TY - JOUR A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Koprinarov, Ivaylo A1 - Ghode, Archana A1 - Geng, Sh. A1 - Kühn, Gerhard T1 - Plasma-based introduction of monosort functional groups of different type and density onto polymer surfaces. Part 1: Behaviour of polymers exposed to oxygen plasma N2 - Several approaches were investigated to produce monosort functionalized polymer surfaces with a high density and homogeneity of functional groups: (i) Plasma oxidation followed by wet-chemical reduction, (ii) formation of radicals and grafting on of functional group carrying molecules, (iii) plasma bromination followed by (iv) Williamson or Gabriel-like synthesis of spacer molecules, and (v) a pulsed plasma polymerization of functional groups bearing monomers or (vi) their copolymerisation with other comonomers. The formation of hydroxyl (OH), primary amino (NH2), and carboxyl (COOH) groups was studied in detail. The oxygen plasma treatment (i) in a low-pressure non-isothermal glow discharge results in the formation of a wide variety of O functional groups, polymer degradation and crosslinking. Low power densities and short exposure times (0.1 to 2 s) are required to functionalize a surface while preserving the original polymer structure. Carbonate, ester, and aromatic groups are rapidly degraded by an oxygen plasma treatment leading to scissions of polymer backbones and loss in molecular weight. Also the formation of macrocycles and C=C bonds was observed in a region of around 4 nm in depth. The investigated polymers could be classified by their degradation behaviour on exposure to the oxygen plasma.___TAGSTART___BR___TAGEND___ In order to maximize the process selectivity for OH groups, the variety of oxygen functionalities formed by the oxygen plasma was wet-chemically reduced by diborane, vitridetrade (Na complex), and LiAlH4. Typical yields were 9 to 14 OH groups per 100 carbon atoms.___TAGSTART___BR___TAGEND___ Plasma bromination (iii) (40 Br per 100 C atoms) of polymers, followed by grafting of spacer molecules (iv), has been proved to be a highly selective reaction.___TAGSTART___BR___TAGEND___ Another way to produce high densities of monosort functionalities was the pulsed plasma polymerization of functional group bearing monomers such as allylamine, allylalcohol or acrylic acid (v). The retention of chemical structure and functional groups during plasma polymerization was achieved by using low power densities and the pulsed plasma technique. The maximum yields were 30 OH, 18 NH2, and 24 COOH groups per 100 C atoms. To vary the density of functional groups a chemical copolymerization with ''chain-extending'' comonomers such as butadiene and ethylene was initiated in the pulsed plasma (vi). Additionally, the often-observed post-plasma oxidations of such layers initiated by reaction of trapped radicals with oxygen from the air were successfully suppressed by using NO gas as radical quencher. PY - 2003 DO - https://doi.org/10.1163/156855403765826865 VL - 10 IS - 2-3 SP - 139 EP - 171 PB - North-Holland CY - New York, NY AN - OPUS4-2705 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Kühn, Gerhard A1 - Retzko, Iris A1 - Schönhals, Andreas A1 - Unger, Wolfgang T1 - Plasma-based introduction of monosort functional groups of different type and density onto polymer surfaces. Part 2: Pulsed plasma polymerization N2 - This new functionalization method consists of the deposition of very thin plasma polymer layers (20 to 100 nm) of functional group bearing monomers in pulsed plasma. With allylalcohol, a maximum of 30 OH groups per 100 C atoms was measured with a selectivity of about 90% and a significant stability at long-time exposure to air. Allylamine was used to produce primary amino groups, with a maximum of 18 NH2 groups per 100 C atoms. Side reactions were observed during the storage in air, such as oxidation of the amino groups. Carboxylic groups could be produced using acrylic acid with a maximum concentration of 24 COOH groups per 100 C atoms. The most prominent side reaction was the decarbonylation/ decarboxylation of the acid group during plasma deposition.