The decomposition of the ruthenium precursor Ru(COD)(COT) (1, COD = 1,5-cyclooctadiene; COT = 1,3,5-cyclooctatriene) in mild conditions (room temperature, 1--3 bar H(2)) in THF leads, in the presence of a stabilizer (polymer or ligand), to nanoparticles of various sizes and shapes. In THF and in the presence of a polymer matrix (Ru/polymer = 5%), crystalline hcp particles of uniform mean size (1.1 nm) homogeneously dispersed in the polymer matrix and agglomerated hcp particles (1.7 nm) were respectively obtained in poly(vinylpyrrolidone) and cellulose acetate. The same reaction, carried out using various concentrations relative to ruthenium of alkylamines or alkylthiols as stabilizers (L = C(8)H(17)NH(2), C(12)H(25)NH(2), C(16)H(33)NH(2), C(8)H(17)SH, C(12)H(25)SH, or C(16)H(33)SH), leads to agglomerated particles (L = thiol) or particles dispersed in the solution (L = amine), both displaying a mean size near 2--3 nm and an hcp structure. In the case of amine ligands, the particles are generally elongated and display a tendency to form worm- or rodlike structures at high amine concentration. This phenomenon is attributed to a rapid amine ligand exchange at the surface of the particle as observed by (13)C NMR. In contrast, the particles stabilized by C(8)H(17)SH are not fluxional, but a catalytic transformation of thiols into disulfides has been observed which involves oxidative addition of thiols on the ruthenium surface. All colloids were characterized by microanalysis, infrared spectroscopy after CO adsorption, high-resolution electron microscopy, and wide-angle X-ray scattering.
Tested in boundary lubrication, inorganic fullerene-like WS 2 nanoparticles used as additives in oil present interesting friction reducing and anti-wear properties. A dispersion with only 1 wt% of particles leads, from a contact pressure of 0.83 GPa, to a drastic decrease of the friction coefficient below 0.04 and to very low wear. High resolution transmission electron microscopy (HRTEM), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Raman Spectroscopy and video imaging were used to explain the lubrication mechanisms. A structural modification of fullerene-like nanoparticles into sheets during the friction test was evidenced to be the main effect at the origin of these properties.
In this work, we theoretically investigated the friction mechanism of hexagonal MoS(2) (a well-known lamellar compound) using a computational chemistry method. First, we determined several parameters for molecular dynamics simulations via accurate quantum chemistry calculations and MoS(2) and MoS(2-x)O(x) structures were successfully reproduced. We also show that the simulated Raman spectrum and peak shift on X-ray diffraction patterns were in good agreement with those of experiment. The atomic interactions between MoS(2) sheets were studied by using a hybrid quantum chemical/classical molecular dynamics method. We found that the predominant interaction between two sulfur layers in different MoS(2) sheets was Coulombic repulsion, which directly affects the MoS(2) lubrication. MoS(2) sheets adsorbed on a nascent iron substrate reduced friction further due to much larger Coulombic repulsive interactions. Friction for the oxygen-containing MoS(2) sheets was influenced by not only the Coulomb repulsive interaction but also the atomic-scale roughness of the MoS(2)/MoS(2) sliding interface.
Using a new quartz-made reactor, large amounts of fullerene-like (IF) MoS 2 nanoparticles were synthesized by reacting MoO 3 vapor with H 2 S in a reducing atmosphere. The nanoparticles were found to be of high crystalline order; with an average size of 70 nm and consist of more than 30 closed shells. Extensive tribological testing of the nanoparticles in two types of synthetic oils-poly-alpha olefins (PAO)-was carried out and compared to that of bulk (2H platelets) MoS 2 and IF-WS 2 . These tests indicated that under high pressure and relatively low humidity, the IF-MoS 2 exhibited a friction coefficient as low as 0.03 and the smallest wear rate of the measured systems. However, its performance was found to be lower in comparison to IF-WS 2 after 2500 cycles, due probably to its inferior chemical stability. This study indicates that the tribological performance of the IF nanoparticles depends strongly on their crystalline order and size.
In this work, the friction anisotropy of hexagonal MoS(2) (a well-known lamellar compound) was theoretically investigated. A molecular dynamics method was adopted to study the dynamical friction of two-layered MoS(2) sheets at atomistic level. Rotational disorder was depicted by rotating one layer and was changed from 0° to 60°, in 5° intervals. The superimposed structures with misfit angle of 0° and 60° are commensurate, and others are incommensurate. Friction dynamics was simulated by applying an external pressure and a sliding speed to the model. During friction simulation, the incommensurate structures showed extremely low friction due to cancellation of the atomic force in the sliding direction, leading to smooth motion. On the other hand, in commensurate situations, all the atoms in the sliding part were overcoming the atoms in counterpart at the same time while the atomic forces were acted in the same direction, leading to 100 times larger friction than incommensurate situation. Thus, lubrication by MoS(2) strongly depended on its interlayer contacts in the atomic scale. According to part I of this paper [Onodera, T., et al. J. Phys. Chem. B 2009, 113, 16526-16536], interlayer sliding was source of friction reduction by MoS(2) and was originally derived by its material property (interlayer Coulombic interaction). In addition to this interlayer sliding, the rotational disorder was also important to achieve low friction state.
Inorganic fullerene-(IF)-like nanoparticles made of metal dichalcogenides (IF-MoS 2 , IF-WS 2 ) have been known to be effective as anti-wear and friction modifier additives under boundary lubrication. The lubrication mechanism of these nanoparticles has been widely investigated in the past and it is now admitted that their lubrication properties are attributed to a gradual exfoliation of the external sheets of the particles during the friction process leading to their transfer onto the asperities of the reciprocating surfaces. However, the chemical interaction between these molecular sheets and the rubbing surfaces has so far never been investigated in detail. In this study, the tribochemistry of the IF nanoparticles was carefully investigated. A series of friction test experiments on different rubbing surfaces (Steel, Alumina, Diamond-Like Carbon) were performed with IF-MoS 2 nanoparticles. High-resolution transmission electron microscopy, scanning electron microscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy were used to characterize the tribostressed areas on rubbing surfaces. A tribofilm composed of hexagonal 2H-MoS 2 nanosheets was only observed on the steel surface. This transfer film was found to be incorporated into an iron oxide layer. A tribochemical reaction between the 2H-MoS 2 nanolayers and the iron/iron oxide has been proposed as an explanation for the adhesion of this tribofilm. The tribochemical mechanism of the IF-MoS 2 nanoparticles is discussed in this article.
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