TY - JOUR A1 - Gross, Thomas A1 - Kühn, Gerhard A1 - Unger, Wolfgang T1 - Photoelectron spectroscopy on organic surfaces: X-ray degradation of oxygen-plasma-treated and chemically reduced poly(propylene) surfaces in comparison to conventional polymers JF - Surface and interface analysis N2 - The X-ray-induced sample damage during mono XPS analysis of an oxygen-plasma-oxidized and subsequently wet-chemically reduced poly(propylene) film was investigated as a showcase for plasma-modified or plasma-deposited samples. By doing this, the degradation index approach as introduced by Beamson and Briggs in the Scienta ESCA300 high-resolution XPS database of organic polymers has been adopted. As to be expected, the sample degrades by loosing oxygen as revealed by observation of decreasing O/C and COR/Csum ratios. However, the X-ray degradation indices are definitely higher than those of conventional reference polymers. Moreover, the COR/Csum degradation index is significantly higher in comparison with one obtained for the O/C ratio. In that context, there is no difference between the plasma sample and a conventional poly(vinyl alcohol) polymer. It is concluded that for reliable quantitative surface chemical analysis, the quality of spectra in terms of acquisition times must be optimized aimed to a minimization of X-ray degradation. Finally, it is proposed to describe the photon flux of an X-ray gun in an XPS experiment, which defines the degradation rate at the end, by using the sample current simply measured with a carefully grounded sputter-cleaned reference silver sample. KW - Photoelectron spectroscopy KW - ESCA/XPS KW - Surfaces KW - Surface modification KW - Poly(propylene) (PP) KW - Plasma treatment KW - X-ray KW - Degradation PY - 2009 DO - https://doi.org/10.1002/sia.3024 SN - 0142-2421 SN - 1096-9918 VL - 41 IS - 5 SP - 445 EP - 448 PB - Wiley CY - Chichester AN - OPUS4-19252 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 JF - Plasma processes and polymers 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 DO - 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 - JOUR A1 - Friedrich, Jörg Florian A1 - Kühn, Gerhard A1 - Mix, Renate A1 - Hoffmann, Katrin A1 - Resch-Genger, Ute T1 - Tailoring of polymer surfaces with monotype functional groups of variable density using chemical and plasma chemical processes JF - Progress in colloid & polymer science N2 - Polymer surfaces were modified in low-pressure glow discharge plasmas for introduction of monotype functional groups of different type and density. For this purpose three ways are selected, (i) oxygen plasma treatment followed by wet-chemical reduction of O functional groups to OH groups, (ii) plasma bromination for introducing C - Br groups and (iii) coating by deposition of thin plasma (co-) polymerized layers of functional groups-bearing monomers with OH, NH2, COOH, epoxy etc. functionalities. Subsequently, these groups were used as anchoring points for chemical grafting of spacer molecules, oligomers, prepolymers, fluorescent labels, ionic and nucleic acid residues, employing different chemical routes. The yield in monosort functional groups at polymer surfaces ranged from 10–14 (process i), 20–40 (process ii) and 18–31 groups per 100 C atoms (process iii) as measured by XPS after derivatization. The consumption of functional groups amounted to 40–90% of all functionalities present at the surface and depended on the dimensions of grafted molecules. For infinitely variably tuning the number of functional groups process iii was performed as copolymerization of a functional group-carrying comonomer with a non-functionalized (“chain-extending”) comonomer. KW - Introduction of functional groups KW - Plasma modification KW - Reactions at Polymer surfaces PY - 2006 SN - 0340-255x SN - 1437-8027 VL - 132 SP - 62 EP - 71 PB - Springer CY - Berlin AN - OPUS4-12515 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Kühn, Gerhard T1 - Adhesion of metals to plasma-induced functional groups at polymer surfaces JF - Surface and coatings technology N2 - The peel strength of aluminium to polypropylene and poly(tetrafluoroethylene) was determined in dependence on the type and the concentration of functional groups on the polymer surface. For this purpose the polymer surface was equipped with monotype functional groups. The first method to produce monotype functionalized surfaces was an introduction of O functional groups using an oxygen plasma treatment and converting these groups to OH groups applying a wet chemical reduction. In result of this two-step treatment the hydroxyl group concentration at the polymer surface could be increased from 3–4 to 10–14 OH groups/100 C atoms. The second method consists in the deposition of a 150 nm adhesion-promoting layer of plasmapolymers or copolymers onto the polymer surface using the pulsed plasma technique. For that purpose functional groups carrying monomers as allyl alcohol, allylamine and acrylic acid were used. Applying the plasma-initiated copolymerization and using neutral “monomers” like ethylene or butadiene the concentration of the functional groups was varied. A correlation of peel strength with the ability of forming chemical interactions between Al atoms and functional groups was found: COOH > OH >> NH2 > H(CH2–CH2). KW - Peel strength KW - Aluminium KW - Polypropylene KW - Poly(tetrafluoroethylene) KW - Pulsed plasma KW - Allyl alcohol KW - Allylamine KW - Acrylic acid KW - Plasma surface treatment KW - Adhesion PY - 2005 SN - 0257-8972 VL - 200 IS - 1-4 SP - 565 EP - 568 PB - Elsevier Science CY - Lausanne AN - OPUS4-10897 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 JF - Plasma processes and polymers 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 - JOUR A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Kühn, Gerhard T1 - Functional groups bearing plasma homo and copolymer layers as adhesion promoters in metal-polymer composites JF - Surface and coatings technology N2 - Functional groups bearing monomers were pulsed plasma polymerised with a degree of retained functional groups of 55–91%. The following functional groups could be produced at a maximum of: 30 OH, 18 NH2, and 24 COOH per 100 C atoms. A plasma-initiated radical copolymerisation could also be realised using the functional group bearing monomers as a source of functionalities, olefins as ‘chain-extenders’ and dienes as ‘chemical cross-linkers’. The peel strengths of Al layers on such plasma polymers were correlated to the type and density of functional groups. KW - Functional groups KW - Adhesion promoters KW - Metal-polymer composites PY - 2003 DO - https://doi.org/10.1016/S0257-8972(03)00350-5 SN - 0257-8972 VL - 174-175 SP - 811 EP - 815 PB - Elsevier Science CY - Lausanne AN - OPUS4-2703 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 - Fritz, Andreas A1 - Schönhals, Andreas T1 - Polymer surface modification with monofunctional groups of variable types and densities JF - Journal of adhesion science and technology N2 - The retention of chemical structure and functional groups during pulsed plasma polymerization was used for producing adhesion-promoting plasma polymer layers with high concentrations of exclusively one kind of functional groups, such as OH, NH2, or COOH. The maximum content of functional groups was 31 OH using allyl alcohol, 18 NH2 using allylamine, or 24 COOH per 100 C atoms using acrylic acid. To vary the density of functional groups, chemical co-polymerization with ethylene as 'chain-extending' co-monomer, or butadiene as 'chemical crosslinker' was initiated in the pulsed plasma. The composition of these co-polymers was investigated by XPS and IR spectroscopy. The concentrations of functional groups were measured by derivatizing with fluorine-containing reagents and using XPS. A set of plasma parameters was found to be a good compromise between a high number of functional groups and complete insolubility in water, ethanol or THF,which is needed for further chemical processing. Here, these monotype-functionalized surfaces were used in metal-polymer systems as adhesion-promoting interlayers to examine the influence of type and density of functional groups on adhesion. As expected, COOH- and OH-group-terminated interlayers showed maximum peel strengths to evaporated aluminium layers. The adhesion increased linearly with the number of OH groups to a maximum at about 27 OH per 100 C atoms. Higher concentrations of OH groups did not increase the peel strength further. KW - Co-polymers KW - Adhesion-promoting interlayers KW - Metal-polymer systems PY - 2003 DO - https://doi.org/10.1163/156856103322396695 SN - 0169-4243 SN - 1568-5616 VL - 17 IS - 12 SP - 1591 EP - 1617 PB - VNU Science Press CY - Utrecht AN - OPUS4-2704 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 - 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 JF - Composite interfaces : proceedings 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 JF - Composite interfaces : proceedings 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 - Schulz, Ulrich A1 - Jansen, Kirsten A1 - Bertus, Angela A1 - Fischer, S. A1 - Möller, B. T1 - Characterization of fluorinated polyethylene surfaces JF - Journal of adhesion science and technology N2 - Polyethylene foils, used as greenhouse foils stabilized with various types of sterically hindered amine light stabilizers (HALS), showed an extraordinary prolonged lifetime on exposure to natural or artificial weathering if a gas-phase fluorination under low-pressure conditions was applied. The fluorination was performed using F2/N2 mixtures and provided ca. 50 F/100 C (fluorination degree ap25%). The lifetimes of fluorinated PE foils on exposure to artificial or natural weathering were increased at least by a factor of 2-4 as measured in terms of tensile strength and elongation at break. KW - Gas phase fluorination of PE KW - Fluorination kinetics KW - Weathering PY - 2003 DO - https://doi.org/10.1163/156856103322113832 SN - 0169-4243 SN - 1568-5616 VL - 17 IS - 8 SP - 1127 EP - 1143 PB - VNU Science Press CY - Utrecht AN - OPUS4-2707 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -