Electrodeposited MoxSyOz/Ni Tribological Coatings.

Deposition of molybdenum disulfide (MoS2) coatings using physical vapor deposition (PVD) and mechanical burnishing has been widely assessed for solid lubricants in space applications but still suffers from line-of-sight constraints on complex geometries. Here, we highlight one of the first demonstrations of electrodeposited MoxSyOz and MoxSyOz/Ni thin-film coatings from aqueous solutions of ammonium tetrathiomolybdate for solid lubricant applications and their remarkable ability to provide low coefficients of friction and high wear resistance. Characterization of the coating morphology shows amorphous microstructures with a high oxygen content and cracking upon drying. Even so, electrodeposited MoxSyOz can achieve low steady-state coefficients of friction (µ ∼ 0.05-0.06) and wear rates (2.6 × 10-7 mm3/(N m)) approaching those of physical vapor deposited coatings (2.3 × 10-7 mm3/(N m)). Additionally, we show that adding dopants such as nickel increased the wear rate (7.5 × 10-7 mm3/(N m)) and initial coefficient of friction (µi = 0.23) due to compositional modifications such as dramatic sub-stoichiometry (S/Mo ∼ 1) and expression of a NiOx surface layer, although doping did reduce the degree of cracking upon drying.

Spectroscopic Evaluation of Surface Chemical Processes Occurring in MoS2 upon Aging.

Molybdenum disulfide (MoS2) coatings have attracted widespread industrial interest owing to their excellent lubricating properties under vacuum and inert conditions. Unfortunately, the increase in MoS2 interfacial shear strength following prolonged exposure to ambient conditions (a process referred to as "aging") has resulted in reliability issues when MoS2 is employed as solid lubricant. While aging of MoS2 is generally attributed to physical and chemical changes caused by adsorbed water and/or oxygen, a mechanistic understanding of the relative role of these two gaseous species in the evolution of the surface chemistry of MoS2 is still elusive. Additionally, remarkably little is known about the effect of thermally- and tribologically-induced microstructural variations in MoS2 on the aging processes occurring in the near-surface region of the coating. Here, we employed three analytical techniques, namely, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and grazing-incidence X-ray diffraction (GIXRD), to gain insights into the aging phenomena occurring in sputtered MoS2 coatings before and after tribological testing, while also evaluating the impact of thermally-induced variations in the coating structure on aging. The outcomes of XPS analyses provide evidence that a substantial surface oxidation of MoS2 only takes place under humid conditions. Furthermore, the correlation of XPS, ToF-SIMS, and GIXRD results allowed for the development of a qualitative model for the impact of shear-induced microstructural variations in MoS2 on the transport of water in the near-surface region of this material and on the extent of surface oxidation. These results add significantly to our understanding of the aging mechanisms of MoS2 coatings used in tribological applications and their dependence on environmental conditions.

Role of Environment on the Shear-Induced Structural Evolution of MoS2 and Impact on Oxidation and Tribological Properties for Space Applications.

This work investigates the role of water and oxygen on the shear-induced structural modifications of molybdenum disulfide (MoS2) coatings for space applications and the impact on friction due to oxidation from aging. We observed from transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) that sliding in both an inert environment (i.e., dry N2) or humid lab air forms basally oriented (002) running films of varying thickness and structure. Tribological testing of the basally oriented surfaces created in dry N2 and air showed lower initial friction than a coating with an amorphous or nanocrystalline microstructure. Aging of coatings with basally oriented surfaces was performed by heating samples at 250 °C for 24 h. Post aging tribological testing of the as-deposited coating showed increased initial friction and a longer transition from higher friction to lower friction (i.e., run-in) due to oxidation of the surface. Tribological testing of raster patches formed in dry N2 and air both showed an improved resistance to oxidation and reduced initial friction after aging. The results from this study have implications for the use of MoS2-coated mechanisms in aerospace and space applications and highlight the importance of preflight testing. Preflight cycling of components in inert or air environments provides an oriented surface microstructure with fewer interaction sites for oxidation and a lower shear strength, reducing the initial friction coefficient and oxidation due to aging or exposure to reactive species (i.e., atomic oxygen).

Achieving Ultralow Wear with Stable Nanocrystalline Metals.

