TY - JOUR A1 - Swaraj, Sufal A1 - Oran, Umut A1 - Lippitz, Andreas A1 - Schulze, Rolf-Dieter A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang T1 - Surface Analysis of Plasma-Deposited Polymer Films, 4 - In situ Characterization of Plasma-Deposited Ethylene Films by XPS and NEXAFS N2 - XPS and NEXAFS spectroscopy were used for the chemical characterization of pulsed plasma-deposited ethylene films before and after exposure to ambient air. The influence of external plasma parameters on the spectroscopic results was investigated. Information on the chemical character of the plasma-polymerized films, such as the regularity of the primary structure, the amount of long-living radicals, and branching or cross-linking or both was derived from this data. Irregularity and radical concentration for post-plasma reactions of the plasma-deposited films increased with the duty cycle or power. A decreased level of monomer fragmentation and, consequently, an increase in regularity is partially concluded from the experimental data when the monomer pressure is increased. The concentration of surface radicals available for post-plasma reactions also increased with monomer pressure. The correlation found between the degree of the post-plasma oxygen incorporation and the variation of the various external parameters agreed with earlier ToF-SSIMS findings. KW - ESCA/XPS KW - NEXAFS KW - Plasma polymerization KW - Polyethylene (PE) KW - Thin films PY - 2005 DO - https://doi.org/10.1002/ppap.200400070 SN - 1612-8850 SN - 1612-8869 VL - 2 IS - 4 SP - 310 EP - 318 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-11940 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Oran, Umut A1 - Swaraj, Sufal A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang T1 - Surface analysis of plasma-deposited polymer films by Time of Flight Static Secondary Ion Mass Spectrometry (ToF-SSIMS) before and after exposure to ambient air N2 - Pulsed plasma deposited styrene and ethylene films were studied by Time of Flight Static Secondary Ion Mass Spectrometry (ToF-SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma deposited films was investigated. Approaches for the interpretation of SSIMS spectra of organic materials were reviewed and applied to the evaluation of SSIMS data of plasma deposited films. From these data, information on the chemical character of the plasma deposited films was derived. When the plasma polymers are exposed to air oxygen incorporation occurs. The oxygen uptake is high at the beginning and then it levels of. A relation that “higher the regularity of the film lower is the oxygen uptake” was found. Harder plasma conditions, which could be obtained by applying higher plasma power or lower monomer flow rate, result in higher oxygen uptake and vice versa. KW - Plasma polymerization KW - Polyethylene (PE) KW - Polystyrene (PS) KW - SIMS KW - Ageing PY - 2005 DO - https://doi.org/10.1016/j.surfcoat.2005.02.032 SN - 0257-8972 VL - 200 IS - 1-4 SP - 463 EP - 467 PB - Elsevier Science CY - Lausanne AN - OPUS4-11044 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Swaraj, Sufal A1 - Oran, Umut A1 - Lippitz, Andreas A1 - Friedrich, Jörg Florian A1 - Unger, Wolfgang T1 - Study of influence of external plasma parameters on plasma polymerised films prepared from organic molecules (acrylic acid, allyl alcohol, allyl amine) using XPS and NEXAFS N2 - Plasma polymerised films of acrylic acid, allyl alcohol and allyl amine were prepared and studied by XPS (X-ray photoelectron spectroscopy) and XAS (X-ray absorption spectroscopy). The influence of external plasma parameters on certain chemical aspects of the films was investigated. The use of XPS and NEXAFS (near edge X-ray absorption fine structure) as complimentary tools in the surface characterisation of thin films has been highlighted. Certain chemical aspects of the plasma polymerised films such as presence of ROCdouble bond; length as m-dashO in the case of plasma polymerised acrylic acid films, presence of RCdouble bond; length as m-dashO and RC–OR bonds in case of plasma polymerised allyl alcohol films and presence of RCdouble bond; length as m-dashN and C?N in case of plasma polymerised allyl amine films were studied. The concentration of ROCdouble bond; length as m-dashO species was found to decrease with increase in r.f. duty cycle in the case of plasma polymerised acrylic acid films. In case of plasma polymerised allyl alcohol films there is a decrease in the concentration of RCdouble bond; length as m-dashO species and increase in the concentration of RC–OR species at higher pressures, while in the case of plasma polymerised allyl amine films the concentration of RCdouble bond; length as m-dashN and C?N increases at higher powers, with an increase in C?N more pronounced at higher powers. KW - Plasma polymerization KW - NEXAFS KW - XPS KW - Plasma parameter PY - 2005 DO - https://doi.org/10.1016/j.surfcoat.2005.01.083 SN - 0257-8972 VL - 200 IS - 1-4 SP - 494 EP - 497 PB - Elsevier Science CY - Lausanne AN - OPUS4-11045 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Swaraj, Sufal A1 - Oran, Umut A1 - Friedrich, Jörg Florian A1 - Lippitz, Andreas A1 - Unger, Wolfgang T1 - Surface Chemical Analysis of Plasma-Deposited Copolymer Films Prepared from Feed Gas Mixtures of Ethylene or Styrene with Allyl Alcohol N2 - Plasma deposited styrene/allyl alcohol and ethylene/allyl alcohol copolymer films were prepared and characterized using XPS, NEXAFS and ToF-SIMS. The relative partial flow rates of the co-monomers are used as deposition process parameters to vary and all other process parameters were constrained to conditions optimized for retention of functional groups. By doing this it is possible to control certain chemical properties of the copolymer films such as unsaturation, oxygen and