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The main objective of this PhD thesis is to design and characterize efficient nanolubricants based on three polyalphaolefins (PAOs) and nanoparticles (NPs) of metal oxides or ceramics coated with organic acids for wind turbine gearboxes and electric transmissions of electric vehicles. First, preliminary tests and an in-depth literature survey on the time stability and tribological behavior of nanodispersions containing chemically modified nanoadditives were performed. Then, the thermophysical and tribological properties of PAO nanolubricants containing coated NPs (ZnO-OA, TiO2-OA, or SiO2-SA) were evaluated; in addition, possible tribological mechanisms were analyzed by confocal Raman microscopy. All the coated NPs studied improve the tribological behavior of their base oil, being the best the SiO2-SA NPs.

This research reports the antifriction and antiwear properties of Mn3O4-Graphene nanocomposites (Mn3O4-G) as additives of a paraffinic base oil commonly used in the formulation of electric vehicles transmission oils, G-III base oil. Four G-III base oil nanodispersions have been designed, G-III base oil + 0.025 wt% Mn3O4-G, G-III base oil + 0.050 wt% Mn3O4-G, G-III base oil + 0.075 wt% Mn3O4-G and G-III base oil + 0.100 wt% Mn3O4-G, to know the optimal concentration of nanoadditive. Tribological experiments were carried out with these nanolubricants and with neat G-III base oil at pure sliding conditions under a working load of 9.43 N. All tested nanolubricants led to similar friction coefficients in comparison to that obtained using G-III base oil. Tribological specimens tested with formulated nanolubricants revealed less wear than that obtained with G-III base oil, obtaining the greatest wear reduction using the G-III base oil + 0.075 wt% Mn3O4-G nanolubricant, with reductions of 25, 50 and 64% in wear scar diameter, maximum depth and transversal area, respectively. Moreover, by means of confocal Raman microscopy and roughness evaluation of worn tribological specimens, it was concluded that synergetic effect, tribofilm formation and rolling mechanisms happen

This Doctoral Thesis presents new designed nanolubricants as potential substitutes of conventional lubricants. Hexagonal boron nitride nanoparticles, graphene nanoplatelets, iron oxide nanoparticles (synthetized from iron mine sludge), three phosphonium ionic liquids and two polyalphaolefin base oils (PAO32 and PAO10) were the materials selected. The techniques used in the characterization of nanoparticles, base oil, ionic liquids, and the worn surfaces from the tribological tests were Raman, SEM, FTIR, HRTEM, XRD or 3D profilometry. Viscosity, density, viscosity index, stability and tribological behavior (friction and wear) of designed nanolubricants were studied. Most of them improved the overall properties of PAO32 40 % reduction in friction and 99 % in wear being stable up to 240 days.

In this work, ZnO nanoparticles (NPs) were successfully synthesized and coated with oleic acid (OA). The mean diameter of these NPs (ZnO-OA) was around 11.5 nm, their core was characterized by XRD and their coating by FTIR and Raman. Homogeneous dispersions at different concentrations (0.10, 0.25, 0.50, 0.75 and 1.00 wt%) of ZnO-OA in polyalphaolefin 40 (PAO40) oil were thermophysically and tribologically characterized. Both density and viscosity values increased with the concentration of NPs, reaching relative increments of 0.5% and 4.0%, respectively, for the 1 wt% nanodispersion. Tribological tests were performed at 353.15 K using an Anton Paar MCR 302 rheometer equipped with a tribological ball-on three-pins configuration testing module. Regarding the tribological behavior, the optimal concentration was 0.25 wt% of ZnO-OA (25% of reduction in the friction coefficient and 82% wear reduction in terms of cross sectional area, respect to those obtained with the neat base oil). The rolling mechanism owing to the spherical shape of the nanoadditives, transforming sliding friction into rolling friction, and the mending effect could explain the better tribological performance of nanolubricants with respect to that of neat PAO40. In addition, the presence of PAO40, ZnO-OA NPs and iron oxides was evidenced from confocal Raman microscopy on the worn surfaces obtained from tribological test with PAO40 + 0.25 wt% ZnO-OA dispersion