Recent work suggests that thermally stable nanocrystallinity in metals is achievable in several binary alloys by modifying grain boundary energies via solute segregation. The remarkable thermal stability of these alloys has been demonstrated in recent reports, with many alloys exhibiting negligible grain growth during prolonged exposure to near-melting temperatures. Pt-Au, a proposed stable alloy consisting of two noble metals, is shown to exhibit extraordinary resistance to wear. Ultralow wear rates, less than a monolayer of material removed per sliding pass, are measured for Pt-Au thin films at a maximum Hertz contact stress of up to 1.1 GPa. This is the first instance of an all-metallic material exhibiting a specific wear rate on the order of 10-9 mm3 N-1 m-1 , comparable to diamond-like carbon (DLC) and sapphire. Remarkably, the wear rate of sapphire and silicon nitride probes used in wear experiments are either higher or comparable to that of the Pt-Au alloy, despite the substantially higher hardness of the ceramic probe materials. High-resolution microscopy shows negligible surface microstructural evolution in the wear tracks after 100k sliding passes. Mitigation of fatigue-driven delamination enables a transition to wear by atomic attrition, a regime previously limited to highly wear-resistant materials such as DLC.

Thermally-activated pentanol delivery from precursor poly(p-phenylenevinylene)s for MEMS lubrication.

The synthesis of two new polyphenylene vinylene (PPV) precursor polymers which can be thermally induced to eliminate pentanol is presented. Pentanol has recently been discovered to be a very useful lubricant in MicroElectroMechanical Systems. The utilization of the elimination reaction of precursor polymers to PPV as a small molecule delivery platform has, to the best of our knowledge, not been previously reported. The elimination reactions were examined using thermal gravimetric analysis, gas chromatography, and UV-Vis spectroscopy. Using PPV precursors allows for (1) a high loading of lubricant (one molecule per monomeric unit), (2) a platform that requires relatively high temperatures (>145 °C) to eliminate the lubricant, and (3) a non-volatile, mechanically and chemically stable by-product of the elimination reaction (PPV).

Tribochemical polymerization of adsorbed n-pentanol on SiO2 during rubbing: when does it occur and is it responsible for effective vapor phase lubrication?

The origin and role of tribochemical reaction products formed while sliding silicon oxide surfaces in the presence of adsorbed alcohol molecules in equilibrium with the vapor phase were studied. Wear and friction coefficient studies with varying contact loads and n-pentanol vapor environments were used to determine under what operating conditions the tribochemical reaction species was produced. Imaging time-of-flight secondary ion mass spectrometry and microinfrared spectroscopy found that hydrocarbon species with a molecular weight higher than the starting vapor molecules are produced when there is wear of the SiO(2) surface. When the n-pentanol vapor lubrication is effective and the silicon oxide surface does not wear, then the tribochemical polymerization products are negligible. These results imply that the tribochemical polymerization is associated with the substrate wear process occurring due to insufficient adsorbate supply or high mechanical load. The tribochemical reactions do not seem to be the primary lubrication mechanism for vapor phase lubrication of SiO(2) surfaces with alcohol, although they may lubricate the substrate momentarily upon failure of the alcohol vapor delivery to the sliding contact.

Macro- to nanoscale wear prevention via molecular adsorption.

As the size of mechanical systems shrinks from macro- to nanoscales, surface phenomena such as adhesion, friction, and wear become increasingly significant. This paper demonstrates the use of alcohol adsorption as a means of continuously replenishing the lubricating layer on the working device surfaces and elucidates the tribochemical reaction products formed in the sliding contact region. Friction and wear of native silicon oxide were studied over a wide range of length scales from macro- to nanoscales using a ball-on-flat tribometer (millimeter scale), sidewall microelectromechanical system (MEMS) tribometer (micrometer scale), and atomic force microscopy (nanometer scale). In all cases, the alcohol vapor adsorption successfully lubricated and prevented wear. Imaging time-of-flight secondary ion mass spectrometry analysis of the sliding contact region revealed that high molecular weight oligomeric species were formed via tribochemical reactions of the adsorbed linear alcohol molecules. These tribochemical products seemed to enhance the lubrication and wear prevention. In the case of sidewall MEMS tests, the lifetime of the MEMS device was radically increased via vapor-phase lubrication with alcohol.