The role of counterions on the elasticity of highly charged lamellar phases: a small-angle x-ray and neutron-scattering determination.
The structure and fluctuations of the swollen L(alpha) lamellar phase of highly charged surfactant didodecyldimethylammonium halide fluid bilayers (DDA+X-) are studied using high-resolution small-angle x-ray scattering and medium-resolution, high-contrast small-angle neutron-scattering. The Caille parameter eta, as a function of the swelling (L(alpha) periodicity d), was determined from the full q-range fits of the measured scattering profiles for three different counterions (X- = Cl-, Br-, and NO3-). This parameter quantifies the amplitude of the membrane fluctuations within the Landau-de Gennes smectic-A linear elasticity theory. The different anions used gave strong specific effects at the maximum swelling of the L(alpha) phase, while at lower swellings a two-phase coexistence of swollen and collapsed lamellae (d approximately 30 and approximately 80 angstroms) was observed for bromide and nitrate ions. Over the intermediate dilution range for all three counterions, a single L(alpha) phase can be continuously swollen with pure water which is governed by an equation of state (i.e., osmotic pressure versus period) and thermally excited fluctuation amplitudes that can be well described by the same Poisson-Boltzmann calculation. The membranes were found to be slightly stiffer than predicted by purely electrostatic repulsions, and this is tentatively attributed to an extra bending rigidity contribution from the surfactant chains.
Brotons
Guillaume
G
Service de Chimie Moléculaire, Commissariat à l'Energie Atomique (CEA)/Saclay, Bâtiment 125, Gif-sur-Yvette Cedex F-91191, France. brotons@univ-lemans.fr
Dubois
Monique
M
Belloni
Luc
L
Grillo
Isabelle
I
Narayanan
Theyencheri
T
Zemb
Thomas
T