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Covalently aminated polyimide membranes are prepared by wet chemistry using different amines as modifiers. During this synthesis process carbonyl groups of the imide ring react with amine groups forming amide groups maintaining the macromolecular structure and an additional amide group bearing free amine groups. The reaction sequence was verified by FTIR-ATR and XPS measurements. Using poly(ethylene imine)s, highly aminated polyimide membranes with amine contents higher than 500 nmol/cm2 membrane can be produced which can be used as basic functions for further modification. As a result of amination, the hydrophobic polyimide membranes were strongly hydrophilized. Depending on the process parameters for functionalization and the applied modifier, a symmetric or an asymmetric distribution of amine functions across the membrane was observed. The distributions of amine functions were determined by SEM microscopy (EDX mode) and by AR-XPS (take-off angle resolved XPS). Calculations suggest that in the case of an asymmetric distribution the pores of the surface layer are almost completely filled with a swollen network of the modifier, which allows the covalent binding of second modifiers in order to obtain new types of composite membranes

Two monomers, ethylenediamine (EDA) and diaminocyclohexane (DACH), were plasma-polymerized in continuous-wave (CW) and pulse modes. The influence of different plasma parameters on the deposition rate and film composition were investigated in detail and the changes in aminofunctionalization with varying pulse parameters were examined by FTIR, ESCA, and chemical-derivatization techniques. It was shown that a varying duty cycle does not produce a considerable effect on the retention of amine groups into the film, while power and t on play a significant role in the polymerization process. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 979 -990, 2004

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SYNOPSISThe emission from low-pressure microwave plasmas in the vacuum-ultraviolet (VUV) region (A < 200 nm) was investigated in order to use these plasmas as light sources for the study of the VUV photochemistry of polyethylene (PE) and polypropylene (PP) as part of the study of plasma-polymer interaction. These polymers, immersed in low-pressure oxygen, were exposed to radiation with wavelengths down to 112 nm, the cutoff of magnesium fluoride used as a window to separate the polymer specimen from the plasma light source. Total oxygen incorporation in the surface [ O ] , and the formation of hydroxyl, carbonyl, and carboxyl groups were measured using XPS in combination with chemical derivatizations, particularly their dependence upon the radiation spectrum and the oxygen pressure around the sample. In most experiments the surface oxygen concentration [ O ] attained a constant value that appears to be related to the initial oxidation rate; this suggests a competition between oxygen incorporation and chain scission reactions, followed by the removal of volatile oxidation products. PE is usually oxidized to a higher level than PP, the latter appearing to be more susceptible to reaction with atomic oxygen than PE. A general initiation mechanism for the VUV experiments is proposed that allows us to explain the observed differences in behavior between PE and PP, and the results obtained under different irradiation conditions. The nature of oxidation products is in both cases very similar to what is observed after direct plasma treatment of the polymers. We conclude that short wavelength radiation contributes very appreciably to the observed surface modification effects during plasma treatment of PE and PP. 0 1995 John Wiley & Sons, Inc.

The determination of functional groups on complex polymer surfaces by X-ray photoelectron spectroscopy (XPS) can be improved considerably by derivatization reactions. Simple polymers containing hydroxyl groups or amino groups were investigated as reference materials for the derivatization with trifluoroacetic anhydride (TFAA).Poly(vinyl alcohol) (PVA), poly(hydroxyethyl methacrylate) (PHEMA), poly(vinyl butyral) (PVB), poly(allylamine) (PAAm), and poly(diallyl amine) (PDAAm) were derivatized using TFAA and analyzed with XPS. Polyethylene (PE) was used as an independent external reference for the binding energy (BE). Applying this procedure, the BE scales of all measurements were referenced to the carbon atoms of PE. It was found that the BE of the CF 3 component in the C1s region is different when bonded as an acetate or as an amide. The CF 3 BE is also influenced by the density of these groups in the polymer molecule. In TFAA-PVA, where every second main chain carbon atom carries a trifluoroacetate (TFAc) group, the BE is 294.3 eV while in TFAA-PVB with only isolated groups, the BE is 293.6 eV. The BE of the CF 3 component in the trifluoroacetamides (TFAAms) prepared from PAAm and PDAAm was found to be 292.5 and 292.3 eV, respectively. Compared with the analog fluorine free compounds, the BE is shifted toward higher values also for the ester carbon atom, the amide carbon atom, and the carbon atom to which the ester or amide is bonded.The data suggest that the gas phase reaction of TFAA with a polymer surface is diffusion limited. The actual ester or amide formation is a fast reaction and runs as a wave into the surface.