Green Alternatives to Zinc Dialkyldithiophosphates: Vanadium Oxide Based Additives

Andrew Johnson; Elizabeth Willneff; Sven Schroeder; Anne Neville; Callum Sweeney; Joshua J. Smith; Kathyola Thokozile; James Parish; Andrew Straiton; Ardian Morina

doi:10.1021/acsaenm.3c00425

Green Alternatives to Zinc Dialkyldithiophosphates: Vanadium Oxide Based Additives

Andrew Johnson, Elizabeth Willneff, Sven Schroeder, Anne Neville, Callum Sweeney, Joshua J. Smith, Kathyola Thokozile, James Parish, Andrew Straiton, Ardian Morina

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Abstract

We demonstrate here that a functionalized vanadyl(IV) acety-lacetonate (acac) complex is a superior and highly effective antiwear agent, affording remarkable wear protection compared to the current industry standard, zinc dialkyldithiophosphates (ZDDPs). Analysis of vanadium speciation and the depth profile of the active tribofilms by a combination of X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) indicated a mixed va-lence oxide composite, comprising V(III), V(IV) and V(V) species. A marked difference in composition between the bulk and the sur-face of the tribofilms was found. The vanadyl(VI) acac precursor has the potential to reduce the use of, or even replace, ZDDP, which would represent a paradigm shift in antiwear agent design. A major benefit relative to ZDDPs is the absence of S and P moieties, eliminating the potential for forming noxious and environmentally harmful by-products of these elements.

Original language	English
Journal	ACS Applied Engineering Materials
Early online date	31 Oct 2023
DOIs	https://doi.org/10.1021/acsaenm.3c00425
Publication status	Published - 31 Oct 2023

Bibliographical note

This manuscript is dedicated to the memory of Prof. Anne Neville (1970−2022). The authors thank the Diamond Light Source for the award of beamtime at I18 and B07 under proposal numbers SP28437 and SI29334. Infineum UK Ltd. is thanked for the provision of PhD studentships for A.J.S. and C.S. and PDRA funding for J.D.P. and T.A.K. We gratefully acknowledge EPSRC support for T.A.K. through the University of Leeds Impact Acceleration Account (EP/R511717/1). A.L.J. wishes to thank the Department of Chemistry at the University of Bath. S.L.M.S. was financially supported by EPSRC through the Future Continuous Manufacturing and Advanced Crystallization (CMAC) Hub (EP/P006965/1) as well as through the Royal Academy of Engineering Bragg Centenary Chair supported by the Diamond Light Source and Infineum UK Ltd. The authors would also like to thank Stuart L. Micklethwaite (University of Leeds), Zabeeda P. Aslam (University of Leeds), Chun Wang (University of Leeds), Paul T. Edwards (University of Leeds), James M. Bucag (University of Leeds), and Stuart A. Bartlett (Diamond Light Source) for their help collecting the SEM–EDX, TEM, AFM, NEXAFS, and XANES data.

Keywords

Antiwear Additives
Molecular Structures
Zirconium
Titanium
Vanadium
metal oxide

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title = "Green Alternatives to Zinc Dialkyldithiophosphates: Vanadium Oxide Based Additives",

abstract = "We demonstrate here that a functionalized vanadyl(IV) acety-lacetonate (acac) complex is a superior and highly effective antiwear agent, affording remarkable wear protection compared to the current industry standard, zinc dialkyldithiophosphates (ZDDPs). Analysis of vanadium speciation and the depth profile of the active tribofilms by a combination of X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) indicated a mixed va-lence oxide composite, comprising V(III), V(IV) and V(V) species. A marked difference in composition between the bulk and the sur-face of the tribofilms was found. The vanadyl(VI) acac precursor has the potential to reduce the use of, or even replace, ZDDP, which would represent a paradigm shift in antiwear agent design. A major benefit relative to ZDDPs is the absence of S and P moieties, eliminating the potential for forming noxious and environmentally harmful by-products of these elements.",

keywords = "Antiwear Additives, Molecular Structures, Zirconium, Titanium, Vanadium, metal oxide",

author = "Andrew Johnson and Elizabeth Willneff and Sven Schroeder and Anne Neville and Callum Sweeney and Smith, {Joshua J.} and Kathyola Thokozile and James Parish and Andrew Straiton and Ardian Morina",

note = "This manuscript is dedicated to the memory of Prof. Anne Neville (1970−2022). The authors thank the Diamond Light Source for the award of beamtime at I18 and B07 under proposal numbers SP28437 and SI29334. Infineum UK Ltd. is thanked for the provision of PhD studentships for A.J.S. and C.S. and PDRA funding for J.D.P. and T.A.K. We gratefully acknowledge EPSRC support for T.A.K. through the University of Leeds Impact Acceleration Account (EP/R511717/1). A.L.J. wishes to thank the Department of Chemistry at the University of Bath. S.L.M.S. was financially supported by EPSRC through the Future Continuous Manufacturing and Advanced Crystallization (CMAC) Hub (EP/P006965/1) as well as through the Royal Academy of Engineering Bragg Centenary Chair supported by the Diamond Light Source and Infineum UK Ltd. The authors would also like to thank Stuart L. Micklethwaite (University of Leeds), Zabeeda P. Aslam (University of Leeds), Chun Wang (University of Leeds), Paul T. Edwards (University of Leeds), James M. Bucag (University of Leeds), and Stuart A. Bartlett (Diamond Light Source) for their help collecting the SEM–EDX, TEM, AFM, NEXAFS, and XANES data.",

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day = "31",

doi = "10.1021/acsaenm.3c00425",

language = "English",

journal = "ACS Applied Engineering Materials",

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T1 - Green Alternatives to Zinc Dialkyldithiophosphates

T2 - Vanadium Oxide Based Additives

AU - Johnson, Andrew

AU - Willneff, Elizabeth

AU - Schroeder, Sven

AU - Neville, Anne

AU - Sweeney, Callum

AU - Smith, Joshua J.

AU - Thokozile, Kathyola

AU - Parish, James

AU - Straiton, Andrew

AU - Morina, Ardian

N1 - This manuscript is dedicated to the memory of Prof. Anne Neville (1970−2022). The authors thank the Diamond Light Source for the award of beamtime at I18 and B07 under proposal numbers SP28437 and SI29334. Infineum UK Ltd. is thanked for the provision of PhD studentships for A.J.S. and C.S. and PDRA funding for J.D.P. and T.A.K. We gratefully acknowledge EPSRC support for T.A.K. through the University of Leeds Impact Acceleration Account (EP/R511717/1). A.L.J. wishes to thank the Department of Chemistry at the University of Bath. S.L.M.S. was financially supported by EPSRC through the Future Continuous Manufacturing and Advanced Crystallization (CMAC) Hub (EP/P006965/1) as well as through the Royal Academy of Engineering Bragg Centenary Chair supported by the Diamond Light Source and Infineum UK Ltd. The authors would also like to thank Stuart L. Micklethwaite (University of Leeds), Zabeeda P. Aslam (University of Leeds), Chun Wang (University of Leeds), Paul T. Edwards (University of Leeds), James M. Bucag (University of Leeds), and Stuart A. Bartlett (Diamond Light Source) for their help collecting the SEM–EDX, TEM, AFM, NEXAFS, and XANES data.

PY - 2023/10/31

Y1 - 2023/10/31

N2 - We demonstrate here that a functionalized vanadyl(IV) acety-lacetonate (acac) complex is a superior and highly effective antiwear agent, affording remarkable wear protection compared to the current industry standard, zinc dialkyldithiophosphates (ZDDPs). Analysis of vanadium speciation and the depth profile of the active tribofilms by a combination of X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) indicated a mixed va-lence oxide composite, comprising V(III), V(IV) and V(V) species. A marked difference in composition between the bulk and the sur-face of the tribofilms was found. The vanadyl(VI) acac precursor has the potential to reduce the use of, or even replace, ZDDP, which would represent a paradigm shift in antiwear agent design. A major benefit relative to ZDDPs is the absence of S and P moieties, eliminating the potential for forming noxious and environmentally harmful by-products of these elements.

AB - We demonstrate here that a functionalized vanadyl(IV) acety-lacetonate (acac) complex is a superior and highly effective antiwear agent, affording remarkable wear protection compared to the current industry standard, zinc dialkyldithiophosphates (ZDDPs). Analysis of vanadium speciation and the depth profile of the active tribofilms by a combination of X-ray absorption near-edge structure (XANES), X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) indicated a mixed va-lence oxide composite, comprising V(III), V(IV) and V(V) species. A marked difference in composition between the bulk and the sur-face of the tribofilms was found. The vanadyl(VI) acac precursor has the potential to reduce the use of, or even replace, ZDDP, which would represent a paradigm shift in antiwear agent design. A major benefit relative to ZDDPs is the absence of S and P moieties, eliminating the potential for forming noxious and environmentally harmful by-products of these elements.

KW - Antiwear Additives

KW - Molecular Structures

KW - Zirconium

KW - Titanium

KW - Vanadium

KW - metal oxide

U2 - 10.1021/acsaenm.3c00425

DO - 10.1021/acsaenm.3c00425

M3 - Article

SN - 2771-9545

JO - ACS Applied Engineering Materials

JF - ACS Applied Engineering Materials

ER -

Green Alternatives to Zinc Dialkyldithiophosphates: Vanadium Oxide Based Additives

Abstract

Bibliographical note

Keywords

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