Self-assembled aggregates of amphiphilic surfactant molecules formed on solid surfaces are similar to biological membranes. To understand the formation mechanism of these aggregates, we have studied the formation of self-organized monolayers from low-concentration sodium dodecyl sulfate (SDS) aqueous solutions (concentration below the critical micelle concentration) on gold surfaces. The study has been carried out by using simultaneously quartz crystal microbalance (QCM) and open circuit potential measurements in situ. We have developed a model which explains the variation of the QCM frequency and open circuit potential following SDS additions to water. The dominant growth mechanism during the major part of film formation was demonstrated to be surface diffusion of surfactant molecules.
Water at room temperature is not simply a medium for which uniform properties can always be assumed. Water close to solid hydrophobic or hydrophilic surfaces has elasticity, which is measured by monitoring the quartz crystal microbalance (QCM) resonant frequency and resistance. Small additions of salt are shown to modify this elasticity. Furthermore, near the hydrophobic QCM gold electrode, undersaturated aqueous NaCl solutions present a high concentration of ion pairs, which is confirmed by atomic force microscopy through force versus distance measurements.
The interaction of liquid with electric fields is investigated in a configuration where up to 13 kV are applied between electrodes resulting in a 106 V/m electric field in the capillaries and where there is the formation of a free-standing fluid bridge in the interelectrode gap. The Mott-Gurney equation was fitted to the measured ionization current vs applied voltage curve which indicates that the ionization rate at the high-voltage anode electrode dimethylsulfoxide (DMSO) interface and space charging in the interelectrode gap determine the floating liquid bridge current for a given cathode-to-anode voltage. Space charge effects were measured in the cathode becker and also at the liquid bridge since the ionized charges at the anode migrate to the bridge outer surface and decrease the interfacial tension from 43 mJ/m2 to 29 mJ/m2. Two distinct structural regions then form the bridge, a charged plastic (bulk modulus ∼100 MPa) conducting outer layer with a surface conductivity of ∼10−9 Ω−1, which shapes and supports the floating fluid structure, and an inner liquid cylinder, where DMSO molecules flow.
While there seems to be broad agreement that cluster
formation
does exist near solid surfaces, its presence at the liquid/vapor interface
is controversial. We report experimental studies we have carried out
on interfacial water attached on hydrophobic and hydrophilic surfaces.
Nanosized steps in the measured force vs distance to the surface curves
characterize water cluster profiles. An expansion of the interfacial
structure with time is observed; the initial profile extent is typically
∼1 nm, and for longer times expanded structures of ∼70
nm are observed. Our previous results showed that the interfacial
water structure has a relative permittivity of ε ≈ 3
at the air/water interface homogeneously increasing to ε ≈
80 at 300 nm inside the bulk, but here we have shown that the interfacial
dielectric permittivity may have an oscillating profile describing
the spatial steps in the force vs distance curves. This low dielectric
permittivity arrangements of clusters extend the region with ε
≈ 3 inside bulk water and exhibit a behavior similar to that
of water networks that expand in time.
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