Our previous work suggested great potential for a phosphonium-organophosphate ionic liquid (IL) as an antiwear lubricant additive. In this study, a set of five ILs were carefully designed and synthesized, with identical organophosphate anions but dissimilar phosphonium cations, to allow systematic investigation of the effects of cation alkyl chain length and symmetry on physicochemical and tribological properties. Symmetric cations with shorter alkyl chains seem to increase the density and thermal stability due to closer packing. On the other hand, either higher cation symmetry or longer alkyl moieties induce a higher viscosity, though the viscosity index is dependent more on molecular mass than on symmetry. While a larger cation size generally increases an IL's solubility in nonpolar hydrocarbon oils, six-carbon seems to be the critical minimum alkyl chain length for high oil miscibility. Both the two ILs, that are mutually oil miscible, have demonstrated promising lubricating performance at 1.04% treat rate, though the symmetric-cation IL moderately outperformed the asymmetric-cation IL. Characterizations on the tribofilm formed by the best-performing symmetric-cation IL revealed the film thickness, nanostructure, and chemical composition. Results here provide fundamental insights for future molecular design in developing oil-soluble ILs as lubricant additives.

Unique synergistic effects between phosphonium-alkylphosphate ionic liquids (ILs) and zinc dialkyldithiophosphate (ZDDP) are discovered when used together as lubricant additives, resulting in significant friction and wear reduction along with distinct tribofilm composition and mechanical properties. The synergism is attributed to the remarkably 30-70× higher-than-nominal concentrations of hypothetical new compounds (via anion exchange between IL and ZDDP) on the fluid surface/interface.

In this work, we investigated the feasibility of five quaternary (aprotic) and four tertiary (protic) ammonium ionic liquids (ILs) with an identical organophosphate anion as lubricant anti-wear additives. Viscosity, oil solubility, thermal stability and corrosivity of the candidate ILs were characterized and correlated to the molecular structure. The protic group exhibits higher oil solubility than the aprotic group, and longer alkyl chains seem to provide better oil solubility and higher thermal stability. Selected ILs were applied as oil additives in steel-cast iron tribological tests and demonstrated promising anti-scuffing and anti-wear functionality. The thickness, nanostructure, and composition of the tribofilm formed by the best performing IL were revealed by surface characterization for mechanistic understanding of the tribochemical interactions between the IL and metal surface. Results provide fundamental insights of the correlations among the molecular structure, physiochemical properties and lubricating performance for ammonium-phosphate ILs.

Multiphase transport inside a proton exchange membrane electrolyzer cell (PEMEC) plays an important role in its performance and design. Most PEMEC modeling studies so far have mainly focused on its electrochemical performance prediction and analysis, and fundamental understanding of the effect of multiphase transport on the cell performance is still lacking. In this study, a two-phase mathematical model is developed to investigate the transport properties inside liquid/gas diffusion layers (LGDLs) and to explore their effects on the PEMEC voltage and efficiency. Sudden changes in the PEMEC voltage and efficiency are captured for the first time as the current density reaches a limiting value, and the limiting current density is greatly impacted by the LGDL contact angle, porosity, and thickness. In addition, the liquid water distribution and cell performance in PEMECs with different important operating and physical parameters are examined and discussed in detail. Increasing the LGDL porosity or/and decreasing its surface contact angle will improve the PEMEC performance especially at the high current density. The thickness changes of the LGDL and membrane also have significant impacts on the cell voltage and efficiency. The model can effectively examine two-phase transport properties and provide useful information for design optimization of a PEMEC.

This article examines the elasticity, hardness, and resistance-to-plastic-deformation (P/S 2 ) measured via nanoindentation of several tribofilms and correlates these properties to friction and wear behavior. The tribofilms were generated by oil ball-on-plate sliding lubricated by a base oil containing an ionic liquid, phosphonium-organophosphate or ammonium-organophosphate, zinc dialkyldithiophosphate (ZDDP), or combinations of IL and ZDDP. Nanoindentation was conducted at room and elevated temperatures. While there seems little correlation between the tribofilm hardness and friction or wear behavior, a higher modulus generally leads to better friction or wear performance. In contrast, a lower P/S 2 ratio tends to reduce friction and improve wear protection, which is in an opposite trend as reported for bulk materials. This is likely attributable to the dynamic self-healing characteristics of tribofilms.

We have previously reported an oil-miscible phosphonium-organophosphate ionic liquid (IL) with an effective anti-wear (AW) functionality when added to a base oil by itself or combined with a conventional zinc dialkyldithiophosphate (ZDDP) for a synergistic effect. In this research, we investigated whether this synergy manifests in formulated engine oils. An experimental SAE 0W-16 engine oil was generated containing a combination of IL and ZDDP with equal phosphorus contribution. The prototype engine oil was first evaluated using tribological bench tests: AW performance in boundary lubrication (BL) and friction behavior (Stribeck curves) in elastohydrodynamic, mixed, and BL. The forthcoming standard Sequence VIE engine dynamometer test was then conducted to demonstrate improved fuel economy. Results were benchmarked against those of another experimental engine oil with almost the same formulation except using ZDDP only without the IL (similar total phosphorus content). The IL-ZDDP formulation consistently outperforms the ZDDP-only formulation in friction reduction and wear protection, and results from the bench and engine tests are well correlated.

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A sustainable and robust electrochemical energy storage and/or a hybrid system to accommodate daily, even hourly changes of renewable resources becomes more critical. An advanced polymer electrolyte membrane water electrolyzer (PEMWE) has been shown to be effective energy storage medium by producing hydrogen/oxygen from water with electricity from renewable sources. When the renewable resources are available, hydrogen will be produced and stored, such that it can later provide a constant power supply with a PEM fuel cell, which is a reverse device of the electrolyzer. This entire portfolio will make renewable and hybrid energy systems effective to provide reliable and multiscale energy whenever needed. In proton exchange membrane water electrolyzers (PEMWEs), water is electrochemically splitting into oxygen and hydrogen. The oxygen generated at the anode side and the circled water flowing over the liquid/gas diffusion layer yield two-phase transport conditions in micro-channels and pores of LGDL, which significantly impact the performance. Due to limitations of the design of conventional PEMWEs and LGDLs,  the in-situ phenomena of two-phase flow has few been explored in operating PEMWEs. In this research, an innovative design of a transparent PEMWE is developed coupled with the thin and well-tuned titanium LGDLs with straight pores. The high-speed and micro-scale visualization system (HMVS), and electrochemical impedance spectroscopy will be used for in-situ characterizations. Visualization results are used for better understanding the behavior of two-phase flow and its effects on the PEMWE performance. Patterns of gas-bubble formation, evolution, departure and transport are identified. The effects of property of materials, including LGDL pore sizes, channel dimensions, are also investigated.