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.
E/Z photo-isomerization of a new surfactant causes substantial changes in interfacial properties, which are a prerequisite for responsive and adaptive material control on a molecular level.
We study dynamically highly asymmetric binary mixtures comprised of small methyl tetrahydrofuran (MTHF) molecules and polystyrene. Combined use of dielectric spectroscopy, 2H nuclear magnetic resonance, incoherent quasielastic neutron scattering, and depolarized dynamic light scattering allows us to selectively probe the dynamics of the components in a broad dynamic range. It turns out that the mixtures exhibit two glass transitions in a wide concentration range although being fully miscible on a macroscopic scale. In between both glass transition temperatures, the dynamics of the small molecules show strong confinement effects, e.g., a crossover from Vogel-Fulcher to Arrhenius behavior of the time constants. Moreover, the dynamical behavior of small molecules close to the slow matrix is consistent with mode coupling theory predictions for a type-A glass transition, which was expected from recent theoretical and simulation studies in comparable systems.
Neutron reflectometry was used to study the assembly of magnetite nanoparticles in a water-based ferrofluid close to a silicon surface. Under three conditions, static, under shear and with a magnetic field, the depth profile is extracted. The particles have an average diameter of 11 nm and a volume density of 5% in a D2O-H2O mixture. They are surrounded by a 4 nm thick bilayer of carboxylic acid for steric repulsion. The reflectivity data were fitted to a model using a least square routine based on the Parratt formalism. From the scattering length density depth profiles the following behavior is concluded: the fits indicate that excess carboxylic acid covers the silicon surface and almost eliminates the water in the densely packed wetting layer that forms close to the silicon surface. Under constant shear the wetting layer persists but a depletion layer forms between the wetting layer and the moving ferrofluid. Once the flow is stopped, the wetting layer becomes more pronounced with dense packing and is accompanied by a looser packed second layer. In the case of an applied magnetic field the prolate particles experience a torque and align with their long axes along the silicon surface which leads to a higher particle density.
We investigate the molecular dynamics in the binary glass forming system methyltetrahydrofuran (M-THF) and tristyrene. Although the components are miscible in the full concentration and temperature range, two glass transitions can clearly be distinguished in differential scanning calorimetry. We selectively probe the reorientational dynamics of M-THF and tristyrene by means of dielectric spectroscopy and depolarized dynamic light scattering, respectively. While, apart from the observed plasticizer effect, the motion of the larger molecules remains almost unchanged, it is shown that the smaller M-THF molecules take part in both glass transitions. Moreover, below the upper T(g) of the mixture, the remaining mobile M-THF molecules clearly show confinement effects in their relaxation behavior. In order to elucidate the nature of the observed secondary relaxation processes, we first characterize the influence of the methyl group of M-THF on the dynamics in the mixtures by comparing the results obtained so far with the relaxation behavior observed in blends of THF and tristyrene. Finally, we employ (2)H NMR spectroscopy to clarify the nature of the secondary relaxations of THF-d(8) in the latter mixtures and conclude on the basis of the NMR and dielectric results that the high-frequency wing observed in neat M-THF appears as a genuine Johari-Goldstein β-relaxation in the mixtures, whereas the faster secondary process is due to internal degrees of freedom of the nonrigid THF ring.
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.
1 This article will form part of a virtual special issue on advanced neutron scattering instrumentation, marking the 50th anniversary of the journal.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.
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 Å is observed, containing essentially no water. Its partial removal by washing and ion exchange is also presented.
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