Critical remarks on chemical derivatization analysis of plasma‐treated polymer surfaces and plasma polymers. Issue 12 (21st November 2016)

• Record Type: Journal Article
• Authors: Klages, Claus‐Peter; Kotula, Stefan
• Other Names: Laroussi Mounir guestEditor.; Bogaerts Annemie guestEditor.; Barekzi Nazir guestEditor.
• Is Part Of: Plasma processes and polymers. Volume 13:Issue 12(2016)
• Page Start: 1213
• Page End: 1223
• Publication Date: 2016-11-21
• Subjects: aldehyde -- amine -- amino -- derivatization -- ATR FT‐IR -- imine -- imino -- selective -- selectively -- selectivity -- TFAA -- TFBA -- XPS; Plasma polymerization -- Periodicals; Plasma-enhanced chemical vapor deposition -- Periodicals; Plasma chemistry -- Periodicals
• DOI: 10.1002/ppap.201600210
• Languages: English
• ISSNs: 1612-8850

Abstract

Abstract : The notion that individual functional groups on plasma‐modified polymer surfaces or in plasma polymers can be detected and quantified using selectively reacting derivatization reagents has dominated the field of plasma‐based surface technology since more than 30 years. For nitrogenated films and surfaces it has traditionally been believed that amino groups can be analyzed selectively using electrophilic reagents such as benzaldehydes or carboxylic acid anhydrides. This article presents arguments indicating that traditionally applied methodologies are partially based on myths. Presumed amino groups are – at least to a substantial extent – probably in fact other nitrogen‐bearing moieties. It is open to question if primary or secondary amino groups could "survive" the physico‐chemical environment typical of a plasma at all. Advancing the chemical understanding of N‐containing plasma‐generated films and surfaces, and plasma‐chemical formation mechanisms requires rethinking the interpretation of derivatization experiments. Abstract : The traditional belief that amino groups of plasma‐treated polymer surfaces or plasma polymers can be quantified using derivatization with "amino‐selective" reagents is a myth. Amino group concentrations in the literature must generally be considered to include substantial contributions from other nitrogen‐containing groups, e.g., imines. It is questionable if amino groups are stable against plasma or VUV exposure at all. Advancing the understanding of plasma‐generated films and surfaces requires new approaches such as FT‐IR spectroscopy combined with H/D isotope exchange.