Performance and Antiwear Mechanism of 1D and 2D Nanoparticles as Additives in a Polyalphaolefin.

This work is focused on the thermophysical and tribological study of eight nanolubricant compositions based on a polyalphaolefin (PAO 20) and two different nanoadditives: multi-walled carbon nanotubes (MWCNTs) and hexagonal boron nitride (h-BN). Regarding the thermophysical properties, density and dynamic viscosity of the base oil and the nanolubricants were measured in the range of 278.15-373.15 K, as well as their viscosity index, with the aim of evaluating the variation of these properties with the addition of the nanoadditives. On the other hand, their lubricant properties, such as contact angle, coefficient of friction, and wear surface, were determined to analyze the influence of the nanoadditives on the tribological performance of the base oil. The results showed that MWCNTs and h-BN nanoadditives improved the wear area by 29% and 37%, respectively, at a 0.05 wt% concentration. The density and dynamic viscosity increased compared with the base oil as the nanoadditive concentration increased. The addition of MWCNTs and h-BN nanoparticles enhanced the tribological properties of PAO 20 base oil.

Modeling of the Production of Lipid Microparticles Using PGSS® Technique.

Solid lipid microparticles (SLMPs) are attractive carriers as delivery systems as they are stable, easy to manufacture and can provide controlled release of bioactive agents and increase their efficacy and/or safety. Particles from Gas-Saturated Solutions (PGSS®) technique is a solvent-free technology to produce SLMPs, which involves the use of supercritical CO2 (scCO2) at mild pressures and temperatures for the melting of lipids and atomization into particles. The determination of the key processing variables is crucial in PGSS® technique to obtain reliable and reproducible microparticles, therefore the modelling of SLMPs production process and variables control are of great interest to obtain quality therapeutic systems. In this work, the melting point depression of a commercial lipid (glyceryl monostearate, GMS) under compressed CO2 was studied using view cell experiments. Based on an unconstrained D-optimal design for three variables (nozzle diameter, temperature and pressure), SLMPs were produced using the PGSS® technique. The yield of production was registered and the particles characterized in terms of particle size distribution. Variable modeling was carried out using artificial neural networks and fuzzy logic integrated into neurofuzzy software. Modeling results highlight the main effect of temperature to tune the mean diameter SLMPs, whereas the pressure-nozzle diameter interaction is the main responsible in the SLMPs size distribution and in the PGSS® production yield.

Tribological Behavior of Nanolubricants Based on Coated Magnetic Nanoparticles and Trimethylolpropane Trioleate Base Oil.

The main task of this work is to study the tribological performance of nanolubricants formed by trimethylolpropane trioleate (TMPTO) base oil with magnetic nanoparticles coated with oleic acid: Fe3O4 of two sizes 6.3 nm and 10 nm, and Nd alloy compound of 19 nm. Coated nanoparticles (NPs) were synthesized via chemical co-precipitation or thermal decomposition by adsorption with oleic acid in the same step. Three nanodispersions of TMPTO of 0.015 wt% of each NP were prepared, which were stable for at least 11 months. Two different types of tribological tests were carried out: pure sliding conditions and rolling conditions (5% slide to roll ratio). With the aim of analyzing the wear by means of the wear scar diameter (WSD), the wear track depth and the volume of the wear track produced after the first type of the tribological tests, a 3D optical profiler was used. The best tribological performance was found for the Nd alloy compound nanodispersion, with reductions of 29% and 67% in friction and WSD, respectively, in comparison with TMPTO. On the other hand, rolling conditions tests were utilized to study friction and film thickness of nanolubricants, determining that Fe3O4 (6.3 nm) nanolubricant reduces friction in comparison to TMPTO.

Ionic liquids based on phosphonium cations as neat lubricants or lubricant additives for a steel/steel contact.

After doing several miscibility essays with eight ionic liquids (ILs) and four base oils, the ILs tri(butyl)ethylphosphonium diethylphosphate [P4,4,4,2][C2C2PO4] and trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate [P6,6,6,14][(C2F5)3PF3] were selected to be studied as lubricant additives. The neat IL [P4,4,4,2][C2C2PO4], the base oils, and several blends were characterized in terms of density, viscosity, and thermal stability. The tribological performance of the miscible base oil/IL blends (1 wt %) and the neat [P4,4,4,2][C2C2PO4] were evaluated for the lubrication of an AISI 420 steel-100Cr6 steel contact pair. The friction coefficients and wear volumes obtained are also compared with those corresponding to the pure base oils and their mixtures with conventional additive zinc dialkyldithiophosphate (ZDDP). As neat lubricants, [P4,4,4,2][C2C2PO4] showed the best antifriction ability, whereas in terms of wear, better results were obtained with [P6,6,6,14][(C2F5)3PF3]. However, higher improvements in both friction and wear were found for blends containing [P4,4,4,2][C2C2PO4]. XPS analyses of the worn surfaces lubricated with these mixtures indicated the presence of phosphorus in the tribofilm formed on the wear track. However, this compound was slightly detected on tribosamples lubricated with blends containing [P6,6,6,14][(C2F5)3PF3].

On the density scaling of pVT data and transport properties for molecular and ionic liquids.

In this work, a general equation of state (EOS) recently derived by Grzybowski et al. [Phys. Rev. E 83, 041505 (2011)] is applied to 51 molecular and ionic liquids in order to perform density scaling of pVT data employing the scaling exponent γ(EOS). It is found that the scaling is excellent in most cases examined. γ(EOS) values range from 6.1 for ammonia to 13.3 for the ionic liquid [C(4)C(1)im][BF(4)]. These γ(EOS) values are compared with results recently reported by us [E. R. López, A. S. Pensado, M. J. P. Comuñas, A. A. H. Pádua, J. Fernández, and K. R. Harris, J. Chem. Phys. 134, 144507 (2011)] for the scaling exponent γ obtained for several different transport properties, namely, the viscosity, self-diffusion coefficient, and electrical conductivity. For the majority of the compounds examined, γ(EOS) > γ, but for hexane, heptane, octane, cyclopentane, cyclohexane, CCl(4), dimethyl carbonate, m-xylene, and decalin, γ(EOS) < γ. In addition, we find that the γ(EOS) values are very much higher than those of γ for alcohols, pentaerythritol esters, and ionic liquids. For viscosities and the self-diffusion coefficient-temperature ratio, we have tested the relation linking EOS and dynamic scaling parameters, proposed by Paluch et al. [J. Phys. Chem. Lett. 1, 987-992 (2010)] and Grzybowski et al. [J. Chem. Phys. 133, 161101 (2010); Phys. Rev. E 82, 013501 (2010)], that is, γ = (γ(EOS)/φ) + γ(G), where φ is the stretching parameter of the modified Avramov relation for the density scaling of a transport property, and γ(G) is the Grüneisen constant. This relationship is based on data for structural relaxation times near the glass transition temperature for seven molecular liquids, including glass formers, and a single ionic liquid. For all the compounds examined in our much larger database the ratio (γ(EOS)/φ) is actually higher than γ, with the only exceptions of propylene carbonate and 1-methylnaphthalene. Therefore, it seems the relation proposed by Paluch et al. applies only in certain cases, and is really not generally applicable to liquid transport properties such as viscosities, self-diffusion coefficients or electrical conductivities when examined over broad ranges of temperature and pressure.

Density scaling of the transport properties of molecular and ionic liquids.

Casalini and Roland [Phys. Rev. E 69, 062501 (2004); J. Non-Cryst. Solids 353, 3936 (2007)] and other authors have found that both the dielectric relaxation times and the viscosity, η, of liquids can be expressed solely as functions of the group (TV (γ)), where T is the temperature, V is the molar volume, and γ a state-independent scaling exponent. Here we report scaling exponents γ, for the viscosities of 46 compounds, including 11 ionic liquids. A generalization of this thermodynamic scaling to other transport properties, namely, the self-diffusion coefficients for ionic and molecular liquids and the electrical conductivity for ionic liquids is examined. Scaling exponents, γ, for the electrical conductivities of six ionic liquids for which viscosity data are available, are found to be quite close to those obtained from viscosities. Using the scaling exponents obtained from viscosities it was possible to correlate molar conductivity over broad ranges of temperature and pressure. However, application of the same procedures to the self-diffusion coefficients, D, of six ionic and 13 molecular liquids leads to superpositioning of poorer quality, as the scaling yields different exponents from those obtained with viscosities and, in the case of the ionic liquids, slightly different values for the anion and the cation. This situation can be improved by using the ratio (D∕T), consistent with the Stokes-Einstein relation, yielding γ values closer to those of viscosity.