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 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 U6 - 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 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 U6 - 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 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 - CONF A1 - Friedrich, Jörg Florian A1 - Kühn, Gerhard A1 - Mix, Renate ED - Pershin, L. T1 - Chemical synthesis at plasma modified polymer surfaces T2 - 17th International Symposium on Plasma Chemistry (ISPC-17) CY - Toronto, Canada DA - 2005-12-07 PY - 2005 SP - 1(?) EP - 6(?) CY - Toronto AN - OPUS4-11944 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Mach, Reinhard A1 - Maneck, Heinz-Eberhard A1 - Röhl-Kuhn, Barbara A1 - Peplinski, Burkhard A1 - Benemann, Sigrid A1 - Strauß, Birgid A1 - Schütz, W. A1 - Kühn, Gerhard A1 - Friedrich, Jörg Florian ED - Pershin, L. T1 - Modification of graphite powders in a thermal RF induction plasma T2 - 17th International Symposium on Plasma Chemistry (ISPC-17) CY - Toronto, Canada DA - 2005-08-07 PY - 2005 SP - 1(?) EP - 6(?) CY - Toronto AN - OPUS4-11942 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Friedrich, Jörg Florian A1 - Kühn, Gerhard A1 - Mix, Renate T1 - Tayloring of polymer surfaces with different monotype functional groups of variable density using chemical and plasma chemical processes T2 - 10th Dresden Polymer Discussion: Characterization of Polymer Surfaces and Thin Films CY - Meißen, Germany DA - 2005-04-10 KW - Plasma modification KW - Introduction of functional groups KW - Reactions at polymer surfaces PY - 2005 SP - 34 EP - 49 PB - Leibniz-Institut für Polymerforschung Dresden CY - Meißen AN - OPUS4-11941 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Weidner, Steffen A1 - Kühn, Gerhard A1 - Just, Ulrich A1 - Werthmann, Barbara A1 - Decker, Renate A1 - Schwarz, Bärbel A1 - Borowski, Renate T1 - MALDI/MS - A New Technique in Characterizing Chemical Heterogeneity of Degradation Products of Poly(Ethylene Terephthalate)s T2 - International GPC Symposium '96 CY - San Diego, CA, USA DA - 1996-09-08 PY - 1996 SP - 632 EP - 651 CY - Milford, Mass. AN - OPUS4-11905 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kühn, Gerhard A1 - Werthmann, Barbara A1 - Schröder, Hartmut A1 - Just, Ulrich A1 - Borowski, Renate A1 - Decker, Renate A1 - Schwarz, Bärbel A1 - Schmücking, I. A1 - Seifert, Ingetraut T1 - A new approach of characterizing the hydrolytic degradation of poly(ethylene terephthalate) by MALDI-MS N2 - The hydrolytic degradation of technical poly(ethylene terephthalate) (PET) was investigated by means of different methods such as size-exclusion chromatography (SEC), viscometry, light-scattering, thin-layer chromatography, end-group titration, and matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The long-term degradation was simulated by exposing PET filament yarns to aqueous neutral conditions at 90°C for up to 18 weeks. By means of MALDI-MS and thin-layer chromatography, the formation of different oligomers was obtained during polymer degradation. As expected, an ester scission process was found generating acid terminated oligomers (H-[GT]m-OH) and T-[GT]m-OH and ethylene glycol terminated oligomers (H-[GT]m-G), where G is an ethylene glycol unit and T is a terephthalic acid unit. Additionally, the scission of the ester bonds during the chemical treatment led to a strong decrease in the number of cyclic oligomers ([GT]m). The occurrence of di-acid terminated species demonstrated a high degree of degradation. PY - 1997 U6 - https://doi.org/10.1002/(SICI)1099-0518(199708)35:11<2183::AID-POLA9>3.0.CO;2-Z SN - 0360-6376 SN - 0887-624X VL - 35 IS - 11 SP - 2183 EP - 2192 PB - Wiley CY - Hoboken, NJ AN - OPUS4-11357 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kühn, Gerhard A1 - Weidner, Steffen A1 - Just, Ulrich A1 - Hohner, G. T1 - Characterization of technical waxes - Comparison of chromatographic techniques and matrix-assisted laser-desorption/ionization mass spectrometry N2 - Technical waxes and paraffins were investigated using supercritical fluid chromatography (SFC), matrix-assisted laser-desorption/ionization mass spectrometry (MALDI-MS) and size-exclusion chromatography (SEC). SEC enables the simultaneous determination of molecular masses up to high values and molecular mass distributions. The resolution of homologous species, however, is poor. In this respect the use of SFC is advantageous. Proper resolution of homologues may be provided up to Mr~1200 without great difficulty. To compare these chromatographic results MALDI-MS was applied for the determination of molecular masses and mass distributions in technical waxes for the first time. Using reflectron mode excellent MALDI mass spectra could be achieved in the molecular mass range up to 1000 Da. The mean values of the molecular masses calculated by MALDI-MS were in sufficient agreement with those of SFC. In the linear mode of MALDI-MS molecular masses could be determined to nearly 3000 Da. Beyond this mass range SEC still remains the method of choice. Advantages and difficulties of the used methods are discussed in this paper. PY - 1996 U6 - https://doi.org/10.1016/0021-9673(95)01255-9 SN - 0021-9673 VL - 732 IS - 1 SP - 111 EP - 117 PB - Elsevier CY - Amsterdam AN - OPUS4-11347 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Weidner, Steffen A1 - Kühn, Gerhard A1 - Just, Ulrich T1 - Characterization of oligomers in poly(ethylene terephthalate) by matrix-assisted laser desorption/ionization mass spectrometry PY - 1995 SN - 0951-4198 SN - 1097-0231 IS - 9 SP - 697 EP - 702 PB - Wiley CY - Chichester AN - OPUS4-11278 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -