Processing and interpretation of core‐electron XPS spectra of complex plasma‐treated polyethylene‐based surfaces using a theoretical peak model

Marc Bruggeman, Mischa Zelzer, Hanshan Dong, Artemis Stamboulis

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Interpretation of X-ray photoelectron spectroscopy (XPS) spectra of complex material surfaces, such as those obtained after surface plasma treatment of polymers, is confined by the available references. The limited understanding of the chemical surface composition may impact the ability to determine suitable coupling chemistries used for surface decoration or assess surface-related properties like biocompatibility. In this work, XPS is used to investigate the chemical composition of various ultra-high-molecular-weight polyethylene (UHMWPE) surfaces. UHMWPE doped with α-tocopherol or functionalised by active screen plasma nitriding (ASPN) was investigated as a model system. Subsequently, a more complex combined system obtained by ASPN treatment of α-tocopherol doped UHMWPE was investigated. Through ab initio orbital calculations and by employing Koopmans' theorem, the core-electron binding energies (CEBEs) were evaluated for a substantial number of possible chemical functionalities positioned on PE-based model structures. The calculated ΔCEBEs showed to be in reasonable agreement with experimental reference data. The calculated ΔCEBEs were used to develop a material-specific peak model suitable for the interpretation of merged high-resolution C 1 s, N 1 s and O 1 s XPS spectra of PE-based materials. In contrast to conventional peak fitting, the presented approach allowed the distinction of functionality positioning (i.e. centred or end-chain) and evaluation of the long-range effects of the chemical functionalities on the PE carbon backbone. Altogether, a more detailed interpretation of the modified UHMWPE surfaces was achieved whilst reducing the need for manual input and personal bias introduced by the spectral analyst.
Original languageEnglish
Pages (from-to)986-1007
Number of pages22
JournalSurface and Interface Analysis
Issue number9
Early online date28 May 2022
Publication statusPublished - Sept 2022

Bibliographical note

Funding Information:
All authors would like to thank Dr Mark Isaacs, for the acquisition of the XPS data at the EPSRC HarwellXPS facility. M.B. would like to thank the School of Metallurgy and Materials at the University of Birmingham for providing a studentship. M.B. and A.S. would also like to thank the NIHR SRMRC at the University of Birmingham as well as the Marie Sklodowska Curie ITN AIMed under the grant agreement 861138 for providing further funding.

Publisher Copyright:
© 2022 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd.


  • ASPN
  • plasma nitriding
  • polyethylene
  • XPS
  • α-tocopherol


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