This new functionalization method consists of the deposition of very thin plasma polymer layers (20 to 100 nm) of functional group bearing monomers in pulsed plasma. With allylalcohol, a maximum of 30 OH groups per 100 C atoms was measured with a selectivity of about 90% and a significant stability at long-time exposure to air. Allylamine was used to produce primary amino groups, with a maximum of 18 NH2 groups per 100 C atoms. Side reactions were observed during the storage in air, such as oxidation of the amino groups. Carboxylic groups could be produced using acrylic acid with a maximum concentration of 24 COOH groups per 100 C atoms. The most prominent side reaction was the decarbonylation/ decarboxylation of the acid group during plasma deposition.___TAGSTART___BR___TAGEND___ The variation of the density of functional groups using the pulsed-plasma polymerization of functional-group-bearing monomers was possible by the chemically-initiated radical copolymerization with either a chain-extending monomer, such as ethylene, or a cross linker, such as butadiene, in plasma. The density of functional groups could be adjusted continuously (0 to 30 OH, 0 to 18 NH2 and 0 to 24 COOH groups per 100 C atoms).___TAGSTART___BR___TAGEND___ The successful application of these densely functionalized polymer surfaces for producing biocompatible surfaces and for use in metalpolymer composites is proposed.
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).
A first inter-laboratory comparison was conducted to demonstrate and document the capability of interested laboratories to measure the fraction of C—OH species on a plasma oxidised poly(propylene) sample by using a chemical derivatisation XPS approach. This report presents the results from that inter-laboratory comparison and includes the data received for the measured values and their associated standard deviations of laboratory means, at a 95% confidence level. The measurements were guided by a protocol developed within the group before and summarised shortly in the paper. Standard deviations that may characterise the state-of-the-art for the nominally simple and rather often practised case of TFAA chemical derivatisation XPS of C—OH species on a plasma oxidised polyolefin surface are calculated following ISO 5725-2:1994. The main conclusion is that the associated degree of equivalence reached by the participating laboratories in this comparison is still low. Further research to improve chemical derivatisation XPS protocols is mandatory.