Aleksey M. Tikhonov

MOLECULAR ORDERING AND PHASE TRANSITIONS IN ALKANOL MONOLAYERS AT THE WATER-HEXANE INTERFACE

The interface between bulk water and bulk hexane solutions of n-alkanols (H(CH(2))(m)OH, where m=20, 22, 24, or 30) is studied with x-ray reflectivity, x-ray off-specular diffuse scattering, and interfacial tension measurements. The alkanols adsorb to the interface to form a monolayer. The highest density, lowest temperature monolayers contain alkanol molecules with progressive disordering of the chain from the -CH(2)OH to the -CH(3) group. In the terminal half of the chain that includes the -CH(3) group the chain density is similar to that observed in bulk liquid alkanes just above their freezing temperature. The density in the alkanol headgroup region is 10% greater than either bulk water or the ordered headgroup region found in alkanol monolayers at the water-vapor interface. We conjecture that this higher density is a result of water penetration into the headgroup region of the disordered monolayer. A ratio of 1:3 water to alkanol molecules is consistent with our data. We also place an upper limit of one hexane to five or six alkanol molecules mixed into the alkyl chain region of the monolayer. In contrast, H(CH(2))(30)OH at the water-vapor interface forms a close-packed, ordered phase of nearly rigid rods. Interfacial tension measurements as a function of temperature reveal a phase transition at the water-hexane interface with a significant change in interfacial excess entropy. This transition is between a low temperature interface that is nearly fully covered with alkanols to a higher temperature interface with a much lower density of alkanols. The transition for the shorter alkanols appears to be first order whereas the transition for the longer alkanols appears to be weakly first order or second order. The x-ray data are consistent with the presence of monolayer domains at the interface and determine the domain coverage (fraction of interface covered by alkanol domains) as a function of temperature. This temperature dependence is consistent with a theoretical model for a second order phase transition that accounts for the domain stabilization as a balance between line tension and long range dipole forces. Several aspects of our measurements indicate that the presence of domains represents the appearance of a spatially inhomogeneous phase rather than the coexistence of two homogeneous phases.

Vaporization and layering of alkanols at the oil/water interface

This study of adsorption of normal alkanols at the oil/water interface with x-ray reflectivity and tensiometry demonstrates that the liquid to gas monolayer phase transition at the hexane/water interface is thermodynamically favourable only for long-chain alkanols. As the alkanol chain length is decreased, the change in excess interfacial entropy per area ΔSaσ decreases to zero. Systems with small values of ΔSaσ form multi-molecular layers at the interface instead of the monolayer formed by systems with much larger ΔSaσ. Substitution of n-hexane by n-hexadecane significantly alters the interfacial structure for a given alkanol surfactant, but this substitution does not fundamentally change the phase transition behaviour of the monolayers. These data show that the critical alkanol carbon number, at which the change in excess interfacial entropy per area decreases to zero, is approximately six carbons larger than the number of carbons in the alkane solvent molecules.

X-ray study of the electric double layer at the n-hexane/nanocolloidal silica interface

The spatial structure of the transition region between an insulator and an electrolyte solution was studied with x-ray scattering. The electron-density profile across the n-hexane/silica sol interface (solutions with 5, 7, and 12 nm colloidal particles) agrees with the theory of the electrical double layer and shows separation of positive and negative charges. The interface consists of three layers, i.e., a compact layer of Na(+), a loose monolayer of nanocolloidal particles as part of a thick diffuse layer, and a low-density layer sandwiched between them. Its structure is described by a model in which the potential gradient at the interface reflects the difference in the potentials of image forces between the cationic Na(+) and anionic nanoparticles and the specific adsorption of surface charge. The density of water in the large electric field (approximately 10(9)-10(10) Vm) of the transition region and the layering of silica in the diffuse layer is discussed.

X-Ray Scattering from Liquid–Liquid Interfaces

We present our recent progress in using synchrotron x-ray surface scattering to study several different aspects of ordering at liquid–liquid interfaces. (1) The interfacial width at the water–alkane interface has been measured for a series of different chain length alkanes. The variation of interfacial width with the carbon number can be described by combining the capillary wave prediction for the width with a contribution from the intrinsic structure. (2) Under appropriate conditions, a surfactant monolayer forms at the interface between water and a hexane solution of a fluorinated surfactant. Reflectivity measurements that probe the electron density profile normal to the interface provide information on the surfactant ordering. This monolayer undergoes a solid to gas transition as a function of temperature. Diffuse scattering near the transition reveals the presence of islands. (3) Equilibrium interfaces between two aqueous phases containing polyethylene glycol and potassium phosphate salts can be studied. We present studies of conformal capillary wave fluctuations between two interfaces of a thin film of this biphase system. We also demonstrate that ferritin can be trapped and studied at this aqueous–aqueous interface.

X‐Ray Studies of Surfactant Ordering and Interfacial Phases at the Water‐Oil Interface

X‐ray reflectivity studies of surfactants at the water‐oil interface yield structural information with sub‐nanometer resolution. In this presentation, we reviewed recent X‐ray reflectivity measurements of the interface between water and a hexane solution of the hydrocarbon alkanol CH3(CH2)19OH and fluorocarbon alkanol CF3(CF2)7(CH2)2OH. The mixed system exhibits three monolayer phases, two of which are similar to single surfactant phases. A transition from a liquid monolayer to a solid monolayer occurs with increasing temperature. This unusual phase transition and the qualitative features of the phase diagram are predicted by an appropriate superposition of the behavior of the two single surfactant systems.

Controlling the nanoscale morphology of organic films deposited by polyatomic ions

Abstract Hyperthermal polyatomic ion beams can be used to fabricate thin film nanostructures with controlled morphology. Several experiments are described in which mass-selected and non-mass-selected polyatomic ion beams are used to create nanometer thick films with controlled surface and buried interface morphologies. Fluorocarbon and thiophenic films are grown on silicon wafers and/or polystyrene from 5 to 200 eV C3F5+ or C4H4S+ ions, respectively. X-ray photoelectron spectroscopy, atomic force microscopy, X-ray reflectivity, and scanning electron microscopy are utilized to analyze the morphology and chemistry of these films. Polyatomic ions are found to control film morphology on the nanoscale through variation of the incident ion energy, ion structure and/or substrate.

Ion-size effect at the surface of a silica hydrosol

Using synchrotron x-ray reflectivity, I studied the ion-size effect for alkali ions (Na(+), K(+), Rb(+), and Cs(+)), with densities as high as 4x10(18)-7x10(18) m(-2), suspended above the surface of a colloidal solution of silica nanoparticles in the field generated by the surface electric-double layer. I found that large alkali ions preferentially accumulate and replace smaller ones at the surface of the hydrosol, a result qualitatively agreeing with the dependence of the Kharkats-Ulstrup single-ion electrostatic free energy on the ions radius.

Wigner crystals of Na+ ions at the surface of a silica hydrosol

The symmetry of the surface of an electrolyte solution can be anisotropic, regardless of the bulks isotropic symmetry, because of spatial correlations between adsorbed ions. The author used x-ray grazing-incidence diffraction to measure the spatial correlations between sodium ions in classical one-component plasma adsorbed with Bjerrums density at the surface of a monodispersed 22 nm particle colloidal silica solution stabilized by NaOH with a total bulk concentration approximately 0.05 mol/L. The authors findings show that the surface compact layer is in a two-dimensional crystalline state (symmetry p2), with four sodium ions forming the unit cell and a approximately 30 A translational correlation length between the ions.

x-ray Surface Scattering Studies of Molecular Ordering at Liquid-Liquid Interfaces

We present our recent progress in using synchrotron x-ray surface scattering techniques to study several different aspects of ordering at liquid-liquid interfaces. (1) We present measurements of the interfacial width at the water-alkane interface for a series of different chain length alkanes. The width for the shortest chain length studied is in agreement with capillary wave theory. However, significant deviations occur for longer chain lengths, indicating the presence of molecular ordering at the interface. (2) Under appropriate conditions, a surfactant monolayer forms at the interface between water and a hexane solution of a fluorinated surfactant. Reflectivity measurements that probe the electron density profile normal to the interface provide information about the surfactant ordering. This monolayer undergoes a solid to gas transition as a function of temperature. Diffuse scattering near the transition reveals the presence of islands. (3) Equilibrium interfaces between two aqueous phases containing PEG (polyethylene glycol) and potassium phosphate salts can be studied. We present studies of coherent capillary wave fluctuations between two interfaces of a thin film of this biphase system. We also demonstrate that biological macromolecules can be trapped and studied at this aqueous-aqueous interface.