Rebecca J. L. Welbourn

Hexadecylamine Adsorption at the Iron Oxide–Oil Interface

The adsorption behavior of a model additive, hexadecylamine, onto an iron surface from hexadecane oil has been characterized using polarized neutron reflectometry, sum-frequency generation spectroscopy, solution depletion isotherm, and X-ray photoelectron spectroscopy (XPS). The amine showed a strong affinity for the metal surface, forming a dense monolayer at relatively low concentrations; a layer thickness of 16 (±3) Å at low concentrations, increasing to 20 (±3) Å at greater amine concentrations, was determined from the neutron data. These thicknesses suggest that the molecules in the layer are tilted. Adsorption was also indicated by sum-frequency generation spectroscopy and XPS, the latter indicating that the most dominant amine–surface interaction was via electron donation from the nitrogen lone pair to the positively charged iron ions. Sum-frequency generation spectroscopy was used to determine the alkyl chain conformation order and orientation on the surface.

Cation Bridging Studied by Specular Neutron Reflection

The binding of an anionic surfactant onto an anionic surface by addition of divalent ions is reported based on experimental data from specular neutron reflection (NR) and attenuated total internal reflection IR spectroscopy (ATR-IR). Similar measurements using monovalent ions (sodium) do not show any evidence of such adsorption, even though the amount of surfactant can be much higher. This data is interpreted in terms of the so-called bridging mechanism of ion binding.

Adsorption of Aerosol-OT at the calcite/water interface--comparison of the sodium and calcium salts.

The adsorption of the surfactant Aerosol-OT (AOT) at the calcite-water interface has been investigated using batch adsorption isotherms and neutron reflection. The adsorption isotherms showed that NaAOT adsorption followed S-type adsorption behaviour with a maximum surface excess of 2.5 mg m(-2) but the method could not be used for the investigation of Ca(AOT)2 adsorption owing to the changes in the bulk phase behaviour of the solution. The surface excess, determined by neutron reflection at the critical micelle concentration (CMC), was 2.5 mg m(-2) for Ca(AOT)2 and 1.8 mg m(-2) for NaAOT. The time dependence of the NaAOT adsorption suggests a slow conversion from the sodium to the calcium salt of AOT at the calcite-water interface by binding calcium ions released from the slightly soluble calcite. The layer thickness in both cases was 35 Å which indicates adsorption as bilayers or distorted micelles. At higher concentrations of NaAOT (~10× CMC) adsorption of an AOT lamellar phase was evident from Bragg peaks in the specular reflection. To our knowledge, this is the first time that adsorption of a surfactant at the calcite-water interface has been investigated by neutron reflection. The technique provided significant new insight into the adsorption behaviour of AOT which would not have been accessible using traditional techniques.

Polarized Neutron Reflectometry of Nickel Corrosion Inhibitors

Polarized neutron reflectometry has been used to investigate the detailed adsorption behavior and corrosion inhibition mechanism of two surfactants on a nickel surface under acidic conditions. Both the corrosion of the nickel surface and the structure of the adsorbed surfactant layer could be monitored in situ by the use of different solvent contrasts. Layer thicknesses and roughnesses were evaluated over a range of pH values, showing distinctly the superior corrosion inhibition of one negatively charged surfactant (sodium dodecyl sulfate) compared to a positively charged example (dodecyl trimethylammonium bromide) due to its stronger binding interaction with the surface. It was found that adequate corrosion inhibition occurs at significantly less than full surface coverage.

Adsorption of Methyl Ester Sulfonate at the Air–Water Interface: Can Limitations in the Application of the Gibbs Equation be Overcome by Computer Purification?

We describe a new laboratory synthesis of the α-methyl ester sulfonates based on direct sulfonation of the methyl ester by SO3 introduced from the vapor phase. This was used to synthesize a chain deuterated sample of αC14MES, which was then used to measure the surface excess of αC14MES directly at the air/water interface over a wide range of concentration using neutron reflection. The adsorption isotherm could be fitted to an empirical equation close to a Langmuir isotherm and gave a limiting surface excess of (3.4 ± 0.1) × 10-6 mol m-2 in the absence of added electrolyte. The neutron-measured surface excesses were combined with the integrated Gibbs equation to fit the variation in surface tension with concentration (σ-ln C curve). The fit was exact provided that we used a prefactor consistent with the counterion at the surface being an impurity divalent ion, as has previously been found for sodium diethylhexylsulfosuccinate (aerosol OT or AOT) and various perfluorooctanoates. The critical micelle concentration (CMC) was determined from this fit to be 2.4 ± 0.3 mM in the absence of electrolyte. In the presence of 100 mM NaCl, this contamination was suppressed and the σ-ln C curve could be fitted using the integrated Gibbs equation with the expected prefactor of 1. The new data were used to reinterpret measurements by Danov et al. on an unpurified sample of αC14MES for which computer refinement was used to try to eliminate the effects of the impurities.

A Neutron Diffraction Study of the Electrochemical Double Layer Capacitor Electrolyte Tetrapropylammonium Bromide in Acetonitrile

Neutron diffraction with isotopic substitution has been used to characterize the bulk liquid structure of the technologically relevant electrolyte solution, 1 M tetrapropylammonium bromide (TPA Br) in acetonitrile (acn), and of pure deuterated acetonitrile. Empirical potential structure refinement modeling procedures have been used to extract detailed structural information about solvent-solvent, solvent-ion, and ion-ion correlations. Analysis of the refined data shows the expected local dipolar conformation of acn in the pure solvent. This short-range dipolar ordering is also present within the solutions of TPA Br in acn, and it affects how the solvent orders itself around the ions. The solvation numbers of the TPA cations and the bromide anions are deduced, 8 and 5, respectively, as are the orientations of the solvent molecules that surround the ions. Evidence for ion association is also presented, with nearly two-thirds of the ions in the system being in associated pairs or clusters.

Adsorption of Sodium Hexanoate on α-Alumina

Neutron reflection and adsorption isotherm measurements have been used to study the adsorption behaviour of hexanoic acid onto α-alumina surfaces. Importantly, the pH dependence of the behaviour has been characterised with a pronounced maximum in adsorption identified at a pH of approximately 5, close to the pKa of the acid. The adsorbed layer is identified as a bilayer, which is reasonable given the hydrophilic nature of both side of the layer, and has a thickness of 13 Å, suggesting significant extent of interdigitation. At pH 5, the layer has much lower extent of hydration relative to the higher pH of 7, consistent with the increased total adsorption at pH 5. A number of different mechanisms for the binding of the hexanoic acid to the surface are considered. The experimental data, combined with calculations using equilibrium/binding constants of the surface and ligands, indicates that a ligand exchange reaction may be the most significant mechanism.

Neutron reflection study of the adsorption of the phosphate surfactant NaDEHP onto alumina from water.

The adsorption of a phosphorus analogue of the surfactant AOT, sodium bis(2-ethylhexyl) phosphate (NaDEHP), at the water/alumina interface is described. The material is found to adsorb as an essentially water-free bilayer from neutron reflection measurements. This is similar to the behavior of AOT under comparable conditions, although AOT forms a thicker, more hydrated layer. The NaDEHP shows rather little variation with added salt, but a small thickening of the layer on increasing the pH, in contrast to the behavior of AOT.

Adsorption and self-assembly in methyl ester sulfonate surfactants, their eutectic mixtures and the role of electrolyte

The α-methyl ester sulfonate, MES, anionic surfactants are a potentially important class of sustainable surfactants for a wide range of applications. The eutectic-like Kraft point minimum in the C16 and C18-MES mixtures is an important feature of that potential. Understanding their individual adsorption properties and the surface mixing of the eutectic mixtures are key to their wider exploitation. Neutron reflectivity has been used to investigate the adsorption at the air-water interface of the C16 and C18-MES surfactants and the eutectic mixture of C16 and C18-MES, in aqueous solution and in electrolyte. The micelle mixing of the eutectic mixture is investigated using small angle neutron scattering. The adsorption isotherms for C14 to C18-MES are found to scale with their critical micelle concentration value. The surface and micelle compositions of the C16 and C18-MES eutectic mixture differ from the eutectic composition; with compositions in the limit of high concentrations richer in C16-MES. The mixing properties are described by the pseudo phase approximation with a repulsive interaction between the two surfactants. The impact of the multivalent ions Al3+ on the adsorption at the air-water interface results in a transition from monolayer to multilayer adsorption.

Anionic Surfactants on Anionic Substrate: Monovalent Cation Binding

Neutron reflectometry has been used to study the adsorption of the anionic surfactant bis(2-ethylhexyl) sulfosuccinate cesium salt on the anionic surface of mica. Evidence of significant adsorption is reported. The adsorption is reversible and changes little with pH. This unexpected adsorption behavior of an anionic molecule on an anionic surface is discussed in terms of recent models for surfactant adsorption such as cation bridging, where adsorption has been reported with the divalent ion calcium but not previously observed with monovalent ions.