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Adverse interaction and subsequent adsorption of biomolecular species (i.e. fouling) pose a great hindrance for medical and clinical applications (e.g. biosensors). Research into the mechanism behind antifouling coatings have shown a strong link between surface hydration and antifouling behaviour due to the existence of a ‘water barrier’ which prevents proteins from adsorbing onto the surface. In a previous study, a short, mono(ethylene-glycol) silane adlayer (MEG-OH) showed significantly different antifouling behaviour in comparison to its homolog – lacking the internal ether oxygen (OTS-OH). In the present work, neutron reflectometry (and modeling) was used to investigate the water density profiles at MEG-OH and OTS-OH silane adlayers on quartz and Si/SiO2 to determine whether the internal ether oxygen affects the adlayers’ interaction with water. Despite the limitations of studying such ultrathin organic films, the two systems showed different hydration profiles supporting the link between surface hydration and antifouling.

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No description available.

No description available.

Protein adsorption at the solid/liquid interface is of wide ranging importance in many different areas of science such as biomaterial design, the fate of nanoparticles and in the food industry. As a result, many studies have been undertaken with varying foci but there still remains a lack of agreement between many working in this field and fundamental questions regarding the adsorption of proteins at the solid/liquid interface. Neutron reflectivity is a powerful technique for probing the properties of adsorbed layers at interfaces due to its high structural resolution and the possibility of using isotopic substitution to distinguish between components of a mixture. In this work, neutron reflectivity has been used as the primary technique for the investigation of proteins adsorbed sequentially or from a binary mixture. Initially, the adsorption of four proteins (carbonic anhydrase II, lysozyme, human serum albumin and maltose binding protein) onto a clean silica surface was investigated which revealed the importance of electrostatic interactions and entropic contributions to the driving forces for adsorption. Most of the adsorbed layers were described by a 2-layer model with a thinner, denser layer adjacent to the surface and a thick, diffuse layer extending into the bulk solution. The presence of impurities is also shown to have a significant impact on the adsorption of HSA. A study of the HSA/myristic acid system shows that the presence of small amphiphiles can inhibit HSA adsorption and also remove a pre-adsorbed layer. A comparison was made between the protonated and deuterated forms of two proteins, HSA & MBP, showing the deuterated proteins to have a higher affinity for the surface with adsorption occurring in a 3:1 ratio when from a 1:1 mixture. Likewise, d-MBP displaced h-MBP more readily than vice versa in an investigation into the effect of incubation time on the properties of the protein layer. The extent of desorption into protein free buffer is not affected by incubation time but the extent to which d-MBP was displaced by h-MBP showed a clear trend of decreased exchange with increasing incubation time indicating an active exchange process was occurring. This was also observed to a lesser extent for the sequential adsorption of binary protein systems, HSA & LYS and HSA & MBP. When investigating binary protein mixtures the higher propensity for deuterated proteins to adsorb is observed. LYS dominates when adsorbed from a mixture with h-HSA but from a d-HSA & LYS mix both proteins were adsorbed. The marked difference between the adsorption characteristics of perdeuterated proteins and their protonated counterparts provides a good case study for testing the neutron reflectivity technique when investigating systems with more than one component. This thesis assesses the limitations of the methodology of contrast variation for investigating mixtures as well as using different solvent contrasts. A comparison of neutron reflectivity and dual polarisation interferometry (DPI) shows that the two techniques are similar and any small differences can be attributed to the small change in surface chemistry. This comparison also highlights the advantages of DPI; high throughput of samples and detailed information but the restriction to using a 1-layer model limits its use.

The preparation of layered magnets needs the knowledge of growth techniques which are focused on the growth of Fe/V(001) superlattices. Such films have been structurally investigated by X-rays reflectivity and diffraction. The magnetic investigations have been carried out by magneto-optic Kerr effect (MOKE), Superconducting Quantum Interference Device (SQUID) magnetometry and polarized neutron reflectivity (PNR). This latter technique has been used in cooperation with the Institute Laue Langvin (Grenoble, France) and Ruhr Universität (Bochum, Germany). The cross-over in universality class is shown in a series of layered magnets where a δ-doping layer of Fe has been embedded between two layers of Pd showing that the magnetization depends on the effective magnetic thickness of the polarized Pd. A model for the cross-over has been developed in terms of magnetic excitations. The interlayer exchange coupling (IEC) mediated by a non-magnetic spacer has been reviewed focusing the attention on the recent theoretical and experimental works based on Fe/V(001) superlattices. The IEC can be tailored at will by reversibly alloying of the spacer with H: this has been proved in Fe/V(001) double layers showing that in the two dimensional limit, the universality class is not affected by the coupling. The magnetic order-disorder transitions in Fe/V(001) superlattices do not seem to belong to any universality class. A phenomenological model which accounts for the effective coupling at the boundaries has been developed. The influence of the inherent ordering temperatures of single magnetic layers has been investigated in Fe/V(001) superlattices proving that the weakest ferromagnetic layer affects the overall magnetic ordering. A new kind of layered magnet has been developed to increase the effect of the boundaries. PNR measurements show that the universality class depends on which length-scale is investigated.

