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Research Article | Open Access

Molecules with a TEMPO-based head group as high-performance organic friction modifiers

Jinchi HOU1, Masaki TSUKAMOTO1, Seanghai HOR1, Xingyu CHEN1, Juntao YANG1, Hedong ZHANG1( ), Nobuaki KOGA1, Koji YASUDA2, Kenji FUKUZAWA3, Shintaro ITOH3, Naoki AZUMA3
Department of Complex Systems Science, Graduate School of Informatics, Nagoya University, Nagoya 464-8601, Japan
Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8601, Japan
Department of Micro-Nano Systems Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
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Abstract

High-performance organic friction modifiers (OFMs) added to lubricating oils are crucial for reducing energy loss and carbon footprint. To establish a new class of OFMs, we measured the friction and wear properties of N-(2,2,6,6-tetramethyl-1-oxyl-4-piperidinyl)dodecaneamide referred to as C12Amide-TEMPO. The effect of its head group chemistry, which is characterized by a rigid six-membered ring sandwiched by an amide group and a terminal free oxygen radical, was also investigated with both experiments and quantum mechanical (QM) calculations. The measurement results show that C12Amide-TEMPO outperforms the conventional OFMs of glyceryl monooleate (GMO) and stearic acid, particularly for load-carrying capacity, wear reduction, and stability of friction over time. The friction and wear reduction effect of C12Amide-TEMPO is also greatly superior to those of C12Ester-TEMPO and C12Amino-TEMPO, in which ester and amino groups replace the amide group, highlighting the critical role of the amide group. The QM calculation results suggest that, in contrast to C12Ester-TEMPO, C12Amino-TEMPO, and the conventional OFMs of GMO and stearic acid, C12Amide-TEMPO can form effective boundary films on iron oxide surfaces with a unique double-layer structure: a strong surface adsorption layer owing to the chemical interactions of the amide oxygen and free radical with iron oxide surfaces, and an upper layer owing to the interlayer hydrogen-bonding between the amide hydrogen and free radical or between the amide hydrogen and oxygen. Moreover, the intralayer hydrogen-bonding in each of the two layers is also possible. We suggest that in addition to strong surface adsorption, the interlayer and intralayer hydrogen‐bonding also increases the strength of the boundary films by enhancing the cohesion strength, thereby resulting in the high tribological performance of C12Amide-TEMPO. The findings in this study are expected to provide new hints for the optimal molecular design of OFMs.

Keywords

organic friction modifiers (OFMs)TEMPOfriction and wearsurface adsorptionmolecular reactivityboundary lubrication

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Friction
Volume 11 Issue 2,
February 2023
Pages 316-332
DOI: 10.1007/s40544-022-0610-0
Cite this article:
HOU J, TSUKAMOTO M, HOR S, et al. Molecules with a TEMPO-based head group as high-performance organic friction modifiers. Friction, 2023, 11(2): 316-332. https://doi.org/10.1007/s40544-022-0610-0

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Received: 25 November 2021
Revised: 18 January 2022
Accepted: 19 February 2022
Published: 25 May 2022
© The author(s) 2022.

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