hydroxyl group relative surface contents. The aging behavior of the plasma copolymer films on air was studied, too. Non-linear variations of relative oxygen contents, contents of C—OR species and contents of carbonyl species are obtained vs. variation of feed gas composition for both monomer combinations. The chemical character of the plasma copolymer films varies between the limits given by the respective plasma homopolymers. The observed non-linear correlations are discussed in terms of approaches developed for classic radical copolymerization. The aging behavior of the different plasma copolymers films depends on the feed gas composition. Principally these aging phenomena known from plasma polymer aging studies of that respective monomer which dominates the character of the plasma copolymer are observed. KW - Plasma polymers KW - Plasma copolymers KW - XPS KW - NEXAFS KW - Allyl alcohol KW - ESCA/XPS KW - Plasma polymerization KW - ToF-SIMS PY - 2007 SN - 1612-8850 SN - 1612-8869 VL - 4 IS - 4 SP - 376 EP - 389 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-14846 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Meyer-Plath, Asmus A1 - Mix, Renate A1 - Friedrich, Jörg Florian ED - Mittal, K. T1 - Aspects of amino functionalization of polypropylene surfaces for adhesion promotion of thermally-evaporated copper films KW - Plasma polymerization KW - Surface functionalization KW - Gas discharge KW - Grafting KW - Amino groups KW - Copper KW - Metallization KW - Adhesion PY - 2007 SN - 978-90-6764-455-6 SN - 90-6764-455-2 VL - 3 SP - 177 EP - 198 PB - VSP CY - Leiden AN - OPUS4-15733 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Friedrich, Jörg Florian T1 - Mechanisms of plasma polymerization - reviewed from a chemical point of view N2 - Several reaction mechanisms have been proposed for the formation of plasma polymers, such as monomer fragmentation followed by poly-recombination into randomly structured and crosslinked films; fragmentation, accompanied by the formation of acetylene or other film-forming intermediates and deposition of polystyrene-like material; plasma-initiation of a radical chain-growth polymerization; and ion-molecule reactions, as well as ionic chain-growth polymerization. The bulk structure of plasma polymers is completely irregular, far from that of conventional polymers. The retention of functional groups during plasma polymerization tends to be greater than that of the entire monomer structure found again as an intact repeat unit in the resulting plasma polymer. An alternative method for depositing ultra-thin, pin-hole free coatings, ones that possess regular structures, is by electrospray ionization (ESI) of pre-fabricated polymers. KW - Fragmentation-recombination KW - Mechanism KW - Plasma polymerization KW - Pulsed plasma KW - Structure of plasma polymers PY - 2011 DO - https://doi.org/10.1002/ppap.201100038 SN - 1612-8850 SN - 1612-8869 VL - 8 IS - 9 SP - 783 EP - 802 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-24502 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 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 - 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 - Mohamed, Zeinab A1 - Krüger, Simone A1 - Hidde, Gundula A1 - Schimanski, A. A1 - Jäger, Christian A1 - Friedrich, Jörg Florian T1 - Deposition of thick polymer or inorganic layers with flame-retardant properties by combination of plasma and spray processes N2 - Mixtures of hexamethyldisiloxane (HMDSO) and oxygen have been used for deposition of SiO2-like layers by plasma polymerization under low-pressure conditions onto polyethylene and polystyrene used as basecoat. Water glass was cast onto these 0.5 µm plasma thick siloxane-like layers with a thickness of 5 to 40 µm. The adhesion of these bilayer systems and their flame resistance were tested. The effect of different plasma parameters such as monomer/gas ratio, pressure and power input into the discharge on the deposition rate and the composition of the formed layers was studied. Characterization and chemical composition of the formed films were performed using infrared, X-ray photoelectron and solid state nuclear magnetic resonance spectroscopy. Peel strengths of composites were measured and the locus of peel front propagation was detected. Thermal properties of composites were analyzed by thermo-gravimetric analysis. Finally, the fire-retardant properties of thick coated polymers were determined by exposure to flames and the behavior of coatings on the polymers during flaming was observed visually. KW - Plasma polymerization KW - Hexamethyldisiloxane plasma polymer KW - Polystyrene KW - Polyethylene KW - Flame retardancy PY - 2013 DO - https://doi.org/10.1016/j.surfcoat.2013.04.039 SN - 0257-8972 VL - 228 SP - 266 EP - 274 PB - Elsevier B.V. CY - Lausanne AN - OPUS4-28735 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schartel, Bernhard A1 - Kühn, Gerhard A1 - Mix, Renate A1 - Friedrich, Jörg Florian T1 - Surface Controlled Fire Retardancy of Polymers Using Plasma Polymerisation N2 - Communication: Fire retardant coatings are deposited on polyamide-66 using plasma polymerisation. Chemical composition and thickness of deposits are adjusted varying the plasma treatment based on hexamethydisiloxane mixed with oxygen. The fire retardancy performances are evaluated using a cone calorimeter. The correlation between fire retardancy and thickness as well as chemical composition is discussed. KW - Cone calorimeter KW - Flame retardance KW - Heat release KW - Plasma polymerization KW - Polyamides PY - 2002 DO - https://doi.org/10.1002/1439-2054(20020901)287:9<579::AID-MAME579>3.0.CO;2-6 SN - 1438-7492 SN - 1439-2054 VL - 287 IS - 9 SP - 579 EP - 582 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-1537 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -