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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.
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.
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.
Plasma-chemical bromination has been shown to be well-suited for highly selective and efficient C–Br-functionalization of polyolefin surfaces and has now been applied to graphitic materials, including highly oriented pyrolytic graphite (HOPG), natural graphite, carbon nanotubes, and graphitized carbon fibres. In contrast to the radical substitution of hydrogen by bromine at hydrogen-terminated sp3-hybridized carbon, bromination of all-carbon bound sp2-hybridized carbon in graphene requires addition to aromatic double bonds. The related change of sp2 to sp3 hybridization of the carbon atoms involved helps to explain experimental results of a loss in surface planarity on brominated HOPG. Bromine concentrations of up to 50 bromine atoms per 100 C-atoms were achieved in elemental bromine vapour under low-pressure plasma conditions using low-energetic inductively coupled radio-frequency plasma excitation. The time scale of the bromination progress was found to increase with the specific surface area of the material. The results of plasma-chemical bromination are compared to that of wet-chemical electrophilic addition reactions, which achieved 28 Br per 100 C for MWCNT. The resulting C–Br bonds from plasma-chemical processing of graphitic materials were shown to be well-suited for hydroxyl functionalization and for grafting of organic molecules by nucleophilic substitution with 1,6-diaminohexane and (3-aminopropyl)triethoxysilane.
Polyolefin surfaces (polyethylene and polypropylene) were exposed to haloform (CHX3) plasmas for introduction of monosort halogen groups. Bromoform and chloroform plasmas produced selectively C-Br (100 Br/100 C) and C-Cl (200 Cl/100 C) groups in high yields. The bromoform plasma showed 1-3 and the chloroform plasma 2-7 post-plasma introduced O-functionalities per 100 C. The polyolefin C-Br groups were grafted wet-chemically or by exposure to the vapour of amines, diols and glycols. Thus, spacer molecules could be covalently bonded to maximal 15 spacer molecules per 100 C for the smallest grafted molecules and 1.2 molecules/100 C for larger molecules as octaaminophenylene-POSS. After metal evaporation the end groups of these polymer-bonded spacer molecules formed also covalent bonds to the metal. Thus, flexible, hydrophobic and barrier elements were introduced into the polymer-metal interfaces for high-impact, high-durable and water-resistant metal-polymer composites as measured by means of peel strengths.
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.
Activators regenerated by electron transfer–atom radical transfer polymerization (ATRP) as a controlled living polymerization are distinguished by their acceptance of small amounts of transition-metal complexes and oxygen and by their tolerance of reducing agents at a high concentration. The precondition of all ATRP applications is the use of homolytic or heterolytic cleavable halides as a dormant species; this allows the propagation of monomer chains. Hence, alkyl bromides are slightly cleavable and are the preferred initiators for ATRP. The bromination of polymer slides used as macroinitiators was carried out under gentle bromoform plasma conditions. This led to an oxidation-resistant stable bromine layer. More than 20 bromines per 100 carbons on the polymer scaffold were permanently bound to the substrate after plasma treatment. The resulting amounts of secondary and tertiary bromines on the polymer scaffold exhibited a suitable macroinitiator concentration for the surface-initiated polymerization of methyl methacrylate and glycidyl methacrylate.