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

Jinchi HOU; Masaki TSUKAMOTO; Seanghai HOR; Xingyu CHEN; Juntao YANG; Hedong ZHANG; Nobuaki KOGA; Koji YASUDA; Kenji FUKUZAWA; Shintaro ITOH; Naoki AZUMA

doi:10.1007/s40544-022-0610-0

Friction 2023, 11(2): 316-332 https://doi.org/10.1007/s40544-022-0610-0

Research Article |

Open Access | Issue | Published: 25 May 2022

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

Show Author's Information Hide Author's Information Jinchi HOU^¹, Masaki TSUKAMOTO^¹, Seanghai HOR^¹, Xingyu CHEN^¹, Juntao YANG^¹, Hedong ZHANG^¹(

), Nobuaki KOGA^¹, Koji YASUDA^², Kenji FUKUZAWA^³, Shintaro ITOH^³, Naoki AZUMA^³

1 Department of Complex Systems Science, Graduate School of Informatics, Nagoya University, Nagoya 464-8601, Japan

2 Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8601, Japan

3 Department of Micro-Nano Systems Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan

Keywords:

boundary lubrication, friction and wear, surface adsorption, organic friction modifiers (OFMs), TEMPO, molecular reactivity

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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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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.

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About this article

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

Show Author's information Hide Author's Information Jinchi HOU^¹, Masaki TSUKAMOTO^¹, Seanghai HOR^¹, Xingyu CHEN^¹, Juntao YANG^¹, Hedong ZHANG^¹(

), Nobuaki KOGA^¹, Koji YASUDA^², Kenji FUKUZAWA^³, Shintaro ITOH^³, Naoki AZUMA^³

1 Department of Complex Systems Science, Graduate School of Informatics, Nagoya University, Nagoya 464-8601, Japan

2 Institute of Materials and Systems for Sustainability, Nagoya University, Nagoya 464-8601, Japan

3 Department of Micro-Nano Systems Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan

Abstract

Keywords: boundary lubrication, friction and wear, surface adsorption, organic friction modifiers (OFMs), TEMPO, molecular reactivity

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Received: 25 November 2021

Revised: 18 January 2022

Accepted: 19 February 2022

Published: 25 May 2022

Issue date: February 2023

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Acknowledgements

This work was supported in part by JSPS KAKENHI Grant (Nos. 19K21915 and 21H01238), JST Adaptable and Seamless Technology Transfer Program through Target-driven R&D (No. JPMJTM19FN), and NSK Foundation for Mechatronics Technology Advancement. We thank Dr. Kin-ichi OYAMA (Research Center for Materials Science, Nagoya University) for mass spectrometry analysis of the synthesized OFMs and associate professor Takayuki TOKOROYAMA (Graduate School of Engineering, Nagoya University) for the help with wear scar measurements. Jinchi HOU is grateful for the financial support from the China Scholarship Council (No. 202006030017).

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