TY - THES A1 - Wettmarshausen, Sascha T1 - Hoch selektive Polyolefin-Oberflächenfunktionalisierung in bromenthaltenden Niederdruckplasmen: Untersuchungen zur Pfropfung, Umfunktionalisierung und Verbesserung der Hafteigenschaften in Metall-Polymer-Verbunden N2 - Selektiv funktionalisierte Oberflächen von Polyolefinen sind für verschiedenste Einsatzgebiete wie Adhäsions-, Chemie-, Medizin- und Biotechnik von großem Interesse. Eine Möglichkeit Polymeroberflächen effizient zu funktionalisieren ist, diese durch eine plasmaphysikalisch angeregte Gasphase unter Einsatz geeigneter Präkursoren chemisch zu modifizieren. Im Rahmen der vorliegenden Arbeit wurde die Wirkung bromhaltiger Gasphasenplasmen, die Bromoform, Allybromid oder tert-Butylbromid enthielten, auf Polyethylen (PE) und Polypropylen (PP) untersucht. Überraschenderweise wurde hierbei eine hochselektive und hochdichte monosortige Br-Funktionalisierung beobachtet. Um die für diese hohe Selektivität verantwortlichen Prozesse zu untersuchen, wurden analoge halogenhaltige Plasmen, die Tetrafluormethan, Fluoroform, Chloroform, Bromoform und Diiodmethan enthielten, auf ihre chemische Selektivität, ihre Funktionalisierungseffizienz und ihr Ionisationspotential und Elektronentemperatur charakterisiert. Es wurde untersucht, ob die Halogenidfunktionalität als CX oder als C-CXn-Gruppe an der Oberfläche gebildet wird. Für die Bewertung der Langzeitstabilität der Funktionalisierung wurde die Nachoxidation der plasmamodifizierten Polymeroberflächen kontrolliert. Im Anschluss wurde die Umsetzbarkeit mit systematisch variierten organischen Verbindungen bestimmt. Ziel hierbei war zu untersuchen, wie gut sich die Bromidfunktionalität als universelle Abgangsgruppe zur Kopplung flexibilisierender Spacer- Moleküle in der Metall-Polymer-Grenzfläche eignet. Es wurden dazu Kopplungsreaktionen mit unterschiedlich langen und steifen endständigen Alkohol-, Amin- und Glykol- Verbindungen durchgeführt. Darüber hinaus wurden Umfunktionalisierungsreaktionen an bromierten Oberflachen durchgeführt. Auf diese Weise konnte gezeigt werden, dass es möglich ist, die C-Br- Funktionalität gegen eine andere auszutauschen. Spezielles Augenmerk wurde auf die Umfunktionalisierung zu primären Aminogruppen gelegt. Diese wurden über einfache Substitutionsreaktionen mit konzentriertem oder verflüssigtem Ammoniak erzeugt. Auch oberflachengebundene Hydroxylgruppen konnten erzeugt werden. Dazu wurden Bromidfunktionen durch Substitution mit Kalium- und Natriumhydroxid in geeigneten Lösungsmitteln umgesetzt. Polypropylenoberflächen, die mit verschiedenen Spacern ausgerüstet worden waren, wurden im Vakuum mit dünnen Filmen aus Aluminium und Kupfer bedampft. Die Haftfestigkeit dieser Beschichtung wurde anschließend durch Schalfestigkeitsmessungen untersucht. N2 - Selectively functionalized polyolefine surfaces are essential for many applications in adhesion, chemistry, medicine and biotechnology. To provide polymer surfaces with special functionalities it is necessary to treat them with according precursors in plasma. In this work polypropylene (PP) and polyethylene (PE) were exposed to bromine containing (bromoform, allylbromide, tert-butylbromide) plasmas. Surpisingly, the bromination appeared as high selective and formed high dense C-Br groups at the polyolefin surface. Halogen containing plasmas like tetrafluormethane, fluoroform, chloroform, bromoform and diiodinemethane were compared with regard to their selectivity, yield as well as ionisation potential and electron temperature of the corresponding plasma. It was also analysed if the halogens are bonded as C-X or C-CXn-fragments onto the surface. Moreover, the post-plasma oxidation stability was also investigated. Subsequently the brominated polyolefine surfaces were allowed to react with different organic compounds. The aim was to demonstrate the universality of the C-Br group for attaching of any OH and NH2 functional group containing molecule. Terminal alcohol, glycols and amines are used. Especially, flexibilizing spacers within the metal-polymer interface of different length, stiffness and functionality were introduced. Besides grafting of spacers it was also shown that it is possible to change the functionality of the surface. Concentrated or liquid ammonia should produce primary amino groups through a simple substitution. Hydroxyl groups were formed by hydrolysis using potassium hydroxide and sodium hydroxide in different solvents. The different grafted polypropylene surfaces were brought into vacuum and were metalized with copper or aluminium. The thus produced metal-polymer composite was then tested on the peel strengths of the evaporated metal film. T3 - BAM Dissertationsreihe - 48 KW - Plasma KW - Pfropfung KW - Funktionalisierung KW - Bromierung KW - Polymere PY - 2009 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-1100 SN - 978-3-9812910-4-9 SN - 1613-4249 VL - 48 SP - 1 EP - 139 PB - Bundesanstalt für Materialforschung und -prüfung (BAM) CY - Berlin AN - OPUS4-110 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Wettmarshausen, Sascha A1 - Meyer-Plath, Asmus A1 - Ziemann, Sylvia A1 - Hidde, Gundula A1 - Zeynalov, Eldar T1 - Plasmabromierung von graphitischen Materialien - Kovalente Anbindung organischer Moleküle N2 - Die hochselektive und ausbeutereiche plasmachemische Bromierung von Polyolefinoberflächen wurde auf graphitische Materialien übertragen. Oberflächen von graphenartigem Highly Oriented Pyrolytic Graphite (HOPG), natürlichem Graphit, mehrwandige Kohlenstoffnanoröhren (MWCNT) sowie Kohlenstoff-Fasern wurden im Bromdampfplasma behandelt. Während die Bromierung von Polyolefinoberflächen als radikalische Wasserstoffabstraktion mit nachfolgender Addition (Rekombination) oder durch nucleophile Substitution an sp³-hybridisierten C-Atomen abläuft, können graphitische Strukturen sowohl an sp³-hybridisierten Strukturdefekten als auch durch elektrophile Addition an vollständig C-substituierte aromatische Doppelbindungen bromiert werden. Dabei werden die planaren (graphitischen) sp²-C-Atome in die tetraedrische sp³-Hybridisierung umgewandelt und zu elektrisch nichtleitenden Strukturen gefaltet. Die maximalen Bromausbeuten bei Verwendung von Brom als Plasmamedium lagen je nach Substrat zwischen 10–50% Br/C, mit Bromoform deutlich darüber, was durch Kombinationen von Bromoform mit Brom oder Allylbromid mit Bromoform durch Schichtbildung auf über 70% Br/C gesteigert werden konnte. An die C-Br-Gruppen wurden nasschemisch verschiedene Amine nucleophil gepfropft. Die Pfropfausbeuten von 1–10 Moleküle je 100 C lagen deutlich niedriger als die erreichten Pfropfgrade von etwa 1–22 Moleküle je 100 C-Atome an Polyolefinoberflächen. Da nach der chemischen Pfropfung nahezu alle nichtgepfropften Br-Gruppen verschwunden waren, muss auf eine bevorzugte Rekonstruktion der planaren sp²-Graphitschicht geschlossen werden. KW - Polymerbromierung PY - 2012 U6 - https://doi.org/10.1002/vipr.201200481 SN - 0947-076X SN - 1522-2454 VL - 24 IS - 1 SP - 24 EP - 29 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-25518 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wettmarshausen, Sascha A1 - Meyer-Plath, Asmus A1 - Friedrich, Jörg F. T1 - Funktionalisierung von Polymeroberflächen mit anschließender Pfropfung und Derivatisierung T2 - 14. Workshop Oberflächentechnologie mit Plasma- und Ionenstrahlprozessen CY - Klingenthal, Germany DA - 2007-03-13 PY - 2007 AN - OPUS4-15346 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Wettmarshausen, Sascha T1 - A new concept for adhesion promotion in metal-polymer systems by introduction of covalently bonded spacers at the interface N2 - A new concept for molecular interface design in metal-polymer systems is presented. The main features of this concept are the replacement of weak physical interactions by strong covalent bonds, the flexibilization of the interface for compensating different thermal expansions of materials by using long-chain flexible and covalently bonded spacers between the metal and the polymer as well as its design as a moisture-repellent structure for hindering diffusion of water molecules into the interface and hydrolysis of chemical bonds. For this purpose, the main task was to develop plasmachemical and chemical techniques for equipping polymer surfaces with monotype functional groups of adjustable concentration. The establishing of monotype functional groups allows grafting the functional groups by spacer molecules by applying usual wet-chemical reactions. Four processes were favoured for production of monotype functional groups by highly selective reactions: the plasma bromination, the plasma deposition of plasma polymers, the post-plasma chemical reduction of O-functionalities to OH-groups, and the chemical replacement of bromine groups by NH2-groups. The grafting of flexible organic molecules as spacers between the metal layer and polymer improved the peel strength of the metal. To obtain maximal peel strength of aluminium coatings to polypropylene films and occurrence of cohesive failure in the polypropylene substrate, about 27 OH groups per 100 C-atoms or 6 COOH groups per 100 C-atoms were needed. Introducing C6-11-aliphatic spacers 1 OH or COOH group per 100 C-atoms contributed about 60% of the maximal peel strength of the Al-PP system, i.e. 2 or 3 spacer molecules per 100 C-atoms were sufficient for maximal peel strength. KW - Polymer surface functionalization KW - Spacer grafting KW - Metal-polymer adhesion PY - 2008 U6 - https://doi.org/10.1163/156856108X309611 SN - 0169-4243 SN - 1568-5616 VL - 22 IS - 10-11 SP - 1123 EP - 1143 PB - VNU Science Press CY - Utrecht AN - OPUS4-17741 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Schulze, Rolf-Dieter A1 - Meyer-Plath, Asmus A1 - Joshi, Ranjit A1 - Wettmarshausen, Sascha T1 - New Plasma Techniques for Polymer Surface Modification with Monotype Functional Groups N2 - The production of chemically-defined plasma polymers and the introduction of monotype functional groups onto polymer surfaces are described. One method is to lower the energetic level of low-pressure plasmas. Pressure- and plasma-pulsed plasmas were successfully tested for the production of chemically-defined plasma polymers by increasing the monomer supply during the plasma-off period. Well-defined ultra-thin polymer films with regular structure were deposited from atmospheric plasmas by electrospray techniques. Post-plasma wet-chemical processing was also applied, as were gas/liquid-based aerosols and underwater plasmas. KW - Plasma KW - Polymer-Oberflächenfunktionalisierung KW - Macromolecular plasma KW - Monotype functional groups KW - Plasma bromination KW - Plasma treatment KW - Pressure-pulsed plasma KW - Underwater plasma PY - 2008 U6 - https://doi.org/10.1002/ppap.200700145 SN - 1612-8850 SN - 1612-8869 VL - 5 IS - 5 SP - 407 EP - 423 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-17742 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wettmarshausen, Sascha A1 - Kühn, Gerhard A1 - Hidde, Gundula A1 - Mittmann, Hans-Ulrich A1 - Friedrich, Jörg Florian T1 - Plasmabromination - the Selective Way to Monotype Functionalized Polymer Surfaces N2 - In contrast to other plasma modification processes of polymer surfaces, the bromination is very selective and shows a high yield in C—Br groups. The most convenient bromination process was found using bromoform, which was thus preferred to elemental bromine, allyl bromide, vinyl bromide or tert-butylbromide. The bromoform process give yields in C—Br up to 40 C—Br or more, with only 2-3% co-introduction of O-functionalities whereas allyl bromide results in yields of about 20 C—Br and more, but in more than 10% oxygen-containing by-products. C—Br groups serve as anchoring points for grafting of molecules, oligomers and pre-polymers of diole or diamine character. KW - Functional groups KW - Grafting KW - Plasma bromination KW - Polymer surfaces KW - Selective plasma process KW - Spacer PY - 2007 U6 - https://doi.org/10.1002/ppap.200700019 SN - 1612-8850 SN - 1612-8869 VL - 4 IS - 9 SP - 832 EP - 839 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-16209 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Wettmarshausen, Sascha A1 - Sturm, Heinz ED - Tachibana, K. ED - Takai, O. T1 - A new concept of adhesion promotion in metal-polymer composites by introduction of covalently bonded hydrophobic spacers at interface T2 - Proceedings of the 18th International Symposium on Plasma Chemistry (ISPC-18) CY - Kyoto, Japan DA - 2007-08-26 PY - 2007 SN - 978-4-9903773-4-2 SP - 27A EP - p5, 1 PB - International Union of Pure and Applied Chemistry CY - Kyoto AN - OPUS4-20668 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Wettmarshausen, Sascha A1 - Meyer-Plath, Asmus A1 - Friedrich, Jörg F. A1 - Hanelt, Sven A1 - Mix, Renate A1 - Mach, Reinhard A1 - Zeynalov, Eldar T1 - Plasma chemical bromination, functionalization and grafting of organic molecules onto graphene-like carbon materials T2 - PSE 2010 CY - Garmisch-Partenkirchen, Germany DA - 2010-09-13 PY - 2010 AN - OPUS4-22108 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Wettmarshausen, Sascha A1 - Hennecke, Manfred T1 - Haloform plasma modification of polyolefin surfaces N2 - Polyolefin surfaces (polyethylene and polypropylene) were exposed to haloform (CHX3) plasmas for introduction of monosort halogen groups. Bromoform and chloroform plasmas produced selectively C-Br (100 Br/100 C) and C-Cl (200 Cl/100 C) groups in high yields. The bromoform plasma showed 1-3 and the chloroform plasma 2-7 post-plasma introduced O-functionalities per 100 C. The polyolefin C-Br groups were grafted wet-chemically or by exposure to the vapour of amines, diols and glycols. Thus, spacer molecules could be covalently bonded to maximal 15 spacer molecules per 100 C for the smallest grafted molecules and 1.2 molecules/100 C for larger molecules as octaaminophenylene-POSS. After metal evaporation the end groups of these polymer-bonded spacer molecules formed also covalent bonds to the metal. Thus, flexible, hydrophobic and barrier elements were introduced into the polymer-metal interfaces for high-impact, high-durable and water-resistant metal-polymer composites as measured by means of peel strengths. KW - Bromination KW - Chlorination KW - Selective plasma processes KW - Spacer grafting PY - 2009 U6 - https://doi.org/10.1016/j.surfcoat.2009.05.050 SN - 0257-8972 VL - 203 IS - 23 SP - 3647 EP - 3655 PB - Elsevier Science CY - Lausanne AN - OPUS4-23204 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Heise, C. A1 - Schedler, U. A1 - Wettmarshausen, Sascha A1 - Friedrich, Jörg Florian T1 - Plasma-brominated cyclo-olefin polymer slides: Suiitable macroinitiators for activator regenerated by electron transfer/atom radical transfer polymerization N2 - Activators regenerated by electron transfer–atom radical transfer polymerization (ATRP) as a controlled living polymerization are distinguished by their acceptance of small amounts of transition-metal complexes and oxygen and by their tolerance of reducing agents at a high concentration. The precondition of all ATRP applications is the use of homolytic or heterolytic cleavable halides as a dormant species; this allows the propagation of monomer chains. Hence, alkyl bromides are slightly cleavable and are the preferred initiators for ATRP. The bromination of polymer slides used as macroinitiators was carried out under gentle bromoform plasma conditions. This led to an oxidation-resistant stable bromine layer. More than 20 bromines per 100 carbons on the polymer scaffold were permanently bound to the substrate after plasma treatment. The resulting amounts of secondary and tertiary bromines on the polymer scaffold exhibited a suitable macroinitiator concentration for the surface-initiated polymerization of methyl methacrylate and glycidyl methacrylate. KW - Copolymers KW - Functionalization of polymers KW - Grafting KW - Monolayers and polymer brushes KW - Radical polymerization PY - 2014 UR - http://onlinelibrary.wiley.com/doi/10.1002/app.40662/full U6 - https://doi.org/10.1002/APP.40662 SN - 0021-8995 SN - 1097-4628 VL - 131 IS - 16 SP - 40662-1 EP - 40662-10 PB - Wiley InterScience CY - Hoboken, NJ AN - OPUS4-30577 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Wettmarshausen, Sascha A1 - Mix, Renate A1 - Meyer-Plath, Asmus A1 - Mittmann, Hans-Ulrich A1 - Friedrich, Jörg Florian ED - K.L. Mittal, T1 - Plasma Bromination - a selective way to monotype functionalized polymer surfaces KW - Functional groups KW - Polymer surfaces KW - Plasma bromination KW - Grafting KW - Spacer KW - Selective plasma process PY - 2009 SN - 978-90-04-16590-8 VL - 5 SP - 3 EP - 18 PB - Koninklijke Brill NV CY - Leiden, The Netherlands AN - OPUS4-18944 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Wettmarshausen, Sascha A1 - Hanelt, Sven A1 - Mach, Reinhard A1 - Mix, Renate A1 - Zeynalov, Eldar A1 - Meyer-Plath, Asmus T1 - Plasma-chemical bromination of graphitic materials and its use for subsequent functionalization and grafting of organic molecules N2 - Plasma-chemical bromination has been shown to be well-suited for highly selective and efficient C–Br-functionalization of polyolefin surfaces and has now been applied to graphitic materials, including highly oriented pyrolytic graphite (HOPG), natural graphite, carbon nanotubes, and graphitized carbon fibres. In contrast to the radical substitution of hydrogen by bromine at hydrogen-terminated sp3-hybridized carbon, bromination of all-carbon bound sp2-hybridized carbon in graphene requires addition to aromatic double bonds. The related change of sp2 to sp3 hybridization of the carbon atoms involved helps to explain experimental results of a loss in surface planarity on brominated HOPG. Bromine concentrations of up to 50 bromine atoms per 100 C-atoms were achieved in elemental bromine vapour under low-pressure plasma conditions using low-energetic inductively coupled radio-frequency plasma excitation. The time scale of the bromination progress was found to increase with the specific surface area of the material. The results of plasma-chemical bromination are compared to that of wet-chemical electrophilic addition reactions, which achieved 28 Br per 100 C for MWCNT. The resulting C–Br bonds from plasma-chemical processing of graphitic materials were shown to be well-suited for hydroxyl functionalization and for grafting of organic molecules by nucleophilic substitution with 1,6-diaminohexane and (3-aminopropyl)triethoxysilane. PY - 2010 U6 - https://doi.org/10.1016/j.carbon.2010.06.054 SN - 0008-6223 SN - 1873-3891 VL - 48 IS - 13 SP - 3884 EP - 3894 PB - Pergamon Press CY - New York, NY AN - OPUS4-21954 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wettmarshausen, Sascha A1 - Min, Hyegeun A1 - Unger, Wolfgang A1 - Jäger, Christian A1 - Hidde, Gundula A1 - Friedrich, Jörg Florian T1 - Significance of hydrogen-deuterium exchange at polyolefin surfaces on exposure to ammonia low-pressure plasma N2 - Since more than 40 years ammonia plasma exposure of polyolefins is used for introduction of primary amino groups. The selectivity of this reaction and the yield in primary amino groups was found to be low. Here, a prominent side-reactions of this process was investigated, the hydrogenation by NH3 plasma. For identification of hydrogenation ammonia (NH3) and deuterated ammonia (ND3) were exposed to Polyethylene (h-PE) and fully deuterated polyethylene (d-PE) as well as hexatriacontane (h-HTC) and fully deuterated hexatriacontane (d-HTC) as low-molecular weight model for PE. H–D exchange was assumed and detected by Time-of-Flight Secondary Ion Mass Spectrometry (ToF–SIMS), X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance (ATR-FTIR) and 1H and 2H Nuclear magnetic Resonance. Results show a significant H–D exchange within the sampling depth of ATR (2.5 µm). However, N- and NH2 introduction was limited to the topmost surface as shown by SIMS and XPS (a few nanometers). KW - Deuterated ammonia KW - Ammonia plasma KW - Deuterated polyolefins KW - Hexatriacontane KW - H-D exchange PY - 2011 U6 - https://doi.org/10.1007/s11090-011-9304-5 SN - 0272-4324 VL - 31 IS - 4 SP - 551 EP - 572 PB - Plenum Publ. Corp. CY - New York, NY, USA AN - OPUS4-24178 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Wettmarshausen, Sascha A1 - Hennecke, Manfred T1 - Neue Molekülarchitekturen an Polyolefinoberflächen T2 - 17. Neues Dresdner Vakuumtechnisches Kolloquium - Beschichtung, Modifizierung und Charakterisierung von Polymeroberflächen CY - Dresden, Deutschland DA - 2009-10-21 KW - Plasma KW - Bromierung KW - Spacer KW - Haftvermittler KW - Metallbedampfung KW - Schälfestigkeit PY - 2009 SN - 978-3-9812550-1-0 SP - 38 EP - 40 AN - OPUS4-20250 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Wettmarshausen, Sascha ED - G. Blasek, T1 - Generelle thermodynamische Probleme bei der Funktionalisierung von Polyolefinoberflächen T2 - 17. Neues Dresdner Vakuumtechnisches Kolloquium - Beschichtung, Modifizierung und Charakterisierung von Polymeroberflächen CY - Dresden, Deutschland DA - 2009-10-21 KW - Plasma KW - Bromierung KW - Spacer KW - Haftvermittler KW - Metallbedampfung KW - Schälfestigkeit KW - Thermodynamik PY - 2009 SN - 978-3-9812550-1-0 SP - 65 EP - 67 AN - OPUS4-20251 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Min, Hyegeun A1 - Wettmarshausen, Sascha A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang T1 - A ToF-SIMS study of the deuterium-hydrogen exchange induced by ammonia plasma treatment of polyolefins N2 - ToF-SIMS has been used to study the surface functionalization of polypropylene and polyethylene samples by exposure to low-pressure ammonia plasma. Static secondary ion mass spectrometry is an appropriate tool to determine hydrogen isotopes as elements and in fragment ions with high sensitivity and selectivity. Specifically the exchange of hydrogen isotopes and the incorporation of N-containing moieties in the near-surface layer of the polyolefins have been studied in ND3 plasma experiments with conventional polypropylene (h-PP) and polyethylene (h-PE) and NH3 plasma experiments with deuterated polyethylene (d-PE). Considering the exchange of hydrogen between the plasma and the polymer surface studied by using deuterated ammonia and polyolefin samples the conclusion has been derived that polypropylene with its side chain methyl groups is more susceptible to hydrogen exchange reactions. For ND3 plasma treatment of polyethylene and polypropylene similar N-containing fragments were obtained and the measured semi-quantitative ToF-SIMS N-uptake data are rather similar. The observation of a wide range of characteristic mixed CkNlHmDn+ secondary fragment ions suggests complex and manifold reaction pathways at the polymer–plasma interface besides simple grafting of –ND2 or –NH2 moieties formed by ammonia fragmentation in the plasma. Finally, indications of an isotopic effect for hydrogen isotopes in the plasma process have been observed by comparison of ND3/h-PE results with those of NH3/d-PE. KW - ToF-SIMS KW - Hydrogen-deuterium exchange KW - Ammonia plasma treatment KW - Amine-functionalized polymer KW - Polyolefins PY - 2011 U6 - https://doi.org/10.1039/c1ja10043b SN - 0267-9477 SN - 1364-5544 VL - 26 SP - 1157 EP - 1165 PB - Royal Society of Chemistry CY - London AN - OPUS4-23754 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wettmarshausen, Sascha A1 - Friedrich, Jörg Florian A1 - Meyer-Plath, Asmus A1 - Kalinka, Gerhard A1 - Hidde, Gundula A1 - Weidner, Steffen T1 - Coating of carbon fibers with adhesion-promoting thin poly(acrylic acid) and poly(hydroxyethylmethacrylate) layers using electrospray ionization N2 - Thin coatings of poly(acrylic acid) (PAA) and poly(hydroxyethylmethacrylate) (PHEMA) were deposited onto carbon fibers by means of the electrospray ionization (ESI) technique in ambient air. These high-molecular weight polymer layers were used as adhesion promoters in carbon fiber–epoxy resin composites. Within the ESI process, the carbon fibers were completely enwrapped with polymer in the upper 10 plies of a carbon fiber roving. As identified with scanning electron microscopy also shadowed fibers in a bundle as well as backsides of fiber rovings were pinhole-free coated with polymers (‘electrophoretic effect'). Under the conditions used, the layers have a granular structure. Residual solvent was absent in the deposit. PAA and PHEMA films did not show any changes in composition and structure in comparison with the original polymers as analyzed by X-ray photo-electron spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Single-fiber pullout tests of coated fibers embedded in epoxy resin showed significantly increased interfacial shear strength. It is assumed that chemical bonds between carbon fiber poly(acrylic acid) and epoxy resin contribute significantly to the improved interactions. KW - Adhesion promotion KW - Thin polymer layers KW - Electrospray ionization (ESI) KW - Carbon fiber–epoxy resin laminates KW - Layer topography PY - 2015 U6 - https://doi.org/10.1080/01694243.2015.1040980 SN - 0169-4243 SN - 1568-5616 VL - 29 IS - 15 SP - 1628 EP - 1650 PB - VNU Science Press CY - Utrecht AN - OPUS4-34564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Lukowiak, M.C. A1 - Wettmarshausen, Sascha A1 - Hidde, Gundula A1 - Landsberger, Petra A1 - Boenke, Viola A1 - Rodenacker, K. A1 - Braun, Ulrike A1 - Friedrich, Jörg Florian A1 - Gorbushina, Anna A1 - Haag, R. T1 - Polyglycerol coated polypropylene surfaces for protein and bacteria resistance N2 - Polyglycerol (PG) coated polypropylene (PP) films were synthesized in a two-step approach that involved plasma bromination and subsequently grafting hyperbranched polyglycerols with very few amino functionalities. The influence of different molecular weights and density of reactive linkers were investigated for the grafted PGs. Longer bromination times and higher amounts of linkers on the surface afforded long-term stability. The protein adsorption and bacteria attachment of the PP-PG films were studied. Their extremely low amine content proved to be beneficial for preventing bacteria attachment. PY - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-325406 SN - 1759-9954 SN - 1759-9962 VL - 6 IS - 8 SP - 1350 EP - 1359 AN - OPUS4-32540 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg A1 - Altmann, Korinna A1 - Wettmarshausen, Sascha A1 - Hidde, Gundula T1 - Coating of carbon fibers with adhesion-promoting thin polymer layers using plasma polymerization or electrospray ionization technique—A comparison N2 - Plasma polymers and electrospray-ionization (ESI) polymer layers are compared for most efficient adhesion promotion in carbon fiber-epoxy resin composites. The ultra-thin ESI layers (2–30 nm) of commercial poly(acrylic acid) and poly-(hydroxyethylmethacrylate) produce an significant increase of adhesion measured by single-fiber pull out tests. However, plasma Treatment has also advantages, such as simultaneous activation of the fiber substrate. Chemical structure and composition are rather far from the regular structure of commercial polymers as deposited by ESI processing. KW - Plasma polymers KW - Electrospray ionization polymers KW - Poly(acrylic acid) KW - Poly- (hydroxyethylmethacrylate) PY - 2017 U6 - https://doi.org/10.1002/ppap.201600074 SN - 1612-8869 SN - 1612-8850 VL - 14 IS - 3 SP - e1600074-1 EP - 14 AN - OPUS4-40510 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -