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 - Hoffmann, Katrin A1 - Resch-Genger, Ute A1 - Mix, Renate A1 - Friedrich, Jörg Florian T1 - Fluorescence Spectroscopic Studies on Plasma-Chemically Modified Polymer Surfaces with Fluorophore-Labeled Functionalities JF - Journal of fluorescence N2 - Molecular engineering of polymer surfaces that includes the attachment of functional molecules to existing or previously generated reactive chemical groups like e.g., - OH, - NH2, or - CHO requires simple strategies and tools for the controlled generation of surface functionalities and their derivatization as well as for their identification and eventually quantification. Here, we systematically investigate the plasma-chemical surface modification of polypropylene films in combination with dansyl labeling chemistry and conventional, yet costly, XPS and highly sensitive fluorescence spectroscopy for the detection of surface groups. Based on these results, the potential of and requirements on the fluorometric characterization and quantification of surfaces functionalities are discussed. KW - Fluorescence spectroscopy KW - Surface functionalization KW - Covalent labeling of polymer surfaces KW - Plasma modification KW - Fluorescent probe PY - 2006 DO - https://doi.org/10.1007/s10895-006-0076-x SN - 1053-0509 SN - 1573-4994 VL - 16 IS - 3 SP - 441 EP - 448 PB - Plenum Publ. Corp. CY - New York, NY AN - OPUS4-12560 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 I dependence on the duty cycle JF - Plasma processes and polymers N2 - Copolymers of acrylic acid and styrene (AA/S) were prepared by pulsed plasma deposition and their structures were studied in dependence on the duty cycle (DC) for a fixed composition of 1:1. As a result, low values of DC doses preserve the structure of monomers in the plasma deposited polymers while high DC leads to a higher degree of fragmentation and a loss in regular structure. Regarding plasma copolymerisation as a feasible method to finish surfaces with a definite number of functional groups it is necessary to characterize both, the chemical nature and the physical properties of the deposited layer. Therefore, a combination of different methods was employed for the characterization of thin plasma copolymer films (FTIR, dielectric spectroscopy, differential scanning calorimetry, X-ray photoelectron spectroscopy (XPS)). Special attention was paid on the unambiguous identification of COOH groups at the surface after derivatization with trifluoroethanol by XPS and in the volume by FTIR. The glass transition temperature of the copolymer system is lower than that for the both plasma deposited homopolymers and increases with the DC in difference to plasma deposited poly(acrylic acid). The dielectric measurements showed that the plasma deposited films were not thermally stable and underwent an undesired post-plasma chemical reaction. The results obtained by dielectric spectroscopy are discussed in detail in comparison with the data from FTIR and XPS measurements. KW - Plasmapolymerisation KW - Copolymerisation KW - Acrylic acid–styrene copolymer KW - Dynamic mobility KW - Plasma copolymerisation KW - Surface functionalization KW - Thin film properties PY - 2012 DO - https://doi.org/10.1002/ppap.201100117 SN - 1612-8850 SN - 1612-8869 VL - 9 IS - 3 SP - 273 EP - 284 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-25654 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mix, Renate A1 - Friedrich, Jörg Florian A1 - Inagaki, N. T1 - Modification of branched polyethylene by aerosol-assisted dielectric barrier discharge JF - Plasma processes and polymers N2 - Three polyethylene (PE) types with different branching structures were subjected to air, water and ethanol aerosol-assisted dielectric barrier discharges (DBD) for surface modification. Using the air DBD the incorporated oxygen concentration was found to be independent on the branching of PE in contrast to the introduction of OH groups, which was PE-2 > PE-1 > PE-3. For water-aerosol DBD the succession of OH concentration was in the order of PE-1 > PE-2 > PE-3. Ethanol aerosol-assisted DBD produced the lowest concentration of OH groups also independent on the branching of PE. The chemical nature of introduced oxygen functional groups was inspected by X-ray photoelectron spectroscopy (XPS) and assigned as C–O, >C=O/CHO/O–C–O and O=C–O. KW - PE KW - Surface modification KW - Aerosol-assisted DBD PY - 2012 DO - https://doi.org/10.1002/ppap.201100052 SN - 1612-8850 SN - 1612-8869 VL - 9 IS - 4 SP - 406 EP - 416 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-25748 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Mix, Renate A1 - Hielscher, Stefan A1 - Beck, Uwe A1 - Friedrich, Jörg Florian T1 - Plasma meets chemistry: Combined methods for tailored interface design in metal-polymer composites by selective chemical reactions on plasma modified surfaces JF - Journal of physics / Conference series N2 - The applicability of polymer-metal composites is mainly determined by the durability of the adhesive strength between both components. Aluminium (Al) deposited on polypropylene (PP) exemplifies different options of interface design. By deposition of plasma polymers on PP the effect of the type of the functionality was investigated. Spacer insertion was accomplished to position the functional group away from the topmost surface. A further kind of interface design involved a partial condensation of functional groups. Hydroxyl and carboxyl groups were most effective to improve adhesion in Al-PP systems. Approximately 7-10 carboxyl or 25-27 hydroxyl groups per 100 C atoms were necessary to increase the peel strength up to ~700 N/m. In this range, the failure of the composite propagated along the interface Al-tape (no peeling of the metal). Spacer molecules between surface and functional groups provoked the effect that the number of needed functional groups for maximum adhesion was strongly reduced. Linking of the functional groups resulted in non-peelable Al-PP laminates. Two adhesion tests were applied - the peel test and the centrifuge technology. For PP foils modified with chemically bonded and additionally linked silanol groups (no peeling) an adhesive strength of (2.5 ± 0.2) N/mm² was determined by centrifuge technology. XPS inspection of both fracture surfaces indicated a sub-surface failure in the polymer. T2 - HTPP-12 - 12th High-tech plasma processes conference CY - Bologna, Italy DA - 2012-06-24 KW - Adhesion PP-Al KW - Modified surfaces KW - Interface design PY - 2012 DO - https://doi.org/10.1088/1742-6596/406/1/012004 SN - 1742-6588 SN - 1742-6596 VL - 406 SP - 012004-1 - 012004-11 PB - IOP Publ. CY - Bristol, UK AN - OPUS4-28658 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ramanujam, Maalolan A1 - Wachtendorf, Volker A1 - Purohit, Purv A1 - Mix, Renate A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian T1 - A detailed dielectric relaxation spectroscopy study of artificial UV weathered low density polyethylene JF - Thermochimica Acta N2 - Artificial weathering of LDPE under dry conditions (<10% of relative humidity) by UV radiation was monitored by dielectric spectroscopy. For an apolar polymer like LDPE, dielectric study yields information about the change in structure and dynamics of the system. The fluctuations of the polar groups which are generated as a result of photooxidation such as carbonyl groups can be monitored as characteristic relaxation processes like the αc or β mode. The dielectric loss characterized by typical dielectric parameters like the activation energy and dielectric strength are strongly dependent upon changes induced by photooxidation in the amorphous and crystalline domains. This paper discusses in detail how the foil reached its mechanical disintegration. It was found that initial stages of weathering induce chain scission and/or crosslinking in the amorphous domains of the polymer and the motional processes in the crystalline regions are not affected. After this induction period, an increase in the degree of crystallization was observed by employing differential calorimetry. The increasing crystallinity is considered as one of the reasons for embrittlement which finally leads to the complete loss of the structural integrity. KW - Artificial weathering KW - UV radiation KW - Dielectric relaxation KW - LDPE PY - 2012 DO - https://doi.org/10.1016/j.tca.2011.12.003 SN - 0040-6031 SN - 1872-762X VL - 530 SP - 73 EP - 78 PB - Elsevier CY - Amsterdam AN - OPUS4-25547 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 - Surface and bulk structure of thin spin coated and plasma-polymerized polystyrene films JF - Plasma chemistry and plasma processing 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 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 - 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 -