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Die hochselektive und ausbeutereiche plasmachemische Bromierung von Polyolefinoberflächen wurde auf graphitische Materialien übertragen. Oberflächen von graphenartigem Highly Oriented Pyrolytic Graphite (HOPG), natürlichem Graphit, mehrwandige Kohlenstoffnanoröhren (MWCNT) sowie Kohlenstoff-Fasern wurden im Bromdampfplasma behandelt. Während die Bromierung von Polyolefinoberflächen als radikalische Wasserstoffabstraktion mit nachfolgender Addition (Rekombination) oder durch nucleophile Substitution an sp³-hybridisierten C-Atomen abläuft, können graphitische Strukturen sowohl an sp³-hybridisierten Strukturdefekten als auch durch elektrophile Addition an vollständig C-substituierte aromatische Doppelbindungen bromiert werden. Dabei werden die planaren (graphitischen) sp²-C-Atome in die tetraedrische sp³-Hybridisierung umgewandelt und zu elektrisch nichtleitenden Strukturen gefaltet.
Die maximalen Bromausbeuten bei Verwendung von Brom als Plasmamedium lagen je nach Substrat zwischen 1050% Br/C, mit Bromoform deutlich darüber, was durch Kombinationen von Bromoform mit Brom oder Allylbromid mit Bromoform durch Schichtbildung auf über 70% Br/C gesteigert werden konnte.
An die C-Br-Gruppen wurden nasschemisch verschiedene Amine nucleophil gepfropft. Die Pfropfausbeuten von 110 Moleküle je 100 C lagen deutlich niedriger als die erreichten Pfropfgrade von etwa 122 Moleküle je 100 C-Atome an Polyolefinoberflächen. Da nach der chemischen Pfropfung nahezu alle nichtgepfropften Br-Gruppen verschwunden waren, muss auf eine bevorzugte Rekonstruktion der planaren sp²-Graphitschicht geschlossen werden.
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.
Since more than 40 years ammonia plasma exposure of polyolefins is used for introduction of primary amino groups. The selectivity of this reaction and the yield in primary amino groups was found to be low. Here, a prominent side-reactions of this process was investigated, the hydrogenation by NH3 plasma. For identification of hydrogenation ammonia (NH3) and deuterated ammonia (ND3) were exposed to Polyethylene (h-PE) and fully deuterated polyethylene (d-PE) as well as hexatriacontane (h-HTC) and fully deuterated hexatriacontane (d-HTC) as low-molecular weight model for PE. HD exchange was assumed and detected by Time-of-Flight Secondary Ion Mass Spectrometry (ToFSIMS), X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance (ATR-FTIR) and 1H and 2H Nuclear magnetic Resonance. Results show a significant HD exchange within the sampling depth of ATR (2.5 µm). However, N- and NH2 introduction was limited to the topmost surface as shown by SIMS and XPS (a few nanometers).
Thin coatings of poly(acrylic acid) (PAA) and poly(hydroxyethylmethacrylate) (PHEMA) were deposited onto carbon fibers by means of the electrospray ionization (ESI) technique in ambient air. These high-molecular weight polymer layers were used as adhesion promoters in carbon fiberepoxy resin composites. Within the ESI process, the carbon fibers were completely enwrapped with polymer in the upper 10 plies of a carbon fiber roving. As identified with scanning electron microscopy also shadowed fibers in a bundle as well as backsides of fiber rovings were pinhole-free coated with polymers (electrophoretic effect'). Under the conditions used, the layers have a granular structure. Residual solvent was absent in the deposit. PAA and PHEMA films did not show any changes in composition and structure in comparison with the original polymers as analyzed by X-ray photo-electron spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Single-fiber pullout tests of coated fibers embedded in epoxy resin showed significantly increased interfacial shear strength. It is assumed that chemical bonds between carbon fiber poly(acrylic acid) and epoxy resin contribute significantly to the improved interactions.
Polyglycerol (PG) coated polypropylene (PP) films were synthesized in a two-step approach that involved plasma bromination and subsequently grafting hyperbranched polyglycerols with very few amino functionalities. The influence of different molecular weights and density of reactive linkers were investigated for the grafted PGs. Longer bromination times and higher amounts of linkers on the surface afforded long-term stability. The protein adsorption and bacteria attachment of the PP-PG films were studied. Their extremely low amine content proved to be beneficial for preventing bacteria attachment.
Plasma polymers and electrospray-ionization (ESI) polymer layers are compared for most efficient adhesion promotion in carbon fiber-epoxy resin composites. The ultra-thin ESI layers (2–30 nm) of commercial poly(acrylic acid) and poly-(hydroxyethylmethacrylate) produce an significant increase of adhesion measured by single-fiber pull out tests.
However, plasma Treatment has also advantages, such as simultaneous activation of the fiber substrate. Chemical structure and composition are rather far from the regular structure of commercial polymers as deposited by ESI processing.