Magnéli-type vanadium oxides form the homologous series VnO2n-1 and exhibit a temperature-induced, reversible metal–insulator first order phase transition (MIT). We studied the change of the adhesion force across the transition temperature between the cleavage planes of various vanadium oxide Magnéli phases (n = 3 ... 7) and spherical titanium atomic force microscope (AFM) tips by systematic force–distance measurements with a variable-temperature AFM under ultrahigh vacuum conditions (UHV). The results show, for all investigated samples, that crossing the transition temperatures leads to a distinct change of the adhesion force. Low adhesion corresponds consistently to the metallic state. Accordingly, the ability to modify the electronic structure of the vanadium Magnéli phases while maintaining composition, stoichiometry and crystallographic integrity, allows for relating frictional and electronic material properties at the nano scale. This behavior makes the vanadium Magnéli phases interesting candidates for technology, e.g., as intelligent devices or coatings where switching of adhesion or friction is desired.
Two new substoichiometric titania (TiOx) coatings designated for cylinder liner application were deposited on specimen of grey cast iron GG20HCN with high carbon content by plasma spraying. First, a TinO2n-1 coating was prepared by atmospheric plasma spraying (APS) using a sintered and agglomerated Magnéli-type spray powder. Second a TiO1.95-x coating was deposited with a vacuum plasma spray (VPS) process using a commercial, fused and crushed TiO1.95 powder. The tribological behaviour of these coatings under lubricated conditions was compared with uncoated specimen of this grey cast iron. As counter bodies a widespread used APS-sprayed Mo-NiCrBSi piston ring coating (MKP81A®), an advanced HVOF-sprayed WC/Cr3C2-based (MKJet502®) ring coating as well as non-commercial prototype APS-sprayed TinO2n-1 and APS-sprayed (Ti,Mo)(C,N) + 23NiMo (TM23-1) coatings were tribotested.
The interaction of the pairs with prototype engine oils based on esters and polyglycols were studied under mixed/boundary lubrication using the BAM test method. Lubricants were factory fill engine oils, ester-containing lubricants with low-SAP (sulphurashphosphor) and/or bio-no-tox properties as well as polyglycole-based lubricants. The ester and polyglycole-based engine oils respond both to bio-no-tox criteria and are polymer-free. They follow different strategies to reduce zinc, phosphorus and sulphur to assure a low ash content.
Both TiOx coatings designated for cylinder liners meet or exceed the wear resistance of the grey cast iron with high carbon content when paired with APS-sprayed TinO2n-1 or Mo-NiCrBSi piston ring coatings. Overall, in nearly all pairs the wear rates of the APS TinO2n-1 coating were lower than those of the VPS TiO1.95-x coating.
In order to characterize the tribological behaviour under oil-off, dry-running conditions, additional tests were performed under unlubricated unidirectional sliding conditions at 22 and 400 °C for a sliding speed of 1 m/s against sintered polycrystalline Al2O3 as stationary specimen.
A correlation of adhesion force and electrical conductivity is established for a vanadium oxide and highly oriented pyrolytic graphite (HOPG). Adhesion forces were determined by analysis of pull-off forces obtained from force–distance curves with atomic force microscopy in ultrahigh vacuum, on clean surfaces and with defined contact conditions. The investigated samples include (i) different stoichiometries of Magnéli-type vanadium oxides (V3O5, V4O7, V6O11, and V7O13), which undergo metal-insulator-transitions as a function of temperature, (ii) the (0001) basal plane and the (10–10) prism plane of highly oriented pyrolytic graphite (HOPG), which differ in their respective perpendicular-plane electrical conductivities by several orders of magnitude, and (iii) the (100) surfaces of pure metal single crystals, i.e., silver (Ag), copper (Cu), iron (Fe) and gold (Au). It is shown, that the vanadium oxides as well as the graphite exhibit significantly lower adhesion forces in their electrical conductive state than in their non-electrical conductive state. The values obtained for the electrical conductive states are quantitatively confirmed by the measurements on the single crystal metals.