Antonella Rossi

The microfibrils of anchoring filaments, a typical ultrastructural feature of initial lymphatic vessels, consist mainly of fibrillin and are similar to the microfibrils of elastic fibers. As we previously demonstrated, they radiate from focal adhesions of lymphatic endothelium to the perivascular elastic network. Although present in large blood vessels, fibrillin microfibrils have never been detected in blood capillaries. Here we report immunohistochemical evidence that cultured bovine aortic and lymphatic endothelial cells express fibrillin microfibrils. These microfibrils form an irregular web in lymphatic endothelial cells, whereas in blood vessel endothelial cells they are arranged in a honeycomb pattern. Cultured lymphatic and blood vessel endothelial cells also produce focal adhesion molecules: focal adhesion kinase, vinculin, talin, and cytoskeletal beta-actin. Our data suggest that anchoring filaments of initial lymphatic vessels in vivo may be produced by endothelium. Through their connection with focal adhesions, they may form a mechanical anchorage for the thin wall of initial lymphatic vessels and a transduction device for mechanical signals from the extracellular matrix into biochemical signals in endothelial cells. The complex anchoring filaments-focal adhesions may control the permeability of lymphatic endothelium and finely adjust lymph formation to the physiological conditions of the extracellular matrix. The different deposition of fibrillin microfibrils in blood vessel endothelial cells may be related to the necessity of withstanding shear forces. Thus, in our opinion, differences in fibrillin deposition imply a different role of fibrillin in blood vessel and lymphatic endothelium.

A new type of combinatorial tribological experiment is presented, which explores a series of tribological conditions, such as load and relative velocity, spatially separated as a “library” on one single sample. As an example, a library displaying the results of tribological testing of an additive under a series of different loads has been prepared and analyzed. The tribological information acquired during the testing has been correlated with spectroscopic information from the tribologically stressed surface. The use of imaging and small-area X-ray photoelectron spectroscopy has allowed the identification of the different tribologically stressed areas and the acquisition of detailed spectroscopic information. The composition and the thickness of the tribofilm were found to be dependent on the applied load. The use of the combinatorial approach shows the potential to greatly facilitate rapid characterization of new lubricant additives.

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-α-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.

Phosphorothionates are anti-wear lubricant additives and potential replacements for zinc dialkyldithiophosphates. In this study, ball-on-disc tests have been carried out combinatorially under extreme pressure (EP) conditions (100–350 MPa at 10 N load). The tests were performed in oil containing triphenyl phosphorothionates substituted with alkyl chains of different lengths. Imaging, small-area and angle-resolved X-ray photoelectron spectroscopy were performed following the tribotest to probe the modification, removal and growth of the surface film. The films were composed, depending on the test conditions, of (i) iron phosphate, (ii) iron phosphates with sulphates or (iii) a mixture of iron phosphates with sulphides and sulphates. With increasing load, the dimensional wear coefficients decreased. Upon increasing temperature from 30 to 150°C, the wear became more severe. These findings suggest the formation of a tribochemical film with some EP performance, despite the severe tribological test conditions applied in this work. Copyright © 2008 John Wiley & Sons, Ltd.

The influence of load on the chemistry of tribofilms formed on a steel surface in solution of pure di-isopropyl zinc dithiophosphate (i-ZnDTP) in n-decane has been investigated by means of a combinatorial tribological experiment involving X-ray photoelectron spectroscopy. The experiment consisted of the preparation of a set of spatially separated areas, produced under various tribological test conditions, and the subsequent spectroscopic probing of the chemical composition of the tribofilm. The experiment was carried out at room temperature under boundary-lubrication conditions and revealed a physically adsorbed layer of the additive in the non-contact area and a thin (ca. 5 nm), inhomogeneous phosphate film covering the tribostressed areas. The total amount of phosphate present in the tribostressed area was found to increase with increasing load. In the contact areas, iron oxides and metal sulfides have also been detected.

Attenuated total reflection infrared (ATR FT-IR) and X-ray photoelectron spectroscopy (XPS) have been used for the in situ and ex situ characterization of thermal and tribological films formed on iron from a commercial zinc dialkyldithiophosphate (ZnDTP). From in situ ATR FT-IR analysis, information on the chemical changes occurring at the iron/lubricant additive interface was obtained during heating and sliding at high temperatures. Different mechanisms and chemical compositions have been found for the thermal and tribochemical reactions between the ZnDTP and the iron surface under the experimental conditions used in this work. Both the ATR FT-IR and the XPS results show the decomposition of ZnDTP with the formation of polyphosphates following thermal testing at 150 °C. However, after tribological testing at the same temperature an inorganic phosphate film has been detected on the iron surface instead.