Layers of the polyelectrolytes poly(allylamine hydrochloride) (PAH, polycationic) and poly(styrene sulfonate) (PSS, polyanionic) are consecutively adsorbed on flat silicon oxide surfaces, forming stable, ultrathin multilayer films. Subsequently, a final monolayer of the polycationic copolymer poly(L‐lysine)‐graft‐poly(ethylene glycol) (PLL‐g‐PEG) is adsorbed onto the PSS‐terminated multilayer in order to impart protein resistance to the surface. The growth of each of the polyelectrolyte layers and the protein resistance of the resulting [PAH/PPS]n(PLL‐g‐PEG) multilayer (n = 1–4) are followed quantitatively ex situ using X‐ray photoelectron spectroscopy and in situ using real‐time optical‐waveguide lightmode spectroscopy. In a second approach, the same type of [PAH/PSS]n(PLL‐g‐PEG) multilayer coatings are successfully formed on the surface of colloidal particles in order to produce surface‐functionalized, hollow microcapsules after dissolution of the core materials (melamine formaldehyde (MF) and poly(lactic acid) (PLA; colloid diameters: 1.2–20 μm). Microelectrophoresis and confocal laser scanning microscopy are used to study multilayer formation on the colloids and protein resistance of the final capsule. The quality of the PLL‐g‐PEG layer on the microcapsules depends on both the type of core material and the dissolution protocols used. The greatest protein resistance is achieved using PLA cores and coating the polyelectrolyte microcapsules with PLL‐g‐PEG after dissolution of the cores. Protein adsorption from full serum on [PAH/PPS]n(PLL‐g‐PEG) multilayers (on both flat substrates and microcapsules) decreases by three orders of magnitude in comparison to the standard [PAH/PPS]n layer. Finally, biofunctional capsules of the type [PAH/PPS]n(PLL‐g‐PEG/PEG‐biotin) (top copolymer layer with a fraction of the PEG chains end‐functionalized with biotin) are produced which allow for specific recognition and immobilization of controlled amounts of streptavidin at the surface of the capsules. Biofunctional multilayer films and capsules are believed to have a potential for future applications as novel platforms for biotechnological applications such as biosensors and carriers for targeted drug delivery.

Antiwear additives, such as zinc dialkyldithiophosphate (ZnDTP), find application in many different industrial sectors. Although it is understood that certain ZnDTP concentrations need to be used to achieve an effective antiwear performance, there has been very little work published concerning the effect of temperature on the interactions of the additive and its adsorption mechanism on steel. In this article, 100Cr6 (52100) steel ball-on-disc experiments under solutions of zinc dialkyldithiophosphate (ZnDTP) in poly-a-olefin (PAO) were performed at different temperatures, ranging from 25 to 180°C. The discs were analysed after the experiments by means of small-area, imaging and angle-resolved X-ray photoelectron spectroscopy (XPS). The composition of the reaction film was found to change as a function of the applied temperature and also to vary within the film as a function of depth: Longer polyphosphate chains were found at higher temperatures as well as towards the outer part of the reaction film.

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Combinatorial testing has been performed on zinc dialkyldithiophosphate (ZnDTP)-containing lubricants, to investigate the effects of contact pressure on the formation of tribochemical films. Contact pressures ranging from 25 to 500 MPa were applied in ball-on-disc tribotests with oscillating load. Both the ball and the disc were investigated by means of small-area and imaging X-ray photoelectron spectroscopy (XPS). The thickness and the composition of the reaction layer were estimated from the XPS data. The thickness of the reaction layer in the tribologically stressed areas of the ball and of the disc increased with both temperature and contact pressure. The reaction layer mainly consisted of short-chain poly(thio)phosphates, shorter chains being observed at higher contact pressures. At high pressures, the presence of a thick, high-toughness short-chain poly(thio)phosphate layer can explain the lower friction and dimensional wear coefficients observed. On the ball, similar anti-wear film formation mechanisms were observed as on the disc, zinc sulphide being deposited in the post-contact region.