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To decrease wear and friction, zinc dialkyldithiophosphate (ZDDP) has been used in engine oil for several decades, but the mechanism of the tribofilm formation is still unclear. The purpose of this study is to characterize the chemical details of the tribofilm by using high-resolution approaching.

An ISO VG 100 mineral oil mixed with ZDDP was used in sliding tests on cylindrical roller bearings. Tribofilm formation was observed after 2 h of the sliding test. X-ray photoelectron spectroscopy (XPS) and atom probe tomography (APT) were used for chemical analysis of the tribofilm.

The results show that the ZDDP tribofilm consists of the common ZDDP elements along with iron oxides. A considerable amount of zinc and a small amount of sulfur were observed. In particular, an oxide interlayer with sulfur enrichment was revealed by APT between the tribofilm and the steel substrate. The depth profile of the chemical composition was obtained, and a tribofilm of approximately 40 nm thickness was identified by XPS.

A sulfur enrichment at the interface is observed by APT, which is beneath an oxygen enrichment. The clear evidence of the S interlayer confirms the hard and soft acids and bases principle.

The peer review history for this article is available at: https://publons.com/publon/10.1108/ILT-01-2020-0035/

The purpose of this paper is to provide a general picture for describing the formed tribofilm, including chemical and physical aspects in the micro-scale and the nano-scale. In a previous study, the durability of zinc dialkyl dithiophosphate (ZDDP) tribofilms on cylinder liner samples has been investigated in a tribometer model system by using fresh and aged fully formulated oils and replacing them with PAO8 without additives. Analyses of the derived tribofilms by means of X-ray photoelectron spectroscopy and scanning electron microscopy could give some hints about the underlying mechanisms of the tribofilm build-up and wear performance, but a final model has not been achieved.

Thus, characterisation of these tribofilms by means of focused ion beam-transmission electron microscopy (FIB-TEM) and energy dispersive X-ray spectroscopy is presented and a concluding model of the underlying mechanisms of tribofilm build-up is discussed in this paper.

For tribotests running first with fresh fully formulated engine oil, a rather homogeneous ZDDP-like tribofilm is found underneath a carbon rich tribofilm after changing to non-additivated PAO8. However, when the tests run first with aged fully formulated engine oil, no ZDDP-like tribofilm has been found after changing to non-additivated PAO8, but a wear protective carbon rich tribofilm.

The obtained results provide insights into the structure and durability of tribofilms. Carbon-based tribofilms are built up on the basis of non-additivated PAO8 because of the previously present ZDDP tribofilms, which suggests an alternative way to reducing the consumption of antiwear additives.

Dry eye syndrome is one of the most common reasons for eye-related discomfort which, without treatment, in some cases may even lead to corneal damage. Blinking, baseline and reflex lachrymation and drainage compromise the topical application of therapeutics demanding repeated, often hourly applications of common lubricants. In contrast, topically administered chitosan-N-acetylcysteine-based eye drops were reported to sustain on the ocular surface for more than 24 h. The thiolated biopolymer can interact with the corneal mucin layer thereby forming covalent disulphide bridges, which may contribute to extended residence times.

In this study, the tribological characteristics of four different lubricants including hyaluronic acid and chitosan-N-acetylcysteine containing commercially available eye drops were investigated. For this purpose, a representative test setup was developed, which mimics the contact between the cornea and the eyelid wiper. Gels with different elastic properties coated with a mucin layer were used as a substrate to mimic the corneal surface. Tests were conducted with a micro-tribometer, and friction values were recorded. Contact zones were characterized by X-ray photoelectron spectroscopy to investigate wear and thiol bonding on the surface.

Results revealed the lowest average coefficient of friction values for chitosan-N-acetylcysteine-based eye drops and substrate dependence of the test setup.

In this study, the authors introduced an in vitro system to test different types of eye drops so that chemical interaction with the mucin layer can be observed. These interactions change the tribological performance significantly and must be considered to have results relevant to the actual application.