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Three nonhalogenated ionic liquids (ILs) dissolved in 2-ethylhexyl laurate (2-EHL), a biodegradable oil, are investigated in terms of their bulk and electro-interfacial nanoscale structures using small-angle neutron scattering (SANS) and neutron reflectivity (NR). The ILs share the same trihexyl(tetradecyl)phosphonium ([P6,6,6,14]+) cation paired with different anions, bis(mandelato)borate ([BMB]−), bis(oxalato)borate ([BOB]−), and bis(salicylato)borate ([BScB]−). SANS shows a high aspect ratio tubular self-assembly structure characterized by an IL core of alternating cations and anions with a 2-EHL-rich shell or corona in the bulk, the geometry of which depends upon the anion structure and concentration. NR also reveals a solvent-rich interfacial corona layer. Their electro-responsive behavior, pertaining to the structuring and composition of the interfacial layers, is also influenced by the anion identity. [P6,6,6,14][BOB] exhibits distinct electroresponsiveness to applied potentials, suggesting an ion exchange behavior from cation-dominated to anion-rich. Conversely, [P6,6,6,14][BMB] and [P6,6,6,14][BScB] demonstrate minimal electroresponses across all studied potentials, related to their different dissociative and diffusive behavior. A mixed system is dominated by the least soluble IL but exhibits an increase in disorder. This work reveals the subtlety of anion architecture in tuning bulk and electro-interfacial properties, offering valuable molecular insights for deploying nonhalogenated ILs as additives in biodegradable lubricants and supercapacitors.

A series of 19 ionic liquids (ILs) based on phosphonium and imidazolium cations of varying alkyl-chain lengths with the orthoborate anions bis(oxalato)borate [BOB](-), bis(mandelato)borate, [BMB](-) and bis(salicylato)borate, [BScB](-), are synthesized and studied using small-angle neutron scattering (SANS). All measured systems display nanostructuring, with 1-methyl-3-n-alkyl imidazolium-orthoborates forming clearly bicontinuous L-3 spongelike phases when the alkyl chains are longer than C-6 (hexyl). L-3 phases are fitted using the Teubner and Strey model, and diffusely-nanostructured systems are primarily fitted using the Ornstein-Zernicke correlation length model. Strongly-nanostructured systems have a strong dependence on the cation, with molecular architecture variation explored to determine the driving forces for self-assembly. The ability to form well-defined complex phases is effectively extinguished in several ways: methylation of the most acidic imidazolium ring proton, replacing the imidazolium 3-methyl group with a longer hydrocarbon chain, substitution of [BOB](-) by [BMB](-), or exchanging the imidazolium for phosphonium systems, irrespective of phosphonium architecture. The results suggest there is only a small window of opportunity, in terms of molecular amphiphilicity and cation:anion volume matching, for the formation of stable extensive bicontinuous domains in pure bulk orthoborate-based ILs. Particularly important for self-assembly processes appear to be the ability to form H-bonding networks, which offer additional versatility in imidazolium systems.

Rolling element bearings, when subjected to small oscillating movements or vibrations, run the risk of being damaged by mechanisms such as Standstill Marks and False Brinelling. Damages resulting from these phenomena can decrease bearing fatigue life and increase wear-induced friction torque. These failures do not correlate well with standard life estimation approaches. Experimental studies play a crucial role in gaining knowledge in this area. The review integrates knowledge from experiments ranging from single contacts to laboratory and full-scale bearings in wind power and aerospace applications. The generalization is achieved using a non-dimensional amplitude parameter that relates rolling element travel during an oscillation to the Hertzian contact size. The review encompasses testing methods, procedures, reporting practices, result scaling, and application-specific considerations., QC 20230830

The structure and interaction of ionic liquids (ILs) influence their interfacial composition, and their arrangement (i.e., electric double-layer (EDL) structure), can be controlled by an electric field. Here, we employed a quartz crystal microbalance (QCM) to study the electrical response of two non-halogenated phosphonium orthoborate ILs, dissolved in a polar solvent at the interface. The response is influenced by the applied voltage, the structure of the ions, and the solvent polarizability. One IL showed anomalous electro-responsivity, suggesting a self-assembly bilayer structure of the IL cation at the gold interface, which transitions to a typical EDL structure at higher positive potential. Neutron reflectivity (NR) confirmed this interfacial structuring and compositional changes at the electrified gold surface. A cation-dominated self-assembly structure is observed for negative and neutral voltages, which abruptly transitions to an anion-rich interfacial layer at positive voltages. An interphase transition explains the electro-responsive behaviour of self-assembling IL/carrier systems, pertinent for ILs in advanced tribological and electrochemical contexts., QC 20230918

A statistical, energy-based approach is employed to experimentally characterize the ability of different greases to reduce friction when a point contact is subjected to repeated reciprocal displacements of smaller magnitude than the contact diameter. This approach allows the assessment of lubricant fretting performance with respect to its ability to remain within the contact and also its boundary lubrication properties. The results indicate that composition-dependent boundary lubrication properties of greases loaded with non-halogenated ionic liquids containing bis(oxalato)borate ([BOB]) and bis(mandelato)borate ([BMB]) anions can result in no detectable wear and low friction, even under conditions of moderately high pressures and where the original contact area is never fully uncovered. This discovery paves the way for the development of anti-fretting ionic greases., QC 20230621

Electric vehicle motors in e-drivetrain are equipped with grease-lubricated bearings operating at both low and high speeds with frequent speed changes. The grease-bearing system must secure a long lifespan and low frictional torque to improve efficiency and sustainability. The present paper focuses on the influence of two types of thickener, lithium complex and polypropylene, on the grease lubrication performance under conditions typical for e-motors. The comparison of both thickeners is performed in terms of friction torque and energy consumption in eight long-duration experiments (337 hr). The results show that the polypropylene thickener provides 21.5% lower energy consumption compared to the lithium complex. Changes in grease rheology and degradation in the tests are analysed and correlated with the grease lubrication performance., QC 20220301

We tested two types of ball bearings with an outer diameter of 750 mm to learn more about the challenges of oscillating motions for pitch bearings. The experimental conditions are derived from aero-elastic simulations, long-term wind speed measurements and a scaling method that considers loads and pitch angles. As a result, the parameters relevant for pitch bearings are represented appropriately, and the findings are transferable to other bearing sizes. For the tested parameter sets, severe wear occurred for over 90% of the exposed contact areas after 12 500 oscillating cycles. Decreasing the number of cycles to 1250 leads to a mix of exposed areas with 13% severe wear, 32% mild wear and 55% no wear, with no apparent pattern. The results demonstrate that a comparatively small amount of consecutive cycles can lead to severe wear. A new type of bearing tested showed less wear for the selected operating conditions., QC 20220602

Four nonhalogenated ionic liquids (ILs) based on the same phosphonium cation are investigated in terms of the anion suitability for enhancing the lubricity of a biodegradable oil. For all test conditions, typical for industrial machine components, the lubrication is shown to be governed by nonsacrificial films formed by the physisorption of ionic species on the tribo-surfaces. The anionic structure appears to have an important role in the formation of friction modifying films. The orthoborate ILs exhibit the formation of robust ionic boundary films, resulting in reduced friction and better wear protection. On the contrary, the surface adsorption of phosphinate and phosphate ILs appears to antagonistically disrupt the intrinsic lubrication properties of the biodegradable oil, resulting in high friction and wear. Through additional investigations, it is postulated that the higher dissociation of orthoborate ILs in the biodegradable oil allows the formation of hierarchical and electrostatically overscreened layer structures with long-range order, whereas the ILs with phosphate and phosphinate anions exhibit low dissociation in biodegradable oil, possibly due to the ion pairs being surrounded by a hydrocarbon halo, which presumably results in weak adsorption to form a mixed interfacial layer with no long-range order., QC 20211108

It was found that Li[BOB]center dot nH(2)O salts were not readily suitable for the synthesis of high-purity orthoborate-based tetraalkylphosphonium ionic liquids, as exemplified here for trihexyl(tetradecyl)phosphonium bis(oxalato)borate, [P-6,P-6,P-6,P-14][BOB]; along with [BOB](-), a metastable transition anionic complex (TAC) of dihydroxy(oxalato)borate with oxalic acid, [B(C2O4)(OH)(2)center dot(HOOC-COOH)](-), was also formed and passed into the ionic liquid in the course of the metathesis reaction with trihexyl(tetradecyl)phosphonium chloride. On the contrary, Na[BOB] was found to be a more suitable reagent for the synthesis of this IL, because [BOB](-) anions safely passed into the final IL without hydrolysis, when metathesis reactions were performed using aqueous-free media. Since ultra-pure Na[BOB] is not commercially available, in this work, a preparation protocol for ultra-pure (>99%) Na[BOB] was developed: (i) molar ratios of boric and oxalic acids were optimised to minimise boron-containing impurities, (ii) the Na[BOB] product was thoroughly purified by sequential washing of a fine powder product in hot acetonitrile and ethanol and (iii) characterised using powder X-ray diffraction and solid-state B-11 MAS NMR spectroscopy. The physico-chemical properties of the prepared boron-impurity-free IL, i.e., its density, viscosity, electric conductivity, glass-transition temperature and thermal stability, were found to be significantly different from those of the previously reported [P-6,P-6,P-6,P-14][BOB], containing ca. 45 mol% of TAC, [B(C2O4)(OH)(2)center dot(HOOC-COOH)](-). It was found that a high-purity [P-6,P-6,P-6,P-14][BOB] prepared in this work has a considerably lower viscosity, a higher viscosity index and a wider electro-chemical window (ECW) compared to those of the sample of [P-6,P-6,P-6,P-14][BOB] with ca. 45 mol% of TAC. Interestingly, [B(C2O4)(OH)(2)center dot(HOOC-COOH)](-) in the latter sample almost completely transformed into [BOB](-), QC 20210422