This work presents the antifriction and antiwear properties of TiO2 nanoparticles coated with oleic acid, TiO2-OA, as additives of a low viscosity polyalphaolefin base oil, PAO8. To find the optimal concentration of nanoadditives that minimize friction and wear, four PAO8 based nanodispersions were formulated: PAO8 + 0.10 wt% TiO2-OA, PAO8 + 0.25 wt% TiO2-OA, PAO8 + 0.35 wt% TiO2-OA and PAO8 + 0.50 wt% TiO2-OA. Tribological experiments were performed under pure sliding and rolling-sliding conditions at 120 °C, with the four formulated nanolubricants and with PAO8 base oil. All the nanolubricants showed lower friction coefficients than that obtained with the PAO8 base oil, reaching maximum reductions for the 0.35 wt% TiO2-OA nanolubricant, for both types of test conditions. The tribological specimens tested under pure sliding conditions with the nanolubricants showed fewer wear than those tested with PAO8, finding the highest wear decreases also with the PAO8 + 0.35 wt% TiO2-OA nanolubricant, being 26 %, 65 % and 73 %, in wear track width, depth and area, in that order. Through Raman microscopy and roughness study of the worn samples, it can be inferred that tribofilm, mending and polishing mechanisms occur. Moreover, the thermal conductivity of the optimal nanolubricant (0.35 wt%) was measured at 20, 30, 40 and 50 °C

Antifriction synergies between an ionic liquid (IL) and nanopowders as additives of an ester base oil were analysed at rolling conditions. For this aim, two nanodispersions based on hybrid combinations of hexagonal boron nitride nanoparticles (h-BN) or graphene nanoplatelets (GnP) with tri(butyl) ethylphosphonium diethylphosphate ionic liquid as additives in triisotridecyltrimellitate (TTM) base oil and the mixture of TTM and IL were analysed using two tribometer techniques. Film thickness characterisation and tribological tests were performed at rolling conditions [5% slide-roll-ratio (SRR)], under 50N and at operating temperatures of 30, 50 and 80°C. Stribeck curves showed that friction coefficients for the prepared lubricants are lower than those found for the TTM, being the best friction behaviour for the hybrid GnP nanolubricant. Furthermore, friction torque loss tests were performed in rolling ball bearings, observing that for the two hybrid nanolubricants lower friction torque values were obtained

Tribological performance of three ionic liquids (ILs), trihexyltetradecylphosphonium bis(2-ethylhexyl)phosphate (IL1), tributylethylphosphonium diethylphosphate (IL2) and trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate (IL3) combined with graphene nanoplatelets (GnP) as hybrid additives for a polyalphaolefin (PAO 32) base oil was studied. For this purpose, several dispersions were prepared by mixing, stirring, and then sonicating according to the following combinations: PAO 32 + (a wt%) IL + (b wt%) GnP, where a and b represent the concentration of the additives added to the PAO 32 base oil. In this study a is 0 or 1 and b is 0.05 or 0.1. Three PAO 32 + 1 wt% IL mixtures were also prepared. Thermophysical properties and stability against sedimentation of the dispersions were studied by means of a rotational viscometer and visual observation, respectively. Furthermore, friction and wear behaviors were analyzed using a ball-on-disk configuration tribometer operating in rotational mode and both a 3D optical profiler and a scanning electronic microscope, respectively. Confocal Raman microscopy was used to identify compounds in the tribofilms formed on the wear tracks. The hybrid combinations of PAO 32/ILs/GnP improved the friction reduction of the corresponding binary PAO 32/GnP nanolubricants and PAO 32/IL mixtures. Interestingly, the hybrid dispersions with low concentrations of GnP (with 0.05 wt% GnP) are more effective than those of 0.1 wt% GnP. Results also show that the addition of both 0.05 wt% graphene nanoplatelets and 1 wt% IL led to friction reductions up to 36% and wear reductions up to 27%, compared with the capabilities of neat PAO 32. IL1 and IL3, containing the trihexyltetradecylphosphonium cation, generate the hybrid lubricants with the best combined properties (stability, viscosity and tribological properties) of all the lubricants tested

