Interplay of mechanics and chemistry governs wear of diamond-like carbon coatings interacting with ZDDP-additivated lubricants

Valentin R Salinas Ruiz,Mohamed Ben Hassine,Jean Michel Martin,Gianpietro Moras,Leonhard Mayrhofer,Jules Galipaud,Melissa Stoll,Karine Masenelli-Varlot,Christophe Héau,Michael Moseler,Takuya Kuwahara,Maria-Isabel De Barros Bouchet

doi:10.1038/s41467-021-24766-6

Abstract

Friction and wear reduction by diamond-like carbon (DLC) in automotive applications can be affected by zinc-dialkyldithiophosphate (ZDDP), which is widely used in engine oils. Our experiments show that DLC’s tribological behaviour in ZDDP-additivated oils can be optimised by tailoring its stiffness, surface nano-topography and hydrogen content. An optimal combination of ultralow friction and negligible wear is achieved using hydrogen-free tetrahedral amorphous carbon (ta-C) with moderate hardness. Softer coatings exhibit similarly low wear and thin ZDDP-derived patchy tribofilms but higher friction. Conversely, harder ta-Cs undergo severe wear and sub-surface sulphur contamination. Contact-mechanics and quantum-chemical simulations reveal that shear combined with the high local contact pressure caused by the contact stiffness and average surface slope of hard ta-Cs favour ZDDP fragmentation and sulphur release. In absence of hydrogen, this is followed by local surface cold welding and sub-surface mechanical mixing of sulphur resulting in a decrease of yield stress and wear.

Highlights

Friction and wear reduction by diamond-like carbon (DLC) in automotive applications can be affected by zinc-dialkyldithiophosphate (ZDDP), which is widely used in engine oils
Diamond-like carbon is an excellent solid lubricant that exhibits high wear resistance and superlubricity under boundary[1,2] and mixed lubrication[3] with organic friction modifiers (FM), including oleic acid and glycerol. It has been increasingly applied as a protective coating in internal combustion engines, where operating conditions are extremely severe and the use of antiwear (AW) additives, e.g. zinc dialkyldithiophosphate (ZDDP) and FM additives, e.g. molybdenum dithiocarbamate (MoDTC), admixed with base oils is essential for reducing wear and friction
Particular attention is paid to whether ZDDP is effective with DLC, which has been already investigated for various types of DLC coatings[5,6,9,17,18], including hydrogen-free tetrahedral amorphous carbon and hydrogenated amorphous carbon (a-C:H)

Summary

Introduction

Friction and wear reduction by diamond-like carbon (DLC) in automotive applications can be affected by zinc-dialkyldithiophosphate (ZDDP), which is widely used in engine oils. Diamond-like carbon is an excellent solid lubricant that exhibits high wear resistance and superlubricity (i.e. friction coefficient μ below 0.01) under boundary[1,2] and mixed lubrication[3] with organic friction modifiers (FM), including oleic acid and glycerol It has been increasingly applied as a protective coating in internal combustion engines, where operating conditions are extremely severe and the use of antiwear (AW) additives, e.g. zinc dialkyldithiophosphate (ZDDP) and FM additives, e.g. molybdenum dithiocarbamate (MoDTC), admixed with base oils is essential for reducing wear and friction. Vengudusamy et al carried out comprehensive experimental studies on the effect of different types of DLC coatings, such as a-C:H, a-C, ta-C and doped DLCs5–7 They reported that ta-C lowers boundary friction, but exhibits higher wear compared with a-C:H and a-C. The former three factors alter chemical reactivity of DLC surfaces and reaction rates of ZDDP, whereas the latter two factors affect the mechanical response of the system such as contact pressure and geometry, and elastic/plastic deformation of surface asperities

Methods

Results

Conclusion