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Linking Molecular Structure and Lubrication Mechanisms in Tetraalkylammonium Orthoborate Ionic Liquids

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Abstract

While ionic liquids (ILs) have gained wide interest as potential alternative lubricants able to meet the requirements of next-generation tribological systems owing to their unique physico-chemical properties and promising lubricating behavior, our understanding of the mechanisms by which ILs reduce friction and/or wear is still elusive. Here, we combine macroscale tribological experiments with surface-analytical measurements to shed light on the lubrication mechanisms of a class of halogen-free ILs, namely tetraalkylammonium orthoborate ILs, at steel/steel sliding contacts. The tribological results indicate an improvement of the friction-reducing properties of these ILs as the length of the alkyl chains attached to ammonium cations increases. X-ray photoelectron spectroscopy analyses provide further evidence for the dependence of the lubrication mechanism of tetraalkylammonium orthoborate ILs on the IL structure. In the case of tetraalkylammonium orthoborate ILs with asymmetric ammonium cations containing a long alkyl chain, no sacrificial tribofilms were formed on steel surfaces, thus suggesting that the friction-reducing ability of these ILs originates from their propensity to undergo a pressure-induced morphological change at the sliding interface that leads to the generation of a lubricious, solid-like layered structure. Conversely, the higher friction response observed in tribological tests performed with tetraalkylammonium orthoborate ILs containing more symmetric ammonium cations and short alkyl chains is proposed to be due to the inability of this IL to create a transient interfacial layer owing to the reduced van der Waals interactions between the cationic alkyl chains. The resulting hard/hard contact between the sliding surfaces is proposed to lead to the cleavage of boron-oxygen bonds in the presence of water to form species that then adsorb onto the steel surface, including trivalent borate esters and oxalic acid from the decomposition of orthoborate anions, as well as tertiary amines from the degradation of alkylammonium cations induced by hydroxides released during the orthoborate decomposition reaction. The results of this work not only establish links between the molecular structure of a class of halogen-free ILs, their lubricating performance, and lubrication mechanism, but also provide evidence for the existence of multiple mechanisms underpinning the promising lubricating properties of ILs in general.

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Data Availability

The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The material is based upon work supported by the Welch Foundation (Grant No. F-2002-20190330) and the National Science Foundation Faculty Early Career Development Program (Grant No. 2042304). The acquisition of the VersaProbe-IV XPS was supported by the National Science Foundation Major Research Instrumentation program (Grant No. 2117623). F.M. acknowledges support from the 2018 Ralph E. Powe Junior Faculty Enhancement Award sponsored by the Oak Ridge Associated Universities (ORAU), and from the Walker Department of Mechanical Engineering and the Texas Materials Institute at the University of Texas at Austin. Last, but not least, this paper is dedicated to the memory of Prof. Anne Neville, whose contributions to tribology are long-standing and generous commitment to the development of the next-generation of scientists and engineers is endless.

Funding

Welch Foundation, F-2002-20190330, National Science Foundation, 2042304 and 2117623, Oak Ridge Associated Universities, 2018 Ralph E. Powe Junior Faculty Enhancement Award.

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Authors and Affiliations

  1. Texas Materials Institute, The University of Texas at Austin, Austin, TX, 78712, USA

    Jieming Yan, Hsu-Ming Lien & Filippo Mangolini

  2. Materials Science and Engineering Program, The University of Texas at Austin, Austin, TX, 78712, USA

    Jieming Yan & Hsu-Ming Lien

  3. Walker Department of Mechanical Engineering, The University of Texas at Austin, Austin, TX, 78712, USA

    Filippo Mangolini

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JY: Conceptualization, Investigation, Data curation, Formal analysis, Writing—original draft, Writing—review & editing; H-ML: Investigation, Data curation, Writing—review & editing; FM: Conceptualization, Investigation, Formal analysis, Writing—original draft, Funding acquisition, Writing—review & editing.

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Yan, J., Lien, HM. & Mangolini, F. Linking Molecular Structure and Lubrication Mechanisms in Tetraalkylammonium Orthoborate Ionic Liquids. Tribol Lett 71, 41 (2023). https://doi.org/10.1007/s11249-023-01714-7

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