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IR- and NEXAFS-spectroscopic characterization of plasma-nitrogenated polyolefin surfaces

  • Modification of polyethylene and polypropylene surfaces by atmospheric-pressure plasmas using mixtures of nitrogen and hydrogen was studied using Fouriertransform infrared spectroscopy in the attenuated total reflection mode (FTIR-ATR) and by near-edge x-ray absorption fine structure spectroscopy (NEXAFS) in order to shed some light on the chemical nature of nitrogen-containing functional Groups on the polymer surface. Using FTIR-ATR spectroscopy combined with hydrogendeuterium isotope exchange of active hydrogen atoms, it was shown that the direct treatment of PE foils by dielectric barrier discharges (DBDs) in N2/H2 mixtures and a subsequent exposure of the samples to the ambient air results in the formation of –NH2 moieties of primary amides on the polymer surface. Corresponding in situ experiments with streaming N2/H2 DBD post-discharges virtually free of H2O and O2, on the other hand, showing the absence of –NH2, proving that no primary amines or amides are formed by thisModification of polyethylene and polypropylene surfaces by atmospheric-pressure plasmas using mixtures of nitrogen and hydrogen was studied using Fouriertransform infrared spectroscopy in the attenuated total reflection mode (FTIR-ATR) and by near-edge x-ray absorption fine structure spectroscopy (NEXAFS) in order to shed some light on the chemical nature of nitrogen-containing functional Groups on the polymer surface. Using FTIR-ATR spectroscopy combined with hydrogendeuterium isotope exchange of active hydrogen atoms, it was shown that the direct treatment of PE foils by dielectric barrier discharges (DBDs) in N2/H2 mixtures and a subsequent exposure of the samples to the ambient air results in the formation of –NH2 moieties of primary amides on the polymer surface. Corresponding in situ experiments with streaming N2/H2 DBD post-discharges virtually free of H2O and O2, on the other hand, showing the absence of –NH2, proving that no primary amines or amides are formed by this treatment although substantial amounts of nitrogen are incorporated. Moreover, directly N2/H2-plasma-treated polymer surfaces, similar to afterglow-treated low-density polyethylene (LDPE), show amphiphilic character as to be seen by chemical derivatization with nucleophilic reagents 4-(trifluoromethyl) phenylhydrazine and 4-(trifluoromethyl)benzylamine, in addition to electrophilic aromatic aldehydes normally used to derivatize such surfaces. The presence of imines or other functional groups with CN moieties which may be invoked to explain the dual (amphiphilic) reactivity is proven by NEXAFS studies on ultrathin plasma-treated PE films, confirming significant amounts of nitrogen in CN bonds and carbon in CC bonds.zeige mehrzeige weniger

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Metadaten
Autor*innen:Z. Khosravi, S. Kotula, Andreas Lippitz, Wolfgang UngerORCiD, C.-P. Klages
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):Plasma Processes and Polymers
Jahr der Erstveröffentlichung:2017
Verlag:WILEY-VCH Verlag GmbH & Co. KGaA,
Verlagsort:Weinheim
Jahrgang/Band:15
Ausgabe/Heft:1
Erste Seite:e1700066, 1
Letzte Seite:15
DDC-Klassifikation:Naturwissenschaften und Mathematik / Chemie / Analytische Chemie
Freie Schlagwörter:IR spectroscopy; NEXAFS; Plasma-nitrogenated polyolefin surfaces; Unsaturated CN bonds; X-ray spectroscopy
DOI:10.1002/ppap.201700066
ISSN:1612-8869
ISSN:1612-8850
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:16.01.2018
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:29.01.2018
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