TY - JOUR A1 - Fahmy, A. A1 - Mix, Renate A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian T1 - Surface and bulk structure of thin spin coated and plasma-polymerized polystyrene films N2 - Polystyrene (PS) spin coated thin films were modified by O2 and Ar plasma as well as by UV irradiation treatments. The modified PS samples were compared with plasma polymerized and commercial polystyrene. The effects of plasma (O2 and Ar) and UV irradiation treatments on the surface and the bulk properties of the polymer layers were discussed. The surface properties were evaluated by X-ray Photoelectron Spectroscopy and Contact angle measurements and the bulk properties were investigated by FTIR and dielectric relaxation spectroscopy. As a result only one second treatment time was sufficient to modify the surface. However, this study was also dedicated to understand the effect of plasma and plasma irradiation on the deposited layers of plasma polymers. The dielectric measurements showed that the plasma deposited films were not thermally stable and underwent an undesired post-plasma chemical oxidation. KW - Surface and bulk characterization KW - Plasma polymerization KW - Polystyrene KW - Surface modification KW - Thermal stability KW - Plasma polymers PY - 2012 DO - https://doi.org/10.1007/s11090-012-9372-1 SN - 0272-4324 VL - 32 IS - 4 SP - 767 EP - 780 PB - Plenum Publ. Corp. CY - New York, NY, USA AN - OPUS4-26264 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 - JOUR A1 - Friedrich, Jörg Florian A1 - Mix, Renate A1 - Kühn, Gerhard T1 - Adhesion of metals to plasma-induced functional groups at polymer surfaces 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 - 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 DO - 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 DO - 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 - Hoffmann, Katrin A1 - Mix, Renate A1 - Resch-Genger, Ute A1 - Friedrich, Jörg Florian T1 - Monitoring of Amino Functionalities on Plasma-Chemically Modified Polypropylene Supports with a Chromogenic and Fluorogenic Pyrylium Reporter N2 - A straightforward strategy toward the sensitive fluorometric detection of primary amino groups on plasma-chemically modified polypropylene supports is presented, exploiting the transformation of the sterically nonhindered pyrylium dye Py-1 into its pyridinium counterpart. The reaction-induced blue-shifted absorption and emission bands and an increased fluorescence quantum yield provide the basis for the spectroscopic distinction between covalently bound and free, that is, nonspecifically adsorbed label molecules. With this label, for the first time, plasma-chemically introduced amino functionalities could be monitored on the surface of a polymer film employing fluorescence spectroscopy and confocal laser scanning microscopy. KW - Fluorescence spectroscopy KW - Surface characterization KW - Covalent labeling KW - Plasma modification KW - Fluorescent label PY - 2007 UR - http://pubs.acs.org/cgi-bin/abstract.cgi/langd5/2007/23/i16/abs/la7004908.html SN - 0743-7463 SN - 1520-5827 VL - 23 IS - 16 SP - 8411 EP - 8416 PB - American Chemical Society CY - Washington, DC AN - OPUS4-15717 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hoffmann, Katrin A1 - Mix, Renate A1 - Resch-Genger, Ute A1 - Friedrich, Jörg Florian T1 - Fluorescence Measurements on Functionalized Polymer Surfaces - Problems and Troubleshooting KW - Fluorescence spectroscopy KW - Polymer functionalization KW - Surface labeling KW - Pyrylium label PY - 2008 DO - https://doi.org/10.1196/annals.1430.015 SN - 0077-8923 SN - 1749-6632 SN - 0094-8500 VL - 1130 SP - 28 EP - 34 PB - New York Academy of Sciences CY - New York, NY AN - OPUS4-17567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Fahmy, A. A1 - Mix, Renate A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian T1 - Structure of plasma-deposited copolymer films prepared from acrylic acid and styrene: Part II variation of the comonomer ratio N2 - Copolymers of acrylic acid and styrene (AA/S) were prepared by pulsed plasma deposition technique. Their structure–property relationships were studied in dependence on the comonomer ratio. Both, the regularity of the structure and the composition of the thin copolymer films were investigated by bulk-sensitive (dielectric spectroscopy, FTIR, and differential scanning calorimetry) as well as surface-sensitive methods such as X-ray photoelectron spectroscopy (XPS). For an unambiguous identification of the functionality of the deposited films the COOH groups were estimated by derivatization with trifluoroethanol and subsequent XPS measurement as well as by the quantitative analysis of the FTIR data. As a result, the concentration of COOH groups on the surface and in the bulk is increasing with the fraction of AA in precursor mixture in a non-monotonous way but similar to the dependence obtained by conventional free radical polymerization. KW - Acrylic acid-styrene copolymer KW - Bulk properties KW - Dielectric properties KW - Plasma polymerization KW - Surface functionalization PY - 2013 DO - https://doi.org/10.1002/ppap.201200110 SN - 1612-8850 SN - 1612-8869 VL - 10 IS - 9 SP - 750 EP - 760 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-29096 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Gross, Thomas A1 - Pippig, F. A1 - Merz, B. A1 - Merz, R. A1 - Vohrer, U. A1 - Mix, Renate A1 - Steffen, H. A1 - Bremser, Wolfram A1 - Unger, Wolfgang T1 - Determination of OH groups at plasma oxidised poly(propylene) by TFAA chemical derivatisation XPS: an inter-laboratory comparison N2 - A first inter-laboratory comparison was conducted to demonstrate and document the capability of interested laboratories to measure the fraction of C—OH species on a plasma oxidised poly(propylene) sample by using a chemical derivatisation XPS approach. This report presents the results from that inter-laboratory comparison and includes the data received for the measured values and their associated standard deviations of laboratory means, at a 95% confidence level. The measurements were guided by a protocol developed within the group before and summarised shortly in the paper. Standard deviations that may characterise the state-of-the-art for the nominally simple and rather often practised case of TFAA chemical derivatisation XPS of C—OH species on a plasma oxidised polyolefin surface are calculated following ISO 5725-2:1994. The main conclusion is that the associated degree of equivalence reached by the participating laboratories in this comparison is still low. Further research to improve chemical derivatisation XPS protocols is mandatory. KW - Chemical derivatisation KW - ESCA/XPS KW - Inter-laboratory comparison KW - Photoelectron spectroscopy (PES) KW - Poly(propylene) (PP) PY - 2010 DO - https://doi.org/10.1002/ppap.200900142 SN - 1612-8850 SN - 1612-8869 VL - 7 IS - 6 SP - 494 EP - 503 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-21678 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mix, Renate A1 - Friedrich, Jörg Florian A1 - Neubert, Dietmar A1 - Inagaki, N. T1 - Response of linear, branched or crosslinked polyethylene structures on the attack of oxygen plasma N2 - Linear, branched and crosslinked polyethylenes (PE) were exposed to the low-pressure oxygen plasma for 2–120 s. In the following the samples were washed with solvents to remove low-molecular weight oxidized material and to excavate the subjacent polymer structure for microscopic characterization. X-ray photoelectron spectroscopy (XPS) measurements provided information about changes in elemental composition and chemical structure of PE after plasma exposure and washing. The calculation of the concentration of tertiary C atoms using XPS data was a measure of branches and crosslinking in the polymer before and after exposure to oxygen plasma. Linear PE was most sensitive towards oxygen plasma and showed the highest concentration in tertiary C atoms after plasma exposure. On the other hand branched PE types, which possess originally more tertiary carbon atoms, have lost two-third of them after 2 s oxygen plasma exposure. Branched PE show also topological changes at their surface as detected by atomic force microscopy. Differential scanning calorimetry measurements confirmed strong changes in crystallinity and molecular orientation of linear PE already after 120 s exposure to the oxygen plasma interpreted as amorphization. These effects should be interpreted as result of crosslinking caused by the recombination of dangling bond sites. KW - Linear and branched polyethylene KW - Oxygen plasma KW - Functionalization KW - Crosslinking PY - 2014 UR - http://link.springer.com/article/10.1007%2Fs11090-014-9558-9/fulltext.html DO - https://doi.org/10.1007/s11090-014-9558-9 SN - 0272-4324 VL - 34 IS - 5 SP - 1199 EP - 1218 PB - Plenum Publ. Corp. CY - New York, NY, USA AN - OPUS4-30741 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -