Philipp Gutfreund

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.

Shear induced relaxation of polymer micelles at the solid-liquid interface.

A 20% aqueous solution of (ethylene oxide) 99-(propylene oxide) 65-(ethylene oxide) 99, F127, was investigated by combining rheology in a cone/plate-geometry and surface-sensitive grazing incident neutron scattering. The crystalline structure formed by the polymer micelles becomes less pronounced for low shear rates, but correlations increase for higher shear rates. After stopping shear a slow relaxation of the micelles is found in the vicinity (50 mum thick layer) of a hydrophilic silicon wall (strong micelle-wall interaction), while a fast relaxation is observed in the boundary layer against the hydrophobic silicon wall (weak micelle-wall interaction). The results show that in the vicinity of the interface wall-particle interactions compete heavily with the shear force acting on the liquid.

An improved algorithm for reducing reflectometry data involving divergent beams or non-flat samples

Reflectometry is a powerful technique for determining many physical quantities of stratified media, including length scales, densities and magnetism. However, experimentally neutron reflectometry in particular suffers from the relatively feeble brilliance of the sources compared with those of X-rays, for example. In this paper, a simple modification of existing data-reduction methods is demonstrated, allowing quantitative improvements in the quality of the data. Using the same algorithm, reflections from non-flat surfaces can be treated, leading to a full recovery of the resolution. The method involves re-binning of the data in the linear coordinates of the raw data, which leads to substantial gains in statistical quality, equivalent to a significant flux increase, and also improved resolution.

Solid surface structure affects liquid order at the polystyrene-self-assembled-monolayer interface.

We present a combined x-ray and neutron reflectivity study characterizing the interface between polystyrene (PS) and silanized surfaces. Motivated by the large difference in slip velocity of PS on top of dodecyl-trichlorosilane (DTS) and octadecyl-trichlorosilane (OTS) found in previous studies, these two systems were chosen for the present investigation. The results reveal the molecular conformation of PS on silanized silicon. Differences in the molecular tilt of OTS and DTS are replicated by the adjacent phenyl rings of the PS. We discuss our findings in terms of a potential link between the microscopic interfacial structure and dynamic properties of polymeric liquids at interfaces.

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.

Specular neutron reflection at the mica/water interface – irreversible adsorption of a cationic dichain surfactant

Neutron reflection from the important mineral mica at the solid/liquid interface is presented here using a new approach – a very thin mica crystal supported on a silicon substrate. This approach avoids the problems of crystal defects and surface undulations that have hindered previous work. The use of mica as a reflectivity substrate is important as it is a model surface, which is atomically smooth with a high structural charge. In this work the mica/water interface is fully characterized. In particular, a characteristic double critical edge is observed, arising from the higher scattering length densities of the mica and D2O subphase relative to the silicon support. The experimental data are modelled using a combined approach: conventional amplitude summation (matrix method) for the thin layers and reflected intensity summation with attenuation terms for the thick layers of mica and hydrocarbon adhesive. Reflection data from the adsorption of the dichain cationic surfactant didodecyldimethylammonium bromide (DDAB) to the surface of muscovite mica from aqueous solution are also presented. It is found that, at twice the critical micelle concentration, a bilayer of DDAB with a thickness of 24 A is observed, containing essentially no water. Its partial removal by washing and ion exchange is also presented.

Recent upgrades of the neutron reflectometer D17 at ILL

The vertical sample-plane reflectometer D17 at the Institut Laue–Langevin in Grenoble, France, has undergone several major upgrades since its commissioning, which are summarized in this article. The three major improvements are (i) a new focusing guide, increasing the usable flux on the sample by a factor of 2.5; (ii) a new beam polarizer and new spin flippers, allowing for the use of polarized neutrons in time-of-flight mode; and (iii) a new detector with a particularly uniform response under homogeneous exposure, improved stability and state-of-the-art detector electronics. The combination of these factors has paved the road to new possibilities in fast kinetic measurements, magnetism and off-specular scattering. Examples and scientific references for the new capabilities are presented.

Towards generalized data reduction on a chopper-based time-of-flight neutron reflectometer

The calculation of neutron reflectivity from raw time-of-flight data including instrumental corrections and an improved resolution calculation is presented. The theoretical calculations are compared with experimental data measured on the vertical sample plane reflectometer D17 and the horizontal sample plane reflectometer FIGARO at the Institut Laue–Langevin (ILL), Grenoble, France. This article comprises the mathematical body of the time-of-flight reflectivity data-reduction software COSMOS which is used on D17 and FIGARO.

The Search for Nanobubbles by Using Specular and Off-Specular Neutron Reflectometry

We apply specular and off-specular neutron reflection at the hydrophobic silicon/water interface to check for evidence of nanoscopic air bubbles whose presence is claimed after an ad hoc procedure of solvent exchange. Nanobubbles and/or a depletion layer at the hydrophobic/water interface have long been discussed and generated a plethora of controversial scientific results. By combining neutron reflectometry (NR), off-specular reflectometry (OSS), and grazing incidence small angle neutron scattering (GISANS), we studied the interface between hydrophobized silicon and heavy water before and after saturation with nitrogen gas. Our specular reflectometry results can be interpreted by assuming a submolecular sized depletion layer and the off-specular measurements show no change with nitrogen super saturated water. This picture is consistent with the assumption that, following the solvent exchange, no additional nanobubbles are introduced at significant concentrations (if present at all). Furthermore, we discuss the results in terms of the maximum surface coverage of nanobubbles that could be present on the hydrophobic surface compatibly with the sensitivity limit of these techniques.

Nanoscale discontinuities at the boundary of flowing liquids: a look into structure

When downsizing technology, confinement and interface effects become enormously important. Shear imposes additional anisotropy on a liquid. This may induce inhomogeneities, which may have their origin close to the solid interface. For advancing the understanding of flow, information on structures on all length scales and in particular close to the solid interface is indispensable. Neutron scattering offers an excellent tool to contribute in this context. In this work, surface sensitive scattering techniques were used to resolve the structure of liquids under flow in the vicinity of a solid interface. Our results are summarized as follows. First, for a Newtonian liquid we report a depletion distance on the order of nanometers which is far too small to explain the amount of surface slip, on the order of micrometers, found by complementary techniques. Second, for a grafted polymer brush we find no entanglement-disentanglement transition under shear but the grafted film gets ripped off the surface. Third, by evaluating the local structure factor of a micellar solution close to the solid interface it turns out that the degree of order and local relaxation depends critically on the surface energy of the solid surface.