Tribological performance of polyalphaolefin 32, PAO, is investigated by adding two nanomaterials (graphene nanoplatelets, GnP, and hexagonal boron nitride nanoparticles, h-BN) and an ionic liquid ([P6,6,6,14][DEHP], IL1, [P2,4,4,4][DEP], IL2, or [P6,6,6,14][(iC8)2PO2], IL3). Designed double hybrid nanodispersions are PAO/1 wt% ILX/0.05 wt% GnP/0.1 wt% h-BN (X = 1, 2 or 3). The best anti-friction behavior corresponds to PAO/IL3/GnP/h-BN (40% reduction compared to that achieved with PAO). Anti-wear behavior is similar for the three double hybrid nanodispersions. Roughness of the worn surface tested with PAO is higher than that obtained for each of the nanodispersions. Tribo-film formation and repair effect on worn surfaces due to ILs and nanoparticles are revealed. Some positive synergies were found between each IL and GnP/h-BN as hybrid PAO additives

Esta Tese centrouse no deseño e caracterización de nanolubricantes formados por aceites base e distintos tipos de nanopartículas como aditivos. Para este fin, estudáronse o comportamento termofísico e tribolóxico dos nanolubricantes, e a súa estabilidade. Obtivéronse nanolubricantes cunha estabilidade de ata 11 meses. Para determinar o coeficiente de fricción, o espesor do filme e o par de fricción, empregáronse catro equipos tribométricos e, para cuantificar o desgaste producido, un perfilómetro óptico 3D. Obtivéronse reducións de fricción e de desgaste (ancho de pegada) de ata 36% y 67%, respectivamente. Tamén se estudaron os mecanismos de redución do desgaste dos nanoditivos mediante microscopía electrónica de varrido e microscopía Raman confocal, entre outras.

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

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

Dispersions based on hexagonal boron nitride, h-BN, nanoparticles, at 0.50, 0.75 and 1.0 wt.% mass concentrations, in an ester base oil composed mainly of trimethylolpropane trioleate, were investigated as potential nanolubricants. The stability of the dispersions was assessed to determine the reliability of the tribological, thermophysical and rheological measurements. Density and viscosity were measured from 278.15 to 373.15 K, while rheological behavior was analyzed at shear rates from 1 to 1000 s−1 at 283.15 K. Newtonian behavior was exhibited by all nanolubricants at the explored conditions, with the exception of the highest concentration at the lowest shear rates, where possible non-Newtonian behavior was observed. Tribological tests were performed under a normal load of 2.5 N. Wear was evaluated by means of a 3D profiler, scanning electron microscopy and confocal Raman microscopy. The best tribological performance was achieved by the 0.75 wt.% nanolubricant, with reductions of 25% in the friction coefficient, 9% in the scar width, 14% in the scar depth, and 22% of the transversal area, all with respect to the neat oil. It was observed that physical protective tribofilms are created between rubbing surfaces.

En este trabajo se han analizado diferentes m´etodos experimentales utilizados en la bibliograf´ýa para la investigaci´on del equilibrio de fases a alta presi´on y se presenta un nuevo equipo isoc´orico que ha sido implementado en nuestro laboratorio para la determinaci´on de la solubilidad de gases en l´ýquidos, similar al empleado por Wahlstr¨om y Vamling [1,2]. Adem´as, se ha determinado la solubilidad de CO2 en dos ´esteres de pentaeritritol (PEs), tetrapentanoato de pentaeritritol, PEC5, y tetra-2-etilhexanoato de pentaeritritol, PEBE8, en el rango de (283-333) K y hasta 7 MPa. Nuestros resultados han sido comparados con los obtenidos por Bobbo et al. [3,4] para los is´omeros de estos lubricantes, tetra- 2-metilbutanoato de pentaeritritol, PEBM5 y tetraoctanoato de pentaeritritol, PEC8. Se ha observado como la solubilidad del CO2 expresada en porcentaje en peso del refrigerante disminuye con el tama˜no de la mol´ecula del ´ester de pentaeritritol, mientras que el efecto de la ramificaci´on de las mol´eculas es muy d´ebil.