Fosfoniumjonvätskor har tidigare studerats som potentiella nya avancerade smörjmedel på grund av sina unika fysikaliska egenskaper och fördelar jämfört med både traditionella smörjmedel och andra typer av jonvätskor. Dessa studier har uppvisat lovande resultat med avseende på reducering av nötning och friktion såväl som kontroll av dessa parametrar med en pålagd elektrisk potential. En multitud av frågor återstår dock att besvara om strukturering av jonarter i den skyddande gränssnittfilmen som bildas och kopplingen mellan strukturella drag i de involverade jonarterna och den skyddande funktionen av gränsnittsfilmen. I denna avhandling studeras ett flertal mono och dikatjon fosfoniumjonvätskor med icke halogena bis(oxalato)borat anjoner såväl som en binär blandning av dessa av intresse som nya avancerade smörjmedel och som additiv med neutronreflektometri vid ett elektrifierat elektrodgränssnitt med syfte att studera strukturella egenskaper av den gränsnittsfilmen som bildas samt elektroresponsiviteten av denna film. Resultaten av detta uppvisar egenskaper om både struktureringen av jonarterna och deras elektroresponsivitet av intresse för den fortsatta utvecklingen av avancerade smörjmedelslösningar med fosfoniumjonvätskor. / Phosphonium ionic liquids(ILs) has previously been investigated as advanced novel lubricants because of their physical unique properties and advantages compared to traditional lubricants and other ILs. These studies have showed promising results in wear and friction reduction as well as the tribotronic control of those properties. A multitude of questions however remain about the interfacial structuring of these protective films and the connection between structural features in the ionic species to the protective function of the interfacial film.In this thesis multiple non-halogenated mono- and di-cationic phosphonium ionic liquids with bis(oxalato)borate anion as well as a binary mixture of interest for advanced neat lubricants or additives has been studied by neutron reflectometry at an electrified electrode interface to investigate interfacial properties and electroresponsiveness of the species. The results elucidate properties of the structuring of key to the further development of phosphonium ILs for use in advanced lubrication formulations.

La friction d'une surface en réaction au cisaillement pourrait devenir un élément important dans des diverses technologies telles que la microfluidique, la lubrification ou encore la production et le traitement des polymères. Notre système modèle est constitué d'une brosse polymère sous un écoulement d'une solution de polymère enchevêtrée. La structure de la brosse a été sondée expérimentalement par Rhéo - Réflectométrie Neutronique, ainsi que par la simulation numérique basée sur des globules très "mous" ("blobs" en anglais). Dans les simulations on montre pour la première fois qu'il est bien possible de supprimer le croisement de chaînes de polymères pour ensuite pouvoir observer la dynamique d'enchevêtrement grâce uniquement au potentiel répulsif des globules. Pour confiner ces globules entre deux plaques dures, on propose une nouvelle condition limite, appelée mirror-and-shift, qui produit un comportement de profil de densité monotone et non oscillatoire à l'interface. Ces innovations de simulation sont ensuite combinées et leur résultat est comparé avec nos mesures expérimentales de l'épaisseur de la brosse polymère, en fonction de taux de cisaillement. Un bon accord quantitatif est obtenu, dont la conclusion est que l'épaisseur de la brosse s'effondre perpendiculairement au cisaillement appliqué, ce qui est un effet non-linéaire de second ordre. On attribue cet effet à la différence des contraintes normales, qui se produit communément dans des liquides de polymères enchevêtrés lorsqu'il sont poussés vers leur régime de rhéofluidification par un flot suffisant. / Shear responsive friction at solid-liquid interfaces could become an important component in various technologies such as microfluidics, lubrication and polymer processing. Our model system is a polymer brush grafted on a solid substrate, subject to shear flow by an entangled polymer solution. The structure of the brush was probed both experimentally by Rheo - Neutron Reflectometry, and by computer simulations based on soft blobs. In the simulations we demonstrate for the first time that it is possible to suppress polymer chain crossings and observe entanglement dynamics using only the soft blob repulsive potential. To confine the blobs between two hard plates we introduce a new boundary condition, mirror-and-shift, which enables a monotonic, rather than oscillatory, density profile climb at the interface. The simulation techniques are then combined and compared against experimental measurement of polymer brush thickness as a function of shear rate. A good quantitative agreement is obtained, concluding that the brush thickness collapses perpendicularly to the applied shear flow, and is thus a non-linear second order effect. We attribute this effect to the normal stress difference, commonly occurring in entangled polymer liquids in their shear thinning flow regime.

Colloidal particles suspended in a liquid or gas phase often interact with a solid-liquid or solid-gas interface. In this study, experimental data through atomic force microscopy and neutron reflectometry and theoretical results of colloidal particle-surface interactions were obtained and compared. Atmospheric and aquatic environments were considered for the interactions of microbial colloidal particles and nano-sized silica particles with planar surfaces. Spores of Bacillus thuringiensis, members of the Bacillus cereus group, were examined as the microbial particles, simulating the pathogens Bacillus cereus and Bacillus anthracis which are potentially dangerous to human health. Model planar surfaces used in this study include gold which is an electrically conductive surface, mica which is a highly charged, nonconductive surface, and silica. In atmospheric systems, the interaction forces were found to be strongly affected by the relative humidity, and the total adhesion force of a particle onto a surface was modeled as the addition of the capillary, van der Waals, and electrostatic forces. Each component is influenced by the properties of the particle and surface materials, including hydrophobicity and surface roughness, as well as the humidity of the surrounding atmosphere. In aquatic systems, the interaction forces are mainly affected by the solution chemistry, including pH and ionic strength. The main components of the interaction force between a microbial colloidal particle and a planar surface were found to be the van der Waals and electrostatic forces. The results obtained in this research provide insights into the fundamental mechanisms of colloidal particle interactions with environmental surfaces in both atmospheric and aquatic systems, contributing to the understanding of the phenomena driving such interfacial processes as deposition, aggregation, and sedimentation. Thus, the results can help us describe the behavior of contaminant colloidal particles in environmental systems and subsequently devise better means for their removal from environmental surfaces.