning drop techniques are determined. Overall, results evidence that the curvature sign, as defined by positive and negative values as the chain segments occupy preferentially the water and toluene sides of the interface respectively, reliably predicts the emulsion kind. In contrast, the Bancroft rule failed at foreseeing the emulsion type. In the region of near zero curvature the crossover from direct to inverse emulsions occurs through the formation of either unstable coexisting direct and inverse emulsions (i) or multiple emulsions (ii). The high compact adsorption of the chains at the interface as shown by low interfacial tension values does not allow to discriminate between both cases. However, the toluene-water partitioning of the polymeric emulsifier is still a key factor driving the formation of (i) or (ii) emulsions. Interestingly, the stabilization of the multiple emulsions can be tuned to a large extent as the toluene-water polymer partitioning can be adjusted using quite a large number of physico-chemical parameters linked to polymer architecture like diblock length ratio or polymer total molar mass, for example. Moreover, we show that monitoring the oil-water partitioning aspect of the emulsion system can also be used to lower the interfacial tension at low pH to values slightly higher than 0.01 mN m-1, irrespective of the curvature sign
Long Range Hydration Effects in Electrolytic Free Suspended Black Films
The force law within free suspended black films made of negatively charged
Aerosol-OT (AOT) with added LiCl or CsCl is studied accurately using X-ray
reflectivity (ca. 1{\AA}). We find an electrolyte concentration threshold above
which a substantial additional repulsion is detected in the LiCl films, up to
distances of 100 {\AA}. We interpret this phenomenon as an augmentation of the
Debye screening length, due to the local screening of the condensed hydrophilic
counterions by the primary hydration shell.Comment: 4 pages, 4 figures, to be published Phys. Rev. Let
Counterion Penetration and Effective Electrostatic Interactions in Solutions of Polyelectrolyte Stars and Microgels
Counterion distributions and effective electrostatic interactions between
spherical macroions in polyelectrolyte solutions are calculated via
second-order perturbation (linear response) theory. By modelling the macroions
as continuous charge distributions that are permeable to counterions,
analytical expressions are obtained for counterion profiles and effective pair
interactions in solutions of star-branched and microgel macroions. The
counterions are found to penetrate stars more easily than microgels, with
important implications for screening of bare macroion interactions. The
effective pair interactions are Yukawa in form for separated macroions, but are
softly repulsive and bounded for overlapping macroions. A one-body volume
energy, which depends on the average macroion concentration, emerges naturally
in the theory and contributes to the total free energy.Comment: 15 pages, 5 figure
Organization of Block Copolymers using NanoImprint Lithography: Comparison of Theory and Experiments
We present NanoImprint lithography experiments and modeling of thin films of
block copolymers (BCP). The NanoImprint lithography is used to align
perpendicularly lamellar phases, over distances much larger than the natural
lamellar periodicity. The modeling relies on self-consistent field calculations
done in two- and three-dimensions. We get a good agreement with the NanoImprint
lithography setups. We find that, at thermodynamical equilibrium, the ordered
BCP lamellae are much better aligned than when the films are deposited on
uniform planar surfaces
Spinodal Decomposition in Binary Gases
We carried out three-dimensional simulations, with about 1.4 million
particles, of phase segregation in a low density binary fluid mixture,
described mesoscopically by energy and momentum conserving Boltzmann-Vlasov
equations. Using a combination of Direct Simulation Monte Carlo(DSMC) for the
short range collisions and a version of Particle-In-Cell(PIC) evolution for the
smooth long range interaction, we found dynamical scaling after the ratio of
the interface thickness(whose shape is described approximately by a hyperbolic
tangent profile) to the domain size is less than ~0.1. The scaling length R(t)
grows at late times like t^alpha, with alpha=1 for critical quenches and
alpha=1/3 for off-critical ones. We also measured the variation of temperature,
total particle density and hydrodynamic velocity during the segregation
process.Comment: 11 pages, Revtex, 4 Postscript figures, submitted to PR
Molecular Dynamics Simulation of Spinodal Decomposition in Three-Dimensional Binary Fluids
Using large-scale molecular dynamics simulations of a two-component
Lennard-Jones model in three dimensions, we show that the late-time dynamics of
spinodal decomposition in concentrated binary fluids reaches a viscous scaling
regime with a growth exponent , in agreement with experiments and a
theoretical analysis for viscous growth.Comment: 4 pages, 3 figure
Self-Consistent Field study of Polyelectrolyte Brushes
We formulate a self-consistent field theory for polyelectrolyte brushes in
the presence of counterions. We numerically solve the self-consistent field
equations and study the monomer density profile, the distribution of
counterions, and the total charge distribution. We study the scaling relations
for the brush height and compare them to the prediction of other theories. We
find a weak dependence of the brush height on the grafting density.We fit the
counterion distribution outside the brush by the Gouy-Chapman solution for a
virtual charged wall. We calculate the amount of counterions outside the brush
and find that it saturates as the charge of the polyelectrolytes increases
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