___TAGSTART___BR___TAGEND___ The variation of the density of functional groups using the pulsed-plasma polymerization of functional-group-bearing monomers was possible by the chemically-initiated radical copolymerization with either a chain-extending monomer, such as ethylene, or a cross linker, such as butadiene, in plasma. The density of functional groups could be adjusted continuously (0 to 30 OH, 0 to 18 NH2 and 0 to 24 COOH groups per 100 C atoms).___TAGSTART___BR___TAGEND___ The successful application of these densely functionalized polymer surfaces for producing biocompatible surfaces and for use in metal–polymer composites is proposed. KW - Pulsed plasma polymerization KW - Plasma-initiated copolymerization KW - Charcterization of homo- and copolymers PY - 2003 DO - https://doi.org/10.1163/156855403765826874 VL - 10 IS - 2-3 SP - 173 EP - 223 PB - North-Holland CY - New York, NY AN - OPUS4-2706 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Kühn, Gerhard A1 - Mix, Renate A1 - Unger, Wolfgang T1 - Formation of Plasma Polymer Layers with Functional Groups of Different Type and Density at Polymer Surfaces and their Interaction with Al Atoms N2 - Monotype functionalizations with different types of functional groups (OH, NH2, COOH) on polypropylene and poly(tetrafluoroethylene) surfaces were synthesized using pulsed plasma-initiated homo- or copolymerization of functional group-carrying monomers. The maximum concentrations of functional groups were 31 OH, 18 NH2 or 24 COOH groups per 100 C atoms using allyl alcohol, allylamine or acrylic acid respectively as the monomer. The measured peel strengths of aluminium deposits increased linearly with the concentration of functional groups. Near the maximum concentration of OH (>27 OH/100 C atoms) or at moderate concentrations of COOH groups (>10 COOH/100 C atoms), constant (maximum) peel strengths were measured due to the mechanical collapse of one component in the composite (cohesive failure). Interface failures in Al-PP composites were found with COOH, NH2 and OH groups and cohesive failures were seen when higher concentrations of COOH groups were applied (>10 COOH/100 C atoms). PY - 2004 DO - https://doi.org/10.1002/ppap.200400008 SN - 1612-8850 SN - 1612-8869 VL - 1 IS - 1 SP - 28 EP - 50 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-4707 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Kühn, Gerhard A1 - Unger, Wolfgang A1 - Mix, Renate ED - Radusch, H.-J. ED - Fiedler, L. T1 - Plasma-initiated homo and copolymerisation for modifying polymer surfaces with funtional groups of different type and density T2 - Internationale Fachtagung Polymerwerkstoffe ; P-2002 CY - Halle (Saale), Germany DA - 2002-09-25 PY - 2002 SN - 3-86010-656-2 SP - 534 EP - 539 PB - Martin-Luther-Univ. Halle-Wittenberg CY - Halle (Saale) AN - OPUS4-6969 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Kühn, Gerhard A1 - Unger, Wolfgang T1 - Functional groups bearing plasma homo and copolymer layers as adhesion promoters in metal-polymer composites T2 - 10. Neues Dresdner Vakuumtechnisches Kolloquium (NDVaK) CY - Dresden, Germany DA - 2002-10-17 PY - 2002 SP - 6 EP - 15 PB - DTVa CY - Dresden AN - OPUS4-6970 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kühn, Gerhard A1 - Retzko, Iris A1 - Lippitz, Andreas A1 - Unger, Wolfgang A1 - Friedrich, Jörg Florian T1 - Homofunctionalized polymer surfaces formed by selective plasma processes N2 - Several possibilities exist to produce a modified polymer surface with a high density of only one sort of functional group such as: (i) the plasma grafting of unfragmented monomer molecules and their polymerization forms OH, NH2, COOH groups, etc. in concentrations of approximately 25 groups per 100 C atoms; (ii) selective plasma bromination provides 10–25 CBr groups; (iii) the plasma oxidation of polymer surfaces in an O2 plasma followed by the chemical reduction of all O-containing groups to OH groups by diborane, vitride™ (Na complex) or LiAlH4 yields 9–14 OH groups per 100 carbon atoms; and (iv) the grafting of spacers with different endgroups onto OH or CBr groups produces 7–10 spacer molecules/100 C. This work was focused on the formation of thin plasma deposited polymer layers with a maximum of (homo)functional groups and with a minimum of chemical irregularities using the pulsed plasma technique. The monomers were allylalcohol, allylamine, acrylonitrile and acrylic acid. The further intent was to study the interactions of functional groups (OH, COOH, NH2) and deposited metals (Cr, Al, Ti). It was expected that more basic (NH2), weakly basic or neutral (OH) or more acidic (COOH) groups would show different interactions and chemical reactions with metal atoms. KW - Pulsed plasma polymerization KW - Functional groups KW - Long-term stability KW - Polymer-metal composites PY - 2001 DO - https://doi.org/10.1016/S0257-8972(01)01056-8 SN - 0257-8972 VL - 142-144 SP - 494 EP - 500 PB - Elsevier Science CY - Lausanne AN - OPUS4-6971 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Retzko, Iris A1 - Kühn, Gerhard A1 - Unger, Wolfgang A1 - Lippitz, Andreas T1 - Plasma polymers with chemically defined structures in contact with metals N2 - The retention of chemical structure and functional groups during plasma polymerization was investigated. Usually plasma polymer layers, prepared by a continuous wave radio-frequency plasma, are often chemically irregular in their structure and composition. To minimize these irregularities low wattages and the pulsed plasma technique were applied to avoid fragmentations. The first goal was to produce plasma polymers comprising double or triple bonds as precursors for electrically conducting polymers. Acetylene, ethylene, butadiene and polystyrene were used as monomers and deposited as thin polymer films by pulsed plasmas of low wattages. Styrene polymerization was strongly enhanced in the dark phase (plasma off) of a pulsed r.f. plasma caused by the reactivity of the vinyl-type double bond. This could be confirmed by a verification of a rather high chemical regularity of the film sample. The oxygen content of this film measured by X-ray photoelectron spectrometry (XPS) was in situ 0% and after 24 h exposure to air lower than 1%. Additionally, post-plasma oxidations of trapped radicals with air could be suppressed using NO gas as radical quencher. Such quenched plasma polymer layers were completely stable against oxidation for a number of weeks. During the low-wattage pulse plasma polymerization metal atoms were simultaneously or layer by layer evaporated into the growing layer and in situ measured by XPS. These metal atoms are acting as dopants. Here, Li, K, Mg and Cr were used at different concentrations providing electrical conductivity and magnetic properties for the film. KW - Pulsed plasma KW - Plasma polymerization KW - Doping with metal atoms KW - Encapsulation of nanoparticles PY - 2001 DO - https://doi.org/10.1016/S0257-8972(01)01051-9 SN - 0257-8972 VL - 142-144 SP - 460 EP - 467 PB - Elsevier Science CY - Lausanne AN - OPUS4-6972 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Möller, B. A1 - Kühn, Gerhard A1 - Unger, Wolfgang A1 - Krüger, P. T1 - Improvement of adhesion properties of polymers by producing oxyfluorinated surfaces PY - 2001 SN - 0016-4232 VL - 92 IS - 5 SP - 1334 EP - 1444 PB - Leuze CY - Saulgau, Württ. AN - OPUS4-6973 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Retzko, Iris A1 - Friedrich, Jörg Florian A1 - Kühn, Gerhard A1 - Lippitz, Andreas A1 - Unger, Wolfgang T1 - Eine neue Generation von alterungsbeständigen Plasmapolymeren mit definierter chemischer Struktur T2 - 8. Neues Dresdner Vakuumtechnisches Kolloquium (NDVaK) CY - Dresden, Deutschland DA - 2000-10-19 PY - 2000 VL - 8 SP - 110 EP - 114 CY - Dresden AN - OPUS4-6974 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Retzko, Iris A1 - Kühn, Gerhard A1 - Unger, Wolfgang A1 - Lippitz, Andreas ED - Mittal, K. T1 - Metal doped plasma polymer films T2 - 7th Symposium on Metallized Plastics CY - Newark, NJ, USA DA - 1999-12-02 KW - Plasma polymer KW - r.f. pulsed plasma KW - Conducting films KW - Metal-polymer interface PY - 2001 SN - 90-6764-340-8 VL - 7 SP - 117 EP - 142 PB - VSP CY - Utrecht AN - OPUS4-929 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Koprinarov, Ivaylo A1 - Weidner, Steffen A1 - Kühn, Gerhard ED - Nowack, H. T1 - Wechselwirkungen zwischen plasmamodifizierten Polymeroberflächen und Metallen T2 - 5. Internationale Fachtagung - ND-Plasma-Technologie CY - Duisburg, Deutschland DA - 1997-09-22 PY - 1997 VL - 5 SP - 1(?) EP - 17(?) PB - Print-Service CY - Mülheim AN - OPUS4-6995 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Kühn, Gerhard A1 - Ghode, Archana A1 - Weidner, Steffen A1 - Retzko, Iris A1 - Unger, Wolfgang A1 - Friedrich, Jörg Florian ED - Mittal, K. L. T1 - Chemically well-defined surface functionalization of polyethylene and polypropylene by pulsed plasma modification followed by grafting of molecules T2 - 2nd International Symposium on Polymer Surface Modification: Relevance to Adhesion CY - Newark, NJ, USA DA - 1999-05-24 KW - Plasma modification KW - Chemical conversion of functional groups KW - Spacers KW - Polypropylene KW - Polyethylene PY - 2000 SN - 90-6764-327-0 VL - 2 SP - 45 EP - 64 PB - VSP CY - Utrecht AN - OPUS4-6975 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Koprinarov, Ivaylo A1 - Kühn, Gerhard A1 - Weidner, Steffen A1 - Vogel, Lydia ED - Mittal, K. T1 - Plasma Pretreatment of Polymer Surfaces - Relevance to Adhesion of Metals T2 - 5th Symposium on Metallized Plastics ; 6th Symposium on Metallized Plastics CY - Los Angeles, CA, USA DA - 1996-05-05 PY - 1998 SN - 90-6764-290-8 SP - 271 EP - 293 PB - VSP CY - Utrecht AN - OPUS4-6987 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Giebler, Rainer A1 - Koprinarov, Ivaylo A1 - Weidner, Steffen A1 - Kühn, Gerhard ED - Mittal, K. L. T1 - Significance of interfacial redox reactions and formation of metal-organic complexes for the adhesion of metals on pristine and plasma-treated polymers KW - Oxygen low-pressure plasma treatment of polymers KW - Metal-polymer interactions KW - Peel strength PY - 2000 SN - 90-6764-327-0 VL - 2 SP - 137 EP - 171 PB - VSP CY - Utrecht AN - OPUS4-6979 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Wigant, L. A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Weidner, Steffen A1 - Kühn, Gerhard A1 - Geng, Sh. A1 - Erdmann, J. A1 - Gorsler, H.-V. T1 - Plasmavorbehandlungen von Polymeroberflächen T2 - 2. Freiberger Polymertag CY - Freiberg DA - 1995-05-30 PY - 1995 SP - 17 Seiten CY - Freiberg AN - OPUS4-7014 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Ghode, Archana A1 - Kühn, Gerhard A1 - Weidner, Steffen A1 - Geng, Shiming A1 - Retzko, Iris A1 - Unger, Wolfgang A1 - Lippitz, Andreas ED - Schindel-Bidinelli, E. T1 - Polymeroberflächenfunktionalisierungen im gepulsten Plasma mit nachfolgender chemischer Behandlung T2 - 14. Internationales Symposium Swissbonding ; 14. Internationaler Kongreß Swiss Bonding ; 14th Swiss Bonding 00 CY - Rapperswil, Schweiz DA - 2000-05-16 PY - 2000 SP - 31 EP - 44 PB - SWIBOTECH GmbH CY - Bülach AN - OPUS4-6980 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kühn, Gerhard A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas T1 - Plasmaoxidative Degradation of Polymers Studied by Matrix-assisted Laser Desorption/Ionization Mass Spectrometry PY - 1996 SN - 0951-4198 SN - 1097-0231 VL - 10 SP - 727 EP - 732 PB - Wiley CY - Chichester AN - OPUS4-7004 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Koprinarov, Ivaylo A1 - Weidner, Steffen A1 - Kühn, Gerhard ED - Schindel-Bidinelli, E. T1 - Umweltfreundliches Metallisieren von Kunststoffen durch Plasmavorbehandlung in einem geschlossenen Reaktor T2 - Swissbonding 97 ; 11. Internationales Symposium Klebtechnik und Umwelt ; 11th International Symposium Bonding and Sealing Technology CY - Rapperswil, Schweiz DA - 1997-05-26 PY - 1997 SP - 1(?) EP - 3(?) PB - SWIBOTECH CY - Rorbas AN - OPUS4-6994 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Geng, Sh. A1 - Koprinarov, Ivaylo A1 - Kühn, Gerhard A1 - Weidner, Steffen T1 - Modelling plasma-induced reactions on polymer surfaces using aliphatic self-assembling and LB layers PY - 1998 SN - 0257-8972 VL - 98 SP - 1132 EP - 1141 PB - Elsevier Science CY - Lausanne AN - OPUS4-6999 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas A1 - Koprinarov, Ivaylo A1 - Kühn, Gerhard A1 - Weidner, Steffen A1 - Vogel, Lydia T1 - Chemical reactions at polymer surfaces interacting with a gas plasma or with metal atoms - their relevance to adhesion N2 - The chemical and morphological stabilities of polymer segments in the near-surface layer were investigated by spectroscopic methods such as X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. Model studies were undertaken with Langmuir–Blodgett films, self-assembled monolayers and oligomer films. For thin polymer layers (30 to 500 nm), the changes in molecular-weight distributions of some polymers were investigated systematically by size exclusion chromatography, matrix-assisted laser desorption/ionization–time-of-flight mass spectrometry and thermal-field flow fractionation for oxygen- and helium-plasma exposures. The polymer surfaces were found to be relatively stable at exposure to an oxygen low-pressure plasma up to ca. 2 s. This is important information to get maximum adhesion to metals in composites. In correlation to their redox potentials, potassium, aluminium and chromium react with oxygen functional groups at the polymer/metal interface. In a dedicated study, chromium was found to attack aromatic rings and form different reaction products. PY - 1999 DO - https://doi.org/10.1016/S0257-8972(99)00229-7 SN - 0257-8972 VL - 116-119 SP - 772 EP - 782 PB - Elsevier Science CY - Lausanne AN - OPUS4-6981 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Weidner, Steffen A1 - Kühn, Gerhard A1 - Roessner, D. A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang A1 - Lippitz, Andreas ED - Olefjord, I. ED - Nyborg, L. ED - Briggs, D. T1 - Changes in molecular weight distribution of polymers by plasma treatment T2 - 7th European Conference on Applications of Surface and Interface Analysis CY - Göteborg, Sweden DA - 1997-06-16 PY - 1997 SN - 0-471-97827-2 SP - 795 EP - 799 PB - Wiley CY - Chichester AN - OPUS4-6997 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Friedrich, Jörg Florian A1 - Kühn, Gerhard A1 - Mix, Renate A1 - Retzko, Iris A1 - Gerstung, Vanessa A1 - Weidner, Steffen A1 - Schulze, Rolf-Dieter A1 - Unger, Wolfgang ED - Mittal, K. L. T1 - Plasma polymer adhesion promoters for metal-polymer systems T2 - 2nd International Symposium on Polyimides and Other High Temperature Polymers: Synthesis, Characterization and Applications CY - Newark, NJ, USA DA - 2001-12-03 KW - r.f. pulsed plasma KW - Plasma polymers with functional groups KW - Copolymers KW - Adhesion promoting interlayers KW - Metal-polymer systems PY - 2003 SN - 90-6764-378-5 VL - 2 SP - 359 EP - 388 PB - VSP CY - Utrecht AN - OPUS4-